Synthesis of anthracite networks and room temperature superconductors

Abstract

To provide a new material for constructing an anthracite network from different kinds of two-dimension structural unit including a carbonaceous system and a non-carbonaceous system.SOLUTION: A material comprising synthetic anthracite is provided. The materials can exhibit a variety of properties, including high electrical conductivity. The material may also have favorable structural and mechanical properties. They can form a gas-tight barrier, form an insulating structure, and have unique optical properties.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 039,525, filed June 16, 2020, the disclosure of which is incorporated herein by reference in its entirety. The following applications are incorporated herein by reference in their entirety for all purposes: U.S. Provisional Patent Application Nos. 63 / 039,525 ('525 Application), 63 / 129,154 ('154 Application), 63 / 075,918 ('918 Application), 63 / 806,760 ('760 Application), 63 / 121,308 ('308 Application), U.S. Patent Application Nos. 16 / 758,580 ('580 Application), 16 / 493,473 ('473 Application), International PCT Application / U.S. Serial No. 17 / 17537 ('17537 Application), and U.S. Patent No. 10,717,843(B2) ('843B2 Patent).

[0002] The present disclosure relates to novel methods for constructing microscopic or macroscopic objects from anthracite networks that exhibit molecular-level two-dimensionality. In particular, the present disclosure relates to novel methods for constructing anthracite networks from different types of two-dimensional building blocks, including carbonaceous and non-carbonaceous systems.

[0003] The present disclosure also relates to novel synthetic anthracite networks cross-linked by structural rearrangements. In particular, the present disclosure relates to encased mineral materials and frameworks that include synthetic anthracite networks that achieve hierarchical cross-linking through structural rearrangements.

[0004] Finally, the present disclosure also relates to novel methods for inducing superconductivity in materials under ambient conditions, and to novel room temperature superconductors. [Background technology]

[0005] Two-dimensional molecular-level structures, such as graphene carbon, have been demonstrated to have excellent properties. However, to facilitate the practical application of these two-dimensional structures in many macroscopic and microscopic applications, it is necessary to construct hierarchical materials with three dimensions at a larger level. Constructing such hierarchical materials that are both two-dimensional at the molecular level and three-dimensional at a higher level is challenging.

[0006] A common approach to constructing larger-level systems involves contacting two-dimensional lattices—often graphene lattices—and combining them into systems containing multiple lattices. In this disclosure, we refer to these types of systems, consisting of members from multiple different two-dimensional lattices, as "assemblies." Macroscopic three-dimensional assemblies can be readily constructed from two-dimensional lattices.

[0007] In aggregate-type systems, two-dimensional lattice members are typically bonded together at regions of overlapping van der Waals ("vdW") contacts. Such systems are primarily held together through intermolecular attractive forces at these contacts. As such, aggregates in which intermolecular attractive forces at vdW contacts are the primary bonding mechanism are described as "vdW aggregates." Regardless of their physical structure, vdW aggregates share the common property of broken covalent bonds at the system level.

[0008] The intermolecular forces are weaker than covalent bonds, allowing overlapping vdW aggregate members to slide past each other. This shear yielding property limits the elastic modulus of graphitic carbon and softens it. Because the intermolecular forces between two lattices are a function of their contact area and contact distance, vdW aggregates of small lattice members are often particularly weak.

[0009] In other assemblies, multiple two-dimensional lattice members may be primarily bonded to one another through chemical bonds. In such bonded assemblies, the chemical bonds between individual lattice members can suppress shear yielding, making them more robust than vdW assemblies, which are bonded solely through intermolecular forces. Prior art has created bonded assemblies by chemically modifying the surface of graphene lattices, for example, by grafting chains that can be used to crosslink other lattices. While this is an improvement over vdW assemblies, the connections between bonded lattice members still limit the realization of universal two-dimensional molecular structures.

[0010] In principle, some of the limitations of assemblies may be overcome by constructing "graphene networks," which, as used herein, refer to structures with two-dimensional molecular-level geometry that are crosslinked three-dimensionally at several levels. As a function of the crosslinks and mesh geometry of graphene networks, the network cannot be broken without breaking some of its two-dimensional molecular structure. Intuitively, this should be the best way to construct ordinary objects, typically of macroscopic size, that exhibit properties similar to two-dimensional structures. Such objects can benefit from the ability to rationally design the mesh geometry.

[0011] One inspiration for how to build graphene networks comes from naturally occurring "mature coal," which contains an "anthracite network." Herein, we describe a layered graphene network that is three-dimensionally cross-linked through a specific characteristic rearrangement (the "anthracite rearrangement"), with z-adjacent layers nematically aligned. The three-dimensionally cross-linked anthracite network forms when organic matter is exposed to high temperatures and pressures over geological time. As the organic matter matures, its carbon content increases, and its molecular structure becomes increasingly dominated by two-dimensional polycyclic arrays of carbon that eventually coalesce upon developing structural rearrangements that realize polycyclic cross-links between these polycyclic arrays (thereby forming a unified polycyclic network).

[0012] There are several types of anthracite rearrangements that serve to cross-link the anthracite network. One type is described herein as the "Y rearrangement." Briefly, the Y rearrangement is formed when a monolayer of atoms branches into a bilayer of atoms, the intersection of which contains a polycyclic series of rings (the term "polycyclic" refers to a pure sp 2 Although the term generally applies to hybridized polycyclic structures, it is described as a polycyclic array of rings that may contain multiple orbital hybridization states. The second type of anthracite dislocation is the screw dislocation, which involves a multilayer helical arrangement of atomic monolayers. Other anthracite dislocations may contain elements of both Y-dislocations and screw dislocations. All of these dislocations have the common effect of forming lateral and perpendicular molecular-level polycyclic bridges between two-dimensional molecular structures. These three-dimensional molecular-level bridges have the effect of hardening and rigidifying the anthracite network, which is why anthracite is sometimes referred to as a "hard coal."

[0013] Although its cross-linking makes it an intriguing example of a macroscopic graphene network, natural anthracite has practical limitations. Its geological formation may result in organic and inorganic inclusions embedded as secondary phases. The lack of engineering control during formation precludes imperfections and the application of rational design principles. These drawbacks largely limit the usefulness of anthracite for fuel applications, but could be overcome if synthetic anthracite networks could be created. Exemplary synthesis methods are detailed in the '760 and '918 applications, where an exoskeleton mineral framework is synthesized using template-dependent chemical vapor deposition ("CVD"), or what applicants describe in these applications as "surface replication." If an exoskeleton mineral framework cross-linked via anthracite rearrangements could be rationally designed, this synthetic geomimetic structure would represent an improvement over natural anthracite.

[0014] Non-anthracite-based graphene networks constructed from two-dimensional materials have arguably been demonstrated by prior art surface replication. Small schwarzite-like graphene networks appear to have been synthesized using CVD deposition of zeolite Y template particles. Zeolite Y is considered a macroporous zeolite with a supercage diameter of approximately 13 Å. While its macroporous structure enhances internal gas diffusivity compared to small-pore zeolites, the micropores of zeolite Y are still small enough that spatial confinement effects allow the growing graphene lattice to coalesce into a single, continuous graphene network that is three-dimensionally bridged without anthracite rearrangements.

[0015] The spatial constraints within the zeolite pores appear to allow the lattices to coalesce, but they also create significant challenges. One issue is the tendency of deposited carbon to block the pores of the zeolite template, prematurely terminating deposition within the template. As a result, zeolite-templated carbon is rarely complete. Another issue is the extremely slow, diffusion-limited deposition kinetics within the microporous template. The maximum depth of the template at which a substantially complete schwarzite network (as evidenced by an average of 72 carbon atoms per zeolite supercage) is arguably demonstrated is only about 20 nm. Even at this shallow depth, precipitation of zeolite Y nanoparticles required 6 hours to complete.

[0016] In addition to these challenges, schwarzite may suffer from another fundamental drawback: its approximation of the Schwarzian minimum surface geometry. While theoretical studies support the goal of creating graphene networks modeled on these surfaces due to their minimal nature, Applicant demonstrates herein that minimal surface geometries may not be as favorable as the dense, layered structure of anthracite networks. That is, Applicant finds that schwarzite geometries may limit or virtually eliminate the interlayer vdW interactions that contribute to the systemic bonding of layered anthracite networks. Thus, rather than sacrificing vdW bonding to obtain molecular-level density reduction, it is preferable to obtain density reduction through hierarchical, large-scale pore engineering, as demonstrated by the tunable mesoporous or macroporous exoskeleton mineral frameworks described in the '760 and '918 applications.

[0017] We speculate that the prior art may contain previously unrecognized examples of the synthesis of graphene networks other than schwarzite networks, based on the analysis and concepts developed and presented in this disclosure, which analysis is detailed below.

[0018] In one example, based on our post-mortem analysis, we found evidence of constructing a graphene network on a magnesium oxide (MgO) template by grafting the edges of graphene domains grown on the MgO template surface [1]. Prior to extracting the endohedral MgO, the exohedral carbon phase formed on the MgO contained a monolayer of atoms. Because anthracite transitions contain interlayer bridges between multiple z-neighboring layers, they cannot exist in a monolayer. Post-mortem analysis revealed that the network lacked anthracite transitions, based on the characteristics of the monohedral exohedral mineral phase on the template surface. Therefore, molecular-level crosslinks were only lateral or intralayer, and this anisotropy prevented the framework from realizing some of the fundamental benefits associated with more three-dimensional molecular crosslinks (e.g., hardness and structural rigidity). As a result, when the endohedral mineral template is extracted and the exohedral mineral framework is dried, the pores within the framework collapse, resulting in a dried graphene network with a bilayer structure, but without the molecular-level interlayer crosslinking of these bilayers that occurs due to anthracite rearrangements.

[0019] In another example, we found evidence that nano-onions grown using a metal catalyst contain graphene networks in which substantially parallel-aligned z-adjacent graphene layers (i.e., a more ordered arrangement than the nematic arrangement seen in anthracite networks) are vertically cross-linked via anthracite dislocations, typically with lateral spacings no less than 5 nm. This large nanocrystalline graphitic order results in anisotropic and lateral cross-linking of the graphene network, making it more similar to graphite than anthracite. Therefore, we refer to such graphite-like networks as "graphite networks" to distinguish them from anthracite networks. Similar to the graphene network presumed to exist in the first prior art example, the graphite network exhibits anisotropic and lateral cross-linking. Summary of the Invention

[0020] This disclosure demonstrates a method for synthesizing microscopic or macroscopic anthracite networks by grafting two-dimensional molecular structural units together. In particular, the method can be used to synthesize two types of anthracite networks, "x-carbon" and "z-carbon," with properties described in more detail in the body of this application, as well as other novel graphene networks. The method can optionally include synthesizing anthracite networks with non-carbonaceous chemical compositions or containing compounds. The method can also optionally include synthesizing anthracite networks with templated structural features, hierarchical morphology, controllable crosslink density, and porosity.

[0021] The present disclosure also demonstrates materials containing synthetic anthracite networks. These materials contain x-carbon and z-carbon. These materials also include synthetic anthracite networks containing two-dimensional forms of light elements and compounds containing light elements. In particular, these materials include BN and BC x N. These materials include anthracite networks in any form, particularly templated forms. The present disclosure also relates to derivatives of these novel materials, including chemically or physically modified derivatives.

[0022] The present disclosure also demonstrates methods for inducing superconductivity in materials and objects at ambient conditions. In particular, these methods may include techniques for shielding materials and objects containing two-dimensional molecular structures from collisions with gas molecules, including forming an impermeable barrier phase around the materials and objects while maintaining a vacuum. Optionally, these methods may include placing the materials and objects in a vacuum.

[0023] This disclosure also demonstrates highly correlated materials or objects at room temperature, including room-temperature superconductors, which are described in more detail in the main body of this application. These room-temperature superconductors can include the synthesis of materials or objects that include two-dimensional molecular structures. These room-temperature superconductors can be nanoscale, microscale, or macroscale. Optionally, they can include synthetic anthracite networks. In general, they can include materials or objects that have been stripped of molecules in a liquid or gas phase. In particular, they can include materials or objects that include a barrier phase and an internal phase, where the internal phase includes a porous material protected by the barrier phase from atomic or molecular collisions encountered in non-vacuum environments.

[0024] The present disclosure also describes methods for synthesizing highly correlated materials or objects at room temperature, including room temperature superconductors. These methods can include synthesizing materials or objects comprising two-dimensional molecular structures. In particular, the materials or objects can include anthracite networks. Synthesizing such anthracite networks can include linking smaller structures to the anthracite network by grafting them to each other. These smaller structures can optionally include carbon black or anthracite networks. [Brief explanation of the drawings]

[0025] [Figure 1] Figure 1 shows a classification diagram illustrating how graphene networks are classified in this disclosure, highlighting synthetic anthracite networks containing x and z carbons. Each of these classifications is subclassified into spx networks, intermediate networks, or helical networks formed via maturation of spx networks. [Figure 2] A model of a schwarzite network, an example of a non-layered graphene network with a helical geometry. The schwarzite surface is shown next to the model. [Figure 3] Depicts a curved two-dimensional surface and identifies the z-axis, which is perpendicular to the xy tangent plane. The space above and below the surface comprises z-space. [Figure 4]Molecular model of a curved, ring-disordered graphene structure. The structure has been rotated, as indicated by the arrows, to provide multiple perspectives. The enlarged inset shows regions of positive and negative Gaussian curvature. The edge in the foreground is highlighted in blue, and the enlarged inset shows its undulating shape. [Figure 5] Illustration of two possible scenarios during a structural encounter between two ring-ordered graphene structures. In A, a structural encounter is shown. In B, a subduction event leading to an edge dislocation is shown. The subducted lattice is indicated by an "x". In C, an sp2 grafting event leads to edge coalescence to form a new graphene structure with some ring disorder and the development of curvature. [Figure 6] Five model systems are presented that are used to clarify definitions and concepts related to graphene structures and systems. [Figure 7] Figure 1 shows the model system used to define and conceptualize graphene structure. The model contains a Y-dislocation and highlights the diamond-shaped seam that contains its core. [Figure 8] 1 shows photographs of various devices used in the procedures described in this disclosure. [Figure 9] SEM micrograph of the exocarpic mineral framework of sample A1. The translucent areas of the exocarpic mineral walls are circled in yellow. [Figure 10] TEM micrographs of sample A1 at various magnifications are included. At the highest magnification, the nematic alignment of the enveloping mineral walls is shown. The yellow lines trace the nematically aligned layers. The enlarged view shows the Y dislocations. [Figure 11] 10 is a TEM micrograph of another exoencapsulated mineral framework to further illustrate the concept of nematic ordering. [Figure 12] Diagram from the anthracite literature showing (A) an end dislocation, (B) a Y dislocation, (C) a screw dislocation, and (D) a screw loop (pair of screw dislocations). [Figure 13]This is a portion of the single-point Raman spectrum of sample A1, with the regions of interest, such as the unmatched G band (Gu), unmatched Tr band (Tru), unmatched D band (Du), and unmatched shoulder, between 1100 and 1200 cm-1, circled in yellow. The inset shows the full Raman spectrum of sample A1. The spectrum was acquired using a 532 nm laser with a power of 2 mW. [Figure 14] The figure shows two fitted peaks (f-1, f-2) from the Raman profile of sample A1, the fitted profile, the actual profile, and the residuals representing the difference between the fitted and actual profiles. The fitted peaks' peak shape, peak position, peak height, peak fwhm, and peak area are also shown in table format. [Figure 15] The Raman profile of sample A1 shows three fitted peaks (f-1, f-2, f-3), the fitted profile, the actual profile, and the residuals representing the difference between the fitted and actual profiles. The fitted peaks are also tabulated with their peak shape, peak position, peak height, peak fwhm, and peak area. [Figure 16] The Raman profile of sample A1 shows four fitted peaks (f-1, f-2, f-3, f-4), the fitted profile, the actual profile, and the residuals representing the difference between the fitted and actual profiles. The fitted peaks are also tabulated with their peak shape, peak position, peak height, peak fwhm, and peak area. [Figure 17] The Raman profile of the annealed sample A1 shows two fitted peaks (f-1, f-2, f-3, f-4), the fitted profile, the actual profile, and the residuals representing the difference between the fitted and actual profiles. The fitted peaks are also tabulated with their peak shape, peak position, peak height, peak fwhm, and peak area. [Figure 18] 1 is an XRD profile of sample A1, with three fitted peaks labeled I, II, and III. [Figure 19]Figure 1 shows the thermal oxidation profiles of samples A1, A2, and A3 obtained by thermogravimetric analysis (TGA) at a heating rate of 20°C / min in air. The plot shows the derivative of the mass loss of the samples versus temperature. [Figure 20] 1 is an SEM micrograph of sample A2 showing the exoskeleton mineral framework that appears fragmented and damaged during processing. [Figure 21] TEM micrographs of sample A2 at various magnifications are included. In A, the damaged exoskeleton mineral framework can be seen. In B, fragments of the exoskeleton mineral wall are shown. In C, the graphitic layer of the exoskeleton mineral wall is shown. The dark edge line is traced in yellow. [Figure 22] This shows a single-point Raman spectrum of sample A2 taken using a 532 nm laser with a power setting of 2 mW. [Figure 23] SEM micrograph of sample A1 after compression showing the exoskeleton mineral framework retaining the three-dimensional macropore morphology with linear features in the walls due to distortion. The enlarged inset shows the distorted walls. [Figure 24] 1 is an SEM micrograph of sample A2 after compression, showing the paper-like aggregates of the broken and flattened framework. [Figure 25] SEM micrographs of the exosporium mineral framework of sample A3. A shows its polyhedral morphology and large atomically flat facets. B shows the transparent windows and more opaque framing. The two windows in the wall are circled and shaded yellow. C shows the concave curve of the transparent windows extending across the framing. [Figure 26] 1 is a SEM micrograph of the polyhedral MgO template used to prepare sample A3. [Figure 27]TEM micrographs of sample A3 at various magnifications are included. In A, the cubic shape of the macropore subunits of the exo-mineral framework is shown. The edges of the cubes are highlighted with yellow dotted lines. The solid yellow lines highlight the more electron-transparent windows. B shows a fragment of an exo-mineral wall. The enlarged inset shows an example of a Y dislocation found within the edge. C shows that even in the transparent "window" regions found above the flat regions, there is a uniform wall thickness. This indicates that the electronic transparency is related to the lack of local sp3 states. [Figure 28] A portion of the single-point Raman spectrum of sample A3 is shown. Notable features are circled in yellow. Features include an unfitted G band (Gu), an unfitted Tr feature (Tru), an unfitted D band (Du), and an unfitted shoulder between 1100 and 1200 cm-1. The traditional G peak position at 1585 cm-1 is indicated by a dotted line, revealing that the Gu peak is blue-shifted in sample A3. The inset shows the full Raman spectrum of sample A3. The spectrum was acquired using a 532 nm laser with a power of 2 mW. [Figure 29] The figure shows a hypothetical zigzag-zigzag structural interface formed between two primordial domains of ring disorder (G1 and G2). The involved end segments are labeled E1 and E2. The E1-E2 interface contains three distinct interface zones: offset zone I, offset zone II, and horizontal zone. For ease of visual inspection, vertical (V) and horizontal (H1 and H2) perspective views of labeled and unlabeled regions are shown. In the H2 perspective view, the highlighted yellow region is the background. [Figure 30] The figure shows sp2 grafting across the horizontal zone of the E1-E2 interface. The resulting sp2 rings form ring connections between G1 and G2, creating a new graphene structure, G3. For ease of visualization, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow area is the background. [Figure 31]The figure shows sp3 grafting across the offset zone at the E1-E2 interface. New sp2 atoms are represented by solid circles. New sp3 atoms are represented by solid circles. The resulting spx ring contains four rings in chair conformation (R1, R3, R5, and R6) and two chiral rings (R2-C and R4-C) associated with the transition in the structural zone. The chiral chains within the two chiral rings are indicated by blue arrows, and the five sp3-sp3 bonds are shown in red. The point-symmetry orientation of the rings in chair conformation and the two sp3-sp3 bond lines is shown. The higher tertiary radicals generated by sp3 grafting across the offset zone are labeled. The structure of the chiral ring R2-C is shown, with the chiral ring highlighted in blue and the sp3-sp3 bond highlighted in red. For ease of visual inspection, vertical (V) and horizontal (H1 and H2) perspective views are shown, labeled and unlabeled. In perspective view H2, the highlighted yellow area is the background. [Figure 32] Continued z-growth from the five higher tertiary radicals in Figure 32 is shown. New sp3 atoms are represented by black and white circles. Four rings (R1, R3, R5, R6) in chair conformations and two chiral rings (R2-C, R4-C) are labeled. For ease of visualization, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted area is the background. The second row of sp3-sp3 bonds created is represented by red lines. For ease of visualization, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow area is the background. [Figure 33]This shows the result after continuing the radical addition onto the base layer. New sp2 atoms are represented by solid circles. New sp3 atoms are represented by solid circles. There are three new spx rings (R7, R8, and R9) in the chair conformation, and we label two chiral rings (R2-C, R4-C). The addition of the spx rings to the chair conformation creates two diamond-shaped seams, shown in isolation in the H1 perspective inset. These two diamond-shaped seams form the intersection of two Y-displacements, shown as shaded Y-shapes in the H1 perspective inset. For ease of visual inspection, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspectives are shown. In perspective H2, the highlighted yellow areas are the background. [Figure 34] This shows the result after continuing the radical addition onto the base layer. New sp2 atoms are represented by solid circles, and new sp3 atoms are represented by open circles. The third row of sp3-sp3 bonds is highlighted in red. There are three new spx rings (R10, R13, and R14) in labeled chair conformations and one new chiral ring (R11-C). The chiral ring R11-C sits on top of the chiral ring R4-C, creating a chiral column. The chiral column is shown isolated. Chiral chains 1–6 and 7–12 are indicated by blue arrows. For ease of visualization, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow areas are the background. [Figure 35] This is the image after continuing the radical addition onto the base layer. The rings above the base have coalesced, nucleating a second layer. There are now four chiral rings (R2-C, R4-C, R11-C, and R12-C) containing two chiral columns. For ease of visualization, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective H2, the highlighted yellow area is the background. [Figure 36]After continuing the radical addition onto the base layer, a third layer has nucleated. One of the cubic diamond-shaped seams is darkened in the magnified inset. The other cubic diamond-shaped seam is highlighted in yellow in the second magnified inset, and the chiral columns representing the lateral endpoints of the seam are highlighted in blue (chiral chains) and red (z-directed sp3-sp3 chains). Vertical (V) and horizontal (H1 and H2) perspectives are shown for ease of visualization. [Figure 37] A is a horizontal zoom (H2) showing the chiral columns. Chiral chains within chiral rings are highlighted in blue, and z-directed chains of sp3-sp3 bonds connecting z-adjacent chiral rings are highlighted in red. B shows a simplified schematic representation of the chiral column structure. C shows the spx helices within each chiral column isolated. [Figure 38] A is an SEM of a C@MgO exosporium mineral composite particle, typified by samples B1-B3. The MgO can be seen as a brightly colored, charged area. In the SEM micrograph in B, the endosporium MgO template has been removed, leaving the exosporium mineral framework, typified by samples B1-B3. In the SEM micrograph in C, the pore-sheet exosporium mineral framework, typified by sample B4, is shown. [Figure 39] The Raman spectra of samples B1 to B4 are shown, showing the spectral trends observed with decreasing temperature. [Figure 40] The zigzag-zigzag structural interface is shown, where atoms are grafted through interstitial lines to create spx rings in a boat conformation. [Figure 41] The zigzag-armchair interface is grafted via two z-adjacent rows of five- and seven-membered spx rings, highlighted in yellow. [Figure 42] This shows the zigzag-zigzag structural interfaces grafted through interstitial lines of atoms to create spx rings with boat conformations. These boat conformations are highlighted in yellow. [Figure 43]Schematic representation of the growth of multiple primordial domains on a common substrate surface, their grafting, and the nucleation and growth of higher-order layers. The "X" structures represent diamond-shaped seams, some of which propagate vertically and some of which do not. New diamond-shaped seams are shown as formed by the structural activity of higher-order layers. [Figure 44] 1 is an XRD profile of sample B4. [Figure 45] 10 is an image of Samples C1 and C2 showing how brown these hydrogenated carbons are. [Figure 46] FTIR of sample C2, showing hydrogenation of this brown coal-like sample. [Figure 47] The Raman spectra of Samples C1 and C2 show a small peak at approximately 600 cm-1 due to dehydrogenated nanodiamonds. This indicates the dehydrogenated phase of Samples C1 and C2. [Figure 48] Photograph of equivalent masses of sample E1 and sample E1A, showing the more granular hardness of sample E1 and the finer, more voluminous nature of sample E1A. [Figure 49] A-C are SEM images of sample E1. D-F are SEM images of sample E1A. A shows the granules of sample E1. Compared to sample E1A, D, sample E1A, sample E1 is more densified and granular. B shows the flexibility and textured curvature of the exosporium mineral framework of sample E1. Compared to sample E1A, E, sample E1A, sample E1A is more rigid. C shows the less distinct substructure of the exosporium mineral framework of sample E1. Compared to sample E1A, F, sample E1A, sample E1A is more clearly defined substructure of the rigidified framework. [Figure 50]A-C are SEM images of sample E2. D-F are SEM images of sample E2A. A shows the granules of sample E2. Compared to sample E2A, D, sample E2A, sample E2 shows greater densification and granularity. B shows the flexibility and textured curvature of the exosporium mineral framework of sample E2. Compared to sample E2A, E, sample E2A, sample E2A shows greater rigidity of the exosporium mineral framework. C shows the less distinct substructure of the exosporium mineral framework of sample E2. Compared to sample E2A, F, sample E2A shows a more distinct substructure of the rigidified framework of sample E2A. Sample E2A also shows fusion of the stacked plates. [Figure 51] AB are SEM images of the MgO template used to generate the framework of the sheet-like holes used in experiment E. [Figure 52] 1 shows Raman spectral effects associated with the maturation of spx precursors. [Figure 53] The breakdown of a simplex structure containing a cubic diamond-shaped seam due to maturation is shown. [Figure 54] The role of the chiral rings and columns in maintaining vertical bridges during aging is shown. [Figure 55] FIG. 1 illustrates the conversion of an spx helix to an sp2 helix. [Figure 56] FIG. 1 illustrates the formation of an sp2 helix around an sp2 helix. [Figure 57] Figure 36 shows the maturation of spx precursors into helical monomers. [Figure 58] An alternative perspective view is provided to facilitate visual identification of the ring connectivity of the helical monomer shown in FIG. [Figure 59] 1 is an XRD profile of sample B4A. [Figure 60] An alternative scenario for the E1-E2 interface is shown, in which the edges of G1 and G2 do not intersect, and the chiral rings R2-C and R4-C in this scenario are shown to have opposite chirality, as indicated by the blue arrows. [Figure 61]We show the progressive growth of spx precursors on the E1-E2 C structure interface, which reflects the E1-E2 interface modeled in Figure 29, but assumes that sp2 grafting is not possible and that instead of a horizontal zone, the E1-E2 interface contains a junction. [Figure 62] Figure 61 shows the double helix formed by collapse of the spx precursor assembled on the E1-E2 C structural interface. [Figure 63] The dissociation of the sp3-sp3 bond line formed at the E1-E2 C structure interface indicates the complete dissociation of the base layer. The two chiral chains R3-C within the chiral ring are indicated by blue arrows, and the sp3-sp3 bond is shown in red. The chiral chain is shown to be point symmetric. Sp2 atoms are indicated by black circles, and sp3 atoms are indicated by black and white circles. [Figure 64] Figure 62 shows the formation of the modeled double helix and its degradation upon maturation of the spx precursor assembled on the E1-E2 C structural interface in Figure 61. The chiral column assembled on R3-C is shown to contain an spx double helix that converts to an sp2 double helix upon maturation. [Figure 65] We show how the absence or presence of horizontal zones and the associated sp2 grafting influence the ring connectivity of the resulting helical system. [Figure 66] Individual and linked helices are shown, including linked helices of common and opposite chirality. [Figure 67] We show how uninterlocked truncated double helices form when the monolayer precursors are disrupted during maturation. [Figure 68] We show how bilayer precursors form double helices that are sufficiently elongated so that the helices interlock when they collapse during maturation. [Figure 69] A is a theoretical representation of the diagram of maturation from simple to simple. B is a theoretical representation of the diagram of maturation from simple to aggregate. [Figure 70] It shows how two higher-order layer paths extending upward from the base layer reconnect to form a closed loop. [Figure 71]A shows a macroporous exoskeleton mineral framework from an annealed spx precursor. B shows a cross-section of an exoskeleton mineral wall. The edge lines show a distinctive "sliced" pattern, as shown by the yellow lines, corresponding to the z-displacement of the helical graphene lattice when rotated 180° around the dislocation line. In C, the helices extend across more than 10 layers of the helical network, as shown by the yellow dotted lines. In D, the connected helical loops from the pore wall are enlarged. Analysis of the HRTEM image in Figure 71D reveals that the sp2 helices in the centers of these two adjacent helices were spaced less than 1 nm apart. [Figure 72] A shows a helicoidal x-network containing an exo-mineral framework with an equiaxed cubic morphology. B shows the controlled mesopore structure of the exo-mineral framework, with a high degree of conformity in the exo-mineral wall thickness. B shows the exo-mineral wall at higher magnification. It averages 2-3 layers and appears more twisted than the thicker wall due to increased flexibility. [Figure 73] Figure 1 is a diagram of three exo-mineral frameworks illustrating the concept of meso-scale interlinking. The shading in structures I, II, and III indicates that they have the same molecular-level interlinking. However, their degree of meso-scale interlinking varies, with I having the highest interlinking and III having the lowest interlinking. [Figure 74] A is a diagram of the hydroxylated ends formed by the perpendicular ends of two linked helices. B is a diagram of the mouths that represent entrances to the interlamellar labyrinth of the network. These mouths, as shown in B, provide ubiquitous access points for fluid ingress or egress. [Figure 75] A series of SEM micrographs of fracture surfaces of epoxy nanocomposites containing 0.5 wt% loading of spx networks. Each embedded exoskeleton mineral framework contains sheet-like pore morphology and spx networks, as indicated by the yellow circles in C. [Figure 76]A series of SEM micrographs of fracture surfaces of epoxy nanocomposites. The surface is covered with debris resulting from the explosive fracture of the cured epoxy nanocomposite adjacent to the encapsulating mineral framework. In A, the result of one such explosive fracture can be seen. In C, the debris is seen to be epoxy fragments, physically embedded in the surface. [Figure 77] 1 is a diagram of two spx networks pressed together to form a non-native bilayer that can be crosslinked during maturation. [Figure 78] This is an illustration showing a radical addition reaction between two spx networks, GA and GB, in static vdW contact. This is represented in Frame I. The underlying helix geometry extrudes the sp2 radical of GB toward GA, as shown in Frame II of Figure 78; the radical is circled. A radical cascade reaction bonds the line of sp2 radicals of GB with the z-neighboring atom of GA, forming an sp2 ring. This reaction extends the helix into the non-native bilayer and extrudes the terminal dislocation of the radical end toward the surface, as shown in Frame III of Figure 78. [Figure 79] A is the granules of sample F1, and B is the pellets of sample F2. [Figure 80] 1 shows N2 adsorption isotherms for samples F1 to F4. [Figure 81] FIG. 1 is a pore distribution diagram of samples F1 to F4. [Figure 82] 1 shows Raman spectra of samples F1 to F4. [Figure 83] The figure shows the change in Raman spectrum with aging of pellets of sample F2 to sample F3. [Figure 84] A is a photograph of Buckypaper. B is a photograph of cutting Buckypaper. [Figure 85] A. SEM micrograph of a cross section of buckypaper. B. The collapsed exoskeleton mineral framework containing buckypaper. C. The K2CO3 template. [Figure 86] Solvent immersion of unannealed buckypaper. [Figure 87] Solvent immersion of unannealed buckypaper. [Figure 88] 1 shows Raman spectra of samples F5 and F6. [Figure 89] It is a fibrous buckypaper made from elongated spx microfoam. [Figure 90] A. SEM image showing fibrous buckypaper. B. Flexible, elongated spx microfoam. [Figure 91] SEM micrograph of a fine, compact exosporous mineral framework with unclear substructural features. [Figure 92] 1 is an SEM micrograph of a rough, non-compacted framework. [Figure 93] 1 is an SEM micrograph of a petal-like framework. [Figure 94] 1 is a SEM micrograph of two hollow spherical frameworks. [Figure 95] 1 is a SEM micrograph of two equiaxed frameworks. [Figure 96] This is a photograph of sample G1 being resistively heated at 1 atm. [Figure 97] 1 is a sequence of photographs showing sample G1 exhibiting the Meissner effect. [Figure 98] Photographs of various disordered carbon samples being resistively heated at 1 atm. [Figure 99] 1 is a photograph of a disordered carbon sample exhibiting the Meissner effect. [Figure 100] 1 is a photograph of a disordered carbon sample showing the pinning effect in the presence of a neodymium magnet. [Figure 101] A) TEM micrograph showing a typical exoskeleton mineral framework in sample G1. B) XRD profile of sample G1. C) Raman spectrum of sample G1. [Figure 102] 1 is a model showing an spx layer within an spx network grown to completion around the underlying template surface. This can be thought of as a side cross-section of the spx network. [Figure 103] A is a photograph of the pelleted MgO template utilized in experiment H. B is a photograph of the porous incrustation mineral composite formed on the MgO pellet. [Figure 104] 10 is a photograph showing contact between the four-point probe and the encased mineral composite material in Test H. [Figure 105] 10 is a graph of sample sheet resistance versus chamber pressure for Experiment H. [Figure 106] This is the Raman spectrum of the sample used in Experiment H. The Raman spectrum did not change after the test performed in Experiment H. [Figure 107] FIG. 1 is a schematic diagram illustrating a method for forming a room temperature superconductor such as a filament by evacuating the internal gas, applying an impermeable barrier layer, and then returning the article to room temperature and external pressure. [Figure 108] 1 is a photograph of the probe tip showing the melted area of ​​the plastic housing where heating of the probe tip occurred. The melted area is circled. [Figure 109] A is an HR-TEM image of a BN-containing exo-mineral framework. B shows Y dislocations present throughout the exo-mineral wall. C also shows screw dislocations present throughout the exo-mineral wall. DETAILED DESCRIPTION OF THE INVENTION

[0026] This section is structured according to the following outline:

[0027] I. Basic Terms and Concepts It provides basic definitions and establishes underlying concepts for describing structures.

[0028] II. Surface replication We introduce basic concepts related to templating, particularly surface replication, which are more comprehensively addressed in the '918 and '760 applications.

[0029] III. Growth and structure of free radical condensates We explain how graphene networks nucleate and grow as free radical condensates. We explain the structural interactions between growing graphene domains.

[0030] IV. Three-dimensional surfaces Describe curved surfaces and establish certain rules to provide orientation when discussing complex structures in three-dimensional space.

[0031] V. Clarification of Examples To clarify definitions and underlying concepts, an example structure is analyzed and explained.

[0032] VI. Measurement and Characterization Considerations Details of the metrology employed in this disclosure are provided and the Raman spectroscopic properties of disordered carbon are described.

[0033] VII. Procedure The detailed synthesis procedures for the carbon samples of Experiments A to G are described below.

[0034] VIII. Experiment A - Analysis Experiment A included (i) the synthesis of a synthetic anthracite network, (ii) sp x Network synthesis, (iii) sp 2 and sp 3 (iv) modeling the formation of diamond-shaped layers and chiral columns; (v) modeling multilayer growth; and (vi) consideration of free radical condensation.

[0035] IX. Experiment B - Analysis Experiment B includes (i) sp x and x-sp x This includes (ii) synthesis of networks, (ii) modeling of various structural interactions, and (iii) post-mortem analysis of prior art and consideration of limitations.

[0036] X. Experiment C - Analysis Experiment C includes (i) the demonstration of incomplete dehydrogenation during the growth of free radical condensates, and (ii) the spectral analysis of the hydrogenated and dehydrogenated carbon phases.

[0037] XI. Experiment D - Analysis Experiment D shows that increasing hydrogen during the growth of the free radical condensate improved grafting.

[0038] XII. Experiment E-Analysis Experiment E includes (i) x-sp x Network and z-sp x This includes (ii) maturing the network to form a mature x-network and a mature z-network, (ii) modeling structural changes during maturation, and (iii) analyzing the mature network.

[0039] XIII. Experiment F - Analysis and Discussion Experiment F includes (i) demonstration of interparticle bridging upon maturation, (ii) demonstration of macroscopic sheet-like and block-like morphologies including mature x- and z-networks, and (iii) discussion of bridging upon maturation.

[0040] XIV. Experiment G - Analysis and Discussion Experiment G includes (i) a demonstration of microwave resistive heating, (ii) a demonstration of diamagnetism and room-temperature superconductivity under reduced pressure in a synthetic anthracite network, (iii) a demonstration of diamagnetism and room-temperature superconductivity under reduced pressure in another disordered pyrolytic carbon, and (iv) a discussion of the theoretical basis for the observations.

[0041] XV. Experiment H - Analysis and Discussion Experiment H includes (i) the demonstration of room-temperature superconductivity in vacuum-adsorbed anthracite macrofoam, and (ii) a discussion of the theoretical basis for the observation.

[0042] XVI. Other anthracite networks BN and BC x We describe a synthetic anthracite network of non-carbon chemical composition containing N.

[0043] I. Basic Terms and Concepts As used herein, the term "graphene" refers to sp2 Hybridized atoms or sp 3 Graphene represents a two-dimensional polycyclic structure of hybridized atoms. While graphene refers to one form of carbon, the term graphene is used herein to represent various graphene polymorphs (including known or theoretical polymorphs such as graphene, amorphous graphene, phagraphene, hecklerite, etc.), as well as other two-dimensional graphene analogs (e.g., BN, BC x The term "graphene" is used to describe a monolayer of atoms such as N. The term "graphene" therefore refers to the two-dimensional nature, polycyclic structure, and sp 2 or sp 3 It is intended to encompass any hypothetical polymorphs that meet the basic criterion of hybridization.

[0044] As used herein, "two-dimensional" refers to molecular-level structures comprising a monolayer of atoms. Two-dimensional structures can be embedded or buried in higher-dimensional space to form larger-level structures that can be described as three-dimensional at this larger level. For example, a graphene lattice of sub-nanoscale thickness can bend within three-dimensional space to form the atomically thin walls of a nanoscale, three-dimensional hole. This hole can still be described as two-dimensional at the molecular level.

[0045] A "ring" is defined herein as a covalently bonded chain of atoms comprising a closed polyatomic polygon with vertices of less than 10 atoms. Each of the cyclic structures of a polycyclic array comprises a ring. Each of the atoms comprising a given ring can be represented as an atomic member belonging to that ring, and the ring can be described accordingly (i.e., a "six-membered" ring represents a hexagonal ring formed by six atomic members).

[0046] As used herein, "sp 2 "Ring" means sp 2 Defined as a ring containing all hybridized atomic members.

[0047] As used herein, "sp xA "ring" is defined as a ring that includes atomic members that do not all share the same orbital hybridization.

[0048] As used herein, a "chiral ring" refers to a ring in which the covalently bonded chain of atomic members contains one or more chiral segments. x The two atoms at the ends of these chiral segments are sp 3 -sp 3 sp bonded to each other via bonds 3 Hybridization atoms. Chiral rings arise from transitions in structural bands.

[0049] As used herein, the term "chiral column" refers to a column 3 -sp 3 It is defined as a series of z-adjacent chiral rings connected to each other through one or more z-directed chains of bonds. Chiral columns tend to form on the chiral rings of the base layer and represent the lateral ends of the diamond-shaped seam. A chiral column is composed of one or more sp x It may include a spiral.

[0050] As used herein, "sp x "Spiral" means sp 2 Hybridization atom members and sp 3 It is defined as a type of helical one-dimensional chain composed of both hybridized atomic members. x The axis of the spiral is in the z direction.

[0051] As used herein, "sp x A "double helix" is a structure in which two sp molecules share the same chirality and the same axis. x It is defined as a structure formed by a spiral.

[0052] As used herein, "sp 2 "Spiral" means sp 2 It is defined as a type of helical one-dimensional chain consisting only of hybridized atomic members. x The axis of the spiral is in the z direction.

[0053] As used herein, "sp2 A "double helix" is a structure in which two sp molecules share the same chirality and the same axis. 2 It is defined as a structure formed by a spiral.

[0054] As used herein, "adjacent rings" refers to two rings that have at least two common atomic members and therefore share at least one common face. In organic chemistry, these rings may include fused or bridged rings, but do not include spirocyclic rings. Two adjacent rings may be referred to as "adjacent rings."

[0055] As used herein, the term "ring-connected" refers to a structure that is connected via a "ring path," i.e., a path of adjacent rings. Ring connectivity can be described in two ways. First, one part of a structure can be said to be ring-connected to another part of the structure. This means that there is a ring path connecting the two referenced parts. For example, a ring R1 in a graphene structure is ring-connected to another ring R2 in the structure if there is a path of adjacent rings that starts at R1 and ends at R2. Second, the referenced structure itself can be said to be ring-connected. This means that any part of the referenced structure can be reached from any other part via at least one ring path. Alternatively, a structure that is not ring-connected can be described as ring-disconnected.

[0056] As used herein, the term "ring path" refers to the path of adjacent rings connecting two referenced structures.

[0057] As used herein, the term "ring connection" refers to a ring connecting two referenced structures.

[0058] As used herein, "sp 2 "Sp" means "connected in a ring" 2 "Ring pathway", i.e., adjacent sp 2 It refers to structures connected through a path of rings. Similar to ring connectivity, sp 2In the first usage, one part of a structure is connected to another part of the structure by sp 2 It can be said that the two parts are connected in a ring. 2 The second usage is when the referenced structure itself is sp 2 It can also be said to be ring-connected, meaning that every part of the referenced structure has at least one sp 2 This means that it can be reached from any other moiety via a ring path. 2 Since ring connectivity is a specific case of ring connectivity, it means ring connectivity, but ring connectivity is sp 2 It does not mean ring connectivity. In certain cases, sp 2 Certain ring-connected structures are called "sp" to mean that they are not ring-connected by a ring pathway. 2 This can be expressed as "ring cleavage."

[0059] An "edge atom" is defined as an atom that (i) belongs to a ring and (ii) is not surrounded by a ring on all sides. An edge atom always has multiple nearest neighbors that are also edge atoms, forming a chain.

[0060] An "edge" is defined as a chain of edge atoms. Starting from any given edge atom, it is possible to trace a chain of nearest edge atoms from this first atom, and any given pair of nearest edge atoms in the chain are co-members of exactly one ring. Some edges may form a closed circuit, with the first and last traced atoms being nearest neighbors to each other.

[0061] An "end segment" is defined as the chain of nearest end atoms contained within the larger end.

[0062] An "internal atom" is defined as an atom that (i) belongs to a ring and (ii) is surrounded on all sides by a ring.

[0063] As used herein, a "graphene structure" is defined as a polycyclic group of two or more rings connected together. Every ring in a graphene structure is connected to every other ring, but the sp 2 They do not have to be connected in a ring. Each atom in the graphene structure can be classified as either an internal atom or an edge atom.

[0064] A "graphene domain" or "domain" is defined herein as a subsidiary portion of a larger graphene structure that itself meets all the requirements of a graphene structure.

[0065] "Ring disorder" is defined herein as the presence of non-hexagonal rings in a graphene structure. Ring-disordered graphene structures include amorphous, hecklerite, pentagonal, or other molecular tilings. The presence of non-hexagonal rings creates regions of non-zero Gaussian curvature in the ring-disordered graphene structure. When inserted into a hexagonally tiled lattice, five-membered rings contain positive Gaussian curvature, and seven-membered rings contain negative Gaussian curvature. For example, fullerenes are curved graphene structures formed by 20 hexagons and 12 pentagons.

[0066] "Ring ordering" is defined herein as substantially hexagonal molecular tiling. Ring-ordered graphene structures have low bending stiffness, allowing them to bend and wrinkle.

[0067] A "system" is defined herein as a polyatomic physical structure containing a group of atoms bonded together either through chemical bonds or van der Waals interactions. A system can contain any number of graphene structures or none at all. It is a general term used to describe the physical structure under consideration.

[0068] As used herein, a "graphene system" is defined as a system of one or more distinct graphene structures. A graphene structure that belongs to a graphene system may be referred to as a "graphene member" or a "member" of the graphene system. A graphene system does not include any elements other than its graphene members.

[0069] "Graphene element" or "element" is defined herein as a graphene system that contains a single distinct graphene structure.

[0070] A "graphene aggregate" or "aggregate" is defined herein as a graphene system that includes two or more different graphene structures.

[0071] "Van der Waals aggregates" or "vdW aggregates" are defined herein as multilayer graphene aggregates in which the graphene structures are held together primarily or substantially by intermolecular forces. The graphene structures in vdW aggregates may also be held together by other mechanisms.

[0072] A "double screw dislocation" is defined herein as a dislocation formed by two screw dislocations that share the same chirality and the same dislocation line. A double screw dislocation in graphene forms a graphene double helix. The braid-like shape of the double helix can physically interlock the two helices.

[0073] A "multilayer" graphene system is defined herein as a graphene system containing two or more layers that are, on average, vdW-connected. Multilayer graphene systems may have monolayer regions. Analytical examples include graphene systems with an average BET surface area of ​​2,300 m as measured by N adsorption. 2 / g can be defined as a multi-layer graphene system.

[0074] A "Y transition" is defined herein as a ring-connected Y-shaped graphene region formed by bifurcating a layer into two laterally adjacent layers. The two "branches" of the Y-shaped region are z-adjacent sp xThe laminated laminate comprises a ring, which together define a diamond-shaped seam at the interface of the laterally adjacent layers, and a characteristic Y-shape is associated with the cross-section of the layers and the joining of the diamond-shaped seam.

[0075] As used herein, a "diamond-shaped seam" or "seam" refers to a z-adjacent splice that forms a z-direction interface between the xy-direction layers on either side. x They are defined as two-dimensional sheets of rings. Cubic diamond-shaped seams contain chair conformations, while hexagonal diamond-shaped seams contain chair, boat, and possibly other conformations. Diamond-shaped seams may terminate in chiral columns.

[0076] A "bond line" is a linear arrangement of two or more side-by-side bonds that are generally oriented parallel (but not necessarily perfectly parallel).

[0077] As used herein, the term "graphene network" refers to a structure with a two-dimensional molecular-level geometry that is three-dimensionally crosslinked at several larger levels. As a function of the crosslinking and meshwork of a graphene network, the network cannot be broken without breaking some of its two-dimensional molecular structure. Graphene networks encompass the broadest category of networks composed of graphene structures, as indicated by this category's position at the apex of the classification diagram in Figure 1. Due to the requirement for three-dimensional crosslinking at some level of evaluation, graphene systems (such as simple polycyclic hydrocarbons) that cannot be described as three-dimensionally crosslinked at any level are excluded from this definition. In this disclosure, the term "graphene network" follows Applicant's usage of the term "graphene," in the sense that it is used generally to apply to networks comprising two-dimensional molecular structures of various polymorphs and chemical properties. In the specific case of carbon-graphene networks, the network can be further described in terms of the anisotropy of its molecular-level crosslinking. ·Average I 2Du / I Gu A ratio greater than 0.40 is "highly anisotropic." ·Average I 2Du / I Gu A ratio between 0.20 and 0.40 is "moderately anisotropic." ·Average I 2Du / I Gu If the ratio is below 0.20, there is "minimal anisotropy."

[0078] A "layered" network is defined herein as a multilayer graphene network containing z-adjacent layers with graphitic or nematic xy ordering. Layered graphene networks are shown as a subcategory of graphene networks in the classification diagram in Figure 1. Schwarzite, as shown in Figure 2, does not contain a layered graphene network.

[0079] A "graphitic network" is defined herein as a type of layered graphene network in which z-adjacent layers exhibit graphitic xy ordering - i.e., they are substantially parallel. A graphitic network has an average <002> It may be characterized by an interlayer d-spacing of 3.45 Å or less, with a significant absence of interlayer spacings greater than 3.50 Å. Graphite networks are shown in the classification table of FIG. 1 as a subcategory of layered graphene networks.

[0080] The term "anthracite network" as used herein is defined as a type of layered graphene network comprising two-dimensional molecular structures cross-linked via specific characteristic structural transitions, herein referred to as "anthracite transitions" including Y-dislocations, screw dislocations, and mixed dislocations having characteristics of both Y-dislocations and screw dislocations. The Z-adjacent layers of the anthracite network exhibit a nematic ordering. The anthracite network has a surface roughness greater than 3.50 Å. <002> They may be characterized by the prominent presence of interlayer d-spacing. Anthracite networks are shown as a subclass of graphene networks in the classification table of FIG. 1 and may be further classified as natural (i.e., anthracite) versus synthetic, with synthetic anthracite networks varying in structure and chemistry.

[0081] The term "nematic alignment" is used herein to describe the general xy alignment at the molecular level between z-adjacent layers in multilayer graphene systems. While this term is typically used to describe the consistent but imperfect kind of xy alignment observed between liquid crystal layers, we have found it useful here to describe the imperfect xy alignment of z-adjacent layers in anthracite networks. Nematic alignment occurs when the xy alignment is greater than 3.50 Å. <002> It may be characterized by the pronounced presence of interlayer d-spacing.

[0082] As used herein, "sp x The "network" is defined as a type of synthetic anthracite network containing a single continuous graphene structure, which is cross-linked laterally and vertically via diamond-shaped seams and mixed dislocations (e.g., chiral columns). In relation to the maturation process, sp x The network is "sp x It may be referred to as a "precursor."

[0083] Carbon sp x Networks can be further classified based on their degree of internal grafting, which is the degree of premature sp 2 The degree of grafting can be determined by the percentage of hybridized end states. x The network can be described as follows: (a) Its average D u Position is 1342cm -1 (b) its average D f The peak position is 1342 cm -1 and (c) the point spectrum is located at 1342 cm -1 Lower D u If no peak position is shown, it is "minimally grafted." (a) The average Du peak position is 1332 cm -1 and 1342cm -1 and (b) the point spectrum is located between 1332 cm -1 Lower D u If the peak position is not shown, or (a) its average Du The peak position is 1342 cm -1 (b) The point spectrum is located above 1332 cm -1 and 1340cm -1 D between u If the peak position is indicated, it is "partially grafted." · Its average D u The peak position is 1332 cm -1 or (a) its average D u The peak position is 1332 cm -1 and (b) several point spectra at 1332 cm -1 Lower D u If the peak position is indicated, it is "highly grafted." These conditions are summarized in Table 1 below. [Table 1]

[0084] In this specification, a "spiral network" is defined as a type of synthetic anthracite network containing screw dislocations. These screw dislocations are sp x It can be formed through the maturation of chiral columns present in the network. x The network is a spiral network of "sp x sp precursors. x The induction of the precursor into a helical network is indicated by the dashed arrow labeled “mature” in the classification diagram in Figure 1.

[0085] As used herein, "mature" refers to sp x sp in precursor 3 Hybridized sp 3 From sp 2 It is defined as the structural transformation that accompanies the rehybridization to sp x The precursors eventually mature to form a helical network, the degree of which varies depending on the species. 3 From sp 2The maturation is progressive, so the degree of rehybridization to sp x Intermediate networks can form that contain features of both helical and helical networks. Furthermore, maturation can occur locally: for example, heating a specific location of the network with a laser can result in local maturation of the affected area.

[0086] As used herein, a "highly mature" carbon helical network has a length of at least 1340 cm -1 and its sp x At least 8cm above the precursor -1 High average D u It is defined as a carbon helical network with peak positions.

[0087] As used herein, "x carbon" refers to a category of synthetic anthracite networks constructed from graphene and is defined as including one of the following: Highly grafted sp herein x "x-sp" defined as a network x network" x-sp x "Helical x carbon" formed by maturing precursors to intermediate or highly mature states

[0088] As used herein, "z carbon" refers to a category of synthetic anthracite networks constructed from graphene and is defined as including one of the following: Minimally partially grafted sp x The network is defined as "z-sp x network" z-sp x "Helical z carbon" formed by maturing precursors to intermediate or highly mature states When used in connection with identifying z carbons, the z prefix does not refer to z directionality.

[0089] A "helical monomer" is defined herein as a helical network of monomeric structures, which comprises graphene structures connected in a single ring, and the network is cross-linked laterally and vertically by screw dislocations.

[0090] As used herein, a "helix assembly" is defined as an assembly-type helix network, which comprises an assembly of multiple helix graphene structures that are physically interlocked with each other via braided double helices (i.e., double screw dislocations).

[0091] "sp x "Preform" is a different sp x It is a macroscopic assembly of precursors, here referred to as "sp x They are called "microforms." They can be elongated, flat, or equiaxial in shape. x A variety of forming techniques can be used to impart the desired shape to the preform.

[0092] As used herein, macrofoam means a macroscopic cohesive structure.

[0093] In this specification, "maturation from a single unit to a single unit" means sp x It is defined as the maturation process by which precursors mature to form helical monomers.

[0094] In this specification, "maturation from a single entity to an aggregate" refers to sp x It is defined as the maturation process that collapses precursors into helical assemblies.

[0095] "Collapse" is defined herein as the division of a single graphene network into two or more distinct ring-broken graphene structures.

[0096] A "primitive domain" is defined herein as a graphene domain that nucleates and grows on a substrate before a structural encounter occurs. When primordial domains grow toward each other on a common surface, their edges may have a structural encounter.

[0097] A "primitive region" is defined herein as a region of a graphene network that generally coincides with a primitive domain of the graphene network. A region that was originally a primitive domain is generally referred to as a primitive region when describing some regions of the graphene system.

[0098] A "structural encounter" is a state of near lateral contact between two edge segments during the growth of a two-dimensional lattice. A structural encounter creates a structural interface between the two edge segments involved. The numerous structural encounters that can occur during the nucleation and growth of graphene systems can be described as "structural activity."

[0099] A "structural interface" is defined herein as an edge-to-edge interface formed by a structural encounter between two graphene structures or regions.

[0100] A "zigzag-zigzag interface" is defined herein as a structural interface where both end segments are zigzag shaped.

[0101] A "zigzag-armchair interface" is defined herein as a structural interface where one of the end segments is zigzag shaped and the other is armchair shaped.

[0102] An "offset zone" is defined herein as an interface zone within a structural interface where one of two end segments is vertically offset - i.e., one end segment is positioned above the other.

[0103] As used herein, a "horizontal zone" refers to a zone in which two end segments involved are substantially horizontal with respect to each other and two or more laterally adjacent segments 2 -sp 2A bond line of bonding may be formed across the interface, with one or more sp 2 It is defined as an interfacial zone within a structural interface that is sufficiently aligned to provide ring connectivity.

[0104] As used herein, a "junction" refers to a point where two related end segments intersect and are insufficiently aligned, resulting in two or more laterally adjacent segments. 2 -sp 2 It is defined as the position of the structural interface that forms the bond line of the bond. 2 Edge atom 2p z This may be because the orbitals are misaligned, preventing the formation of a π bond.

[0105] As used herein, "sp 2 "Grafting" refers to the formation of sp between two end atoms. 2 -sp 2 It is defined as forming a bond line. 2 Grafting allows different graphene structures to be connected and combined into larger graphene structures. 2 Create a ring connection. 2 Grafting is favored in the horizontal zone.

[0106] As used herein, "sp 3 "Grafting" refers to the formation of sp between two end atoms. 3 -sp 3 This is defined as forming a bond. 2 sp at edge atom 2 From sp 3 It is possible that they are involved in the rehybridization of sp. 3 Grafting allows different graphene structures to be connected and combined into larger graphene structures. x Create a ring. 3 Grafting is advantageous in the offset zone.

[0107] "Base" or "base layer" is defined herein as the first graphene layer formed by grafting across the structural interface between pristine domains during pyrolytic growth.

[0108] "Mesoscale" is used herein to refer to hierarchical levels or features (e.g., cross-linking, porosity) that relate to relatively larger size levels than molecular features. For example, the mesoscale cross-linking of an exoskeleton mineral framework corresponds to a size-scale cross-linking that is more relevant to a discussion of its particle morphology than to a discussion of its molecular bonding structure.

[0109] "Micropores" are defined herein according to IUPAC rules as pores with a diameter of less than 2 nm. A "microporous" structure or phase is characterized by the presence of micropores.

[0110] "Mesopores" are defined herein according to IUPAC rules as pores with a diameter between 2 nm and 50 nm. A "mesoporous" structure or phase is characterized by the presence of mesopores.

[0111] "Macropores" are defined herein according to IUPAC rules as pores with a diameter greater than 50 nm. A "macroporous" structure or phase is characterized by the presence of macropores.

[0112] In this specification, a "room-temperature superconductor" is defined as a material or article that can enter a superconducting state at a temperature above 0°C and an external pressure between 0 and 2 atm. In this specification, a "room-temperature superconductor" is defined as a superconducting state at a temperature above 0°C and an external pressure between 0 and 2 atm.

[0113] II. Surface replication Pyrolysis is the decomposition of gaseous, liquid, or solid carbonaceous materials and may be utilized to form graphene structures. In pyrolysis procedures, this decomposition occurs on a substrate surface. The substrate may include the simple flat surface of a foil or the more complex surface of a particle. Graphene systems synthesized on particles may inherit some of the morphological characteristics of the particle. The '918 and '760 applications define several terms related to template-dependent synthesis. These terms are defined as follows:

[0114] A "template," as defined herein, is a potentially sacrificial structure that imparts a desired morphology to another material formed within or on it. Relevant to surface replication techniques are the surface of the template (i.e., the "template surface"), which is replicated in a convex manner, and the bulk phase (i.e., the "template bulk"), which is replicated in a concave manner. The template may also serve other functions, such as catalyzing the formation of the encased mineral material. A "templated" structure is one that replicates some features of the template.

[0115] An "encrusted mineral" or "encrusted mineral" material is a material that is formed within or on a solid-state or "hard" template material.

[0116] "Surface replication," as defined herein, includes templating techniques that use a template surface to guide the formation of a thin, encasing mineral wall of an adsorbent material, which wall substantially encapsulates and replicates the templated surface on which it is formed. When subsequently displaced, the bulk of the template is replicated in recesses by the intra-pore spaces within the encasing mineral wall. Surface replication creates an encasing mineral framework with a templated pore and wall structure.

[0117] As defined herein, an "exo-encapsulated mineral framework" (or "framework") refers to a nanostructured exo-encapsulated mineral formed during surface replication. The exo-encapsulated mineral framework includes nanostructured "exo-encapsulated mineral walls" (or "walls") that can range in thickness from less than 1 nm to 100 nm, but preferably between 0.6 nm and 5 nm. The exo-encapsulated mineral walls can be described as "conformal" so long as they substantially encapsulate and replicate the template surface. Exo-encapsulated mineral frameworks have a variety of structures, ranging from simple hollow structures formed on non-porous templates to complex structures formed on porous templates. They can also contain different chemical compositions. A typical framework can be constructed from carbon and can be referred to as a "carbon exo-encapsulated mineral framework."

[0118] As defined herein, an "endoclastic mineral" includes a template that exists within a substantially encapsulated exocytic mineral phase. Thus, after the exocytic mineral phase has formed around it, the template may be referred to as an endocytic mineral, or "endomineralic."

[0119] As defined herein, an "excluded mineral complex" is a composite structure containing an endohedral mineral and an exohedral mineral. An exohedral mineral complex material can be written as x@y, where x is an exohedral mineral element or compound and y is an endohedral mineral element or compound. For example, an exohedral mineral complex containing a carbon exohedral mineral of an MgO endohedral mineral can be written as C@MgO.

[0120] A large number of template elements or compounds can be utilized, including carbon, metal oxides, oxoanion salts, boron nitride, and metal halides. Magnesium oxide (MgO) templates, in particular, are often used in chemical vapor deposition (CVD) processes due to their stability at high temperatures. Many of these templates are described in the '918 and '154 applications. All that is required in many surface replication procedures, including CVD, is a surface and the nucleation of a lattice that can grow via autocatalysis or as free-radical condensation.

[0121] III. Growth and structure of free radical condensates According to the free radical condensate theory, free radical condensates (hereafter "condensates" or "FRCs") are formed during the pyrolysis of reactive vapors. Carbon FRCs are charged, hydrogenated precursors to graphene structures that can rapidly rearrange the carbon backbone without breaking covalent bonds. They can therefore be regarded as a type of charged, covalently bonded liquid. Carbon FRCs grow via radical addition reactions at their edges in the presence of reactive vapors. When the condensate releases hydrogen molecules, the concentration of radicals decreases, self-rearrangement ceases, and the carbon structure becomes uncharged. Gradual release of hydrogen molecules allows the FRCs more time to rearrange into energy-minimizing configurations—configurations that typically eliminate high-energy edge defects. This has been shown to promote edge-free graphene structures, such as fullerenes. On the other hand, rapid loss of hydrogen does not allow sufficient time for such energy-minimizing rearrangements to occur, promoting the formation of graphene structures with more edges.

[0122] When grown on a common substrate surface, graphene structures may come into lateral contact with each other. The underlying factors that determine such structural encounters and how they resolve have been largely unexplored. In one case discovered by the present applicant, researchers observing the growth of ring-ordered crystalline graphene structures on copper foil discovered that structural encounters resolve in one of two ways, as shown in Figure 5A.

[0123] In the first scenario, one edge of a graphene structure is subducted by the other edge—referred to herein as a “subduction event.” As shown in Figure 5B, the subduction event allows the subducted region to continue growing on top of the subducted region. The continued growth of the subducted region is indicated by the black arrow in Figure 5B, while the growth of the subducted region is halted, as indicated by the black “x” in Figure 5B. The subduction event forms an edge dislocation involving two overlapping z-neighboring graphene structures weakly bound by van der Waals interactions.

[0124] In the second scenario described by the researchers, one edge of the graphene structure is connected by sp bonds between the opposing edge atoms. 2 -sp 2 The sp can be grafted to the other end via bond formation. 2 Grafting allows two graphene structures to merge together to form a larger graphene structure. The result of this event is shown in Figure 5C. The researchers discovered that the sp 2 We have shown that grafting can form non-hexagonal rings in new graphene structures. 2 We found that the local presence of these non-hexagonal rings within the grafted domains can induce local lattice curvature, as shown in Figure 5C.

[0125] The structural complexity between graphene structures increases when the substrate surface becomes more morphologically and topographically complex. It further increases when edge disorder is assumed. Applicant speculates that these factors are important in determining the outcome of structural encounters. Finally, it increases when structures occur in a substantially unconfined space, where the steric effects of surrounding structures can be ignored. This is not the case when pyrolysis occurs in certain microporous template particles, such as zeolite Y. Due to the z-direction confinement in the micropores of these templates—i.e., the lack of headroom—the sp 2 Grafting (different from sinking) can be forced.

[0126] IV. Three-dimensional surfaces To describe the local space around a curved, two-dimensional graphene structure, it is useful to establish intuitive directions. On a curved surface, there are several tangent planes at any given point, which can be thought of as xy planes. Figure 3 shows a hypothetical structure with the tangent planes highlighted in yellow at several points. Consistently, the z-axis perpendicular to this xy plane is also shown in Figure 3. While the orientation of the tangent planes and z-axis varies depending on the surface, it generally seems useful to describe the local space above or below the graphene region as "z-space" and the direction in local z-space as "vertical." It also seems useful to describe the direction perpendicular to the local z-axis as "lateral."

[0127] An example of a ring-disordered graphene domain with nonzero curvature is modeled in Figure 4. The model was constructed using Avogadro 1.2.0 software and relaxed to obtain a rough approximation of the actual molecular shape that may exist in free space. The resulting domain can be rotated to facilitate visualization from different perspectives, as indicated by the black arrows in Figure 4. One segment of its edge is highlighted in blue for orientation.

[0128] Viewed vertically in Figure 4, ring disorder is observed. Domains incorporate random tiling of five-, six-, and seven-membered rings. Viewed obliquely, regions with positive (red arrows) or negative (orange arrows) curvature are observed. Viewed horizontally, blue edge segments can be seen, creating a sense of lattice deflection in the z-direction (z-bias) created by ring disorder. The z-bias of the domains, along with the local lattice, imparts an undulating shape to the z-biased edges. Increased ring disorder can increase the amplitude and frequency of the edge z-bias.

[0129] V. Clarification of Examples These concepts can be clarified by analysis of exemplary systems. Unless otherwise stated, all models are based on sp 2 Hybridization or sp 3 Hybridized carbon atoms are shown, hydrogen atoms are not shown.

[0130] A in FIG. 6 shows 26 carbon atoms, each numbered, and R A , R B , R C , …, R H It is a system of eight ring structures represented as R A The ring structure, designated R, consists of seven carbon atoms (i.e., atoms 1, 2, 3, 4, 19, 20, and 21) joined together by covalently bonded chains and together forming a closed heptagon. A meets the definition of a ring. All other ring structures in molecule A in Figure 6 also meet the definition of a ring and can be represented as sets of their atomic members.

[0131] R, which is shown as x in A of Figure 6 A The sides of the pentagonal ring R C It is also shared by R A and R C Since the rings R share a common face, it is also true that they share at least two atomic members. A and R C meets the definition of an adjacent ring.

[0132] In the system A of Figure 6, every atom belongs to a ring, and every ring is connected to every other ring by at least one path through an adjacent ring. For example, ring R A is found by many paths in the adjacent rings. E connected (e.g., R A →R C →R E or R A →R H →R G →R E ). The system can therefore be represented as a ring connection and as a graphene structure.

[0133] Next, the atoms in the graphene structure of Figure 6A are evaluated to determine whether they are interior or edge atoms. Atom 19 is part of the ring R that surrounds it. A , R B and R CTherefore, atom 19 fits the definition of an internal atom. Atoms 20 to 26 also fit this definition. In Figure 1, each internal atom is colored gray.

[0134] Atom 1 is part of a ring R that does not completely surround it. A and R B belongs to the ring. Therefore, 1 meets the definition of an edge atom. Atoms 2 through 18 also fit this definition. All edge atoms are colored blue in Figure 1. Starting from any given edge atom, one can trace a chain of nearest edges from this initial atom, so that any two nearest neighbors in the chain are both edge atoms and co-members of exactly one ring. Continuing this trace to its terminus defines an edge.

[0135] For example, starting from 1, 2 is the nearest atom, the edge atom, and there is exactly one ring (R A ) is a co-member (with 1). Continuing this trace from 2 to 18, a closed circuit is formed by the bond between 18, the last atom in the chain, and its nearest neighbor, 1, the first atom in the chain. Together, these atoms represent the edge of the graphene structure.

[0136] In Figure 6B, a system of 41 carbon atoms and 12 ring structures is shown. Rather than numbering all the atoms, they are grouped based on color coding—gray, blue, and dark blue. Of the 12 ring structures, 11 meet the definition of a ring. The ring structure surrounded by 12 blue atoms is not a ring because it contains nine or more atomic members. Because all 11 rings are ring-connected and there are no atoms that are not members of a ring, the entire system comprises a graphene structure.

[0137] Next, we analyze the atoms of the graphene structure in Figure 6B. Only three atoms belong to rings and are surrounded by rings on all sides. These interior atoms are colored gray in Figure 6B. The remaining 38 atoms in the graphene structure all belong to rings and are incompletely surrounded by rings, so they are all edge atoms. Starting from any given edge atom, we trace the chain of nearest edges, so that any two nearest neighbors in the chain are both edge atoms and co-members of exactly one ring. This results in a traced edge. Following this tracing rule, we find that it is impossible to create a trace that includes all 38 edge atoms in the graphene structure. Therefore, once an edge is traced, we select an edge atom that is not assigned to an edge and trace a new edge, continuing this process until all edge atoms have been assigned to edges. Continuing this process for the system in Figure 6B, we can trace exactly two edges. Edges containing 12-member edges are colored blue, and edge atoms containing 26-member edges are colored dark blue.

[0138] In Figure 6C, a system containing 66 carbon atoms and 21 ring structures is shown. Rather than numbering every atom, they are grouped based on color coding—gray, black, blue, and dark blue. All 21 ring structures are rings, but not every ring is ring-connected to every other ring. Instead, there is a first group of 14 ring-connected rings and a second group of 7 ring-connected rings, but the first and second groups are not ring-connected to each other.

[0139] Thus, system C in Figure 6 contains a 42-member ring-connected graphene structure and another 24-member graphene structure. Because all 66 atoms in system C in Figure 6 are members of several graphene structures, the entire system can be represented as a graphene system, and because the system contains two different graphene member structures, it represents an aggregate. Because the primary cohesive force between the two members is provided by the covalent bond connecting them, the aggregate contains a bonded aggregate.

[0140] In Figure 6D, 38 carbon atoms (all sp 3A system containing 44 hydrogen atoms and 17 ring structures is shown. Rather than numbering every atom, they are grouped based on color coding—gray, light gray, and blue. All hydrogen atoms are colored light gray and appear smaller than carbon atoms. Each of the 17 ring structures contains a five-membered ring, and all 38 carbon atoms are members of one of the 17 rings. Every five-membered ring is ring-connected to every other five-membered ring through a neighboring ring pathway, making the group of 17 rings into a ring-connected graphene structure.

[0141] Because the system in Figure 6, D, includes atoms that are not members of a ring, and because graphene structures include polyatomic rings of carbon atoms, the overall system does not include graphene structures. However, the system does include graphene structures. Because most graphene structures are bonded to hydrogen, oxygen, or other atoms, most graphene structures are subsystems of a larger system that includes non-graphene structural elements. However, this disclosure primarily limits discussion to the polycyclic carbon arrangements that define graphene structures.

[0142] In Figure 6D, the graphene structure contains 15 carbon atoms that both belong to rings and are surrounded by rings on all sides. These interior atoms are colored gray. The remaining 23 atoms in the graphene structure belong to rings that are incompletely surrounded by rings. These edge atoms and the 23-membered edges they contain are colored blue.

[0143] In Figure 6E, a graphene system is shown. The graphene system includes three distinct z-neighboring graphene member structures. Each graphene member structure is ring-disconnected to the other two graphene member structures but is connected by interlayer vdW interactions. Therefore, the graphene system in Figure 6E represents a vdW assembly.

[0144] In Figure 7A, a system containing 42 carbon atoms and 15 ring structures is shown. Figures 7B and 7C show isolated portions of this same system. The 15 ring structures of the system are made up of 13 six-membered rings (R1, R2, R3, ..., R 13(Let be ). Every carbon atom in the system is a member of a ring, and every ring is connected to each other via at least one path through adjacent rings. Thus, the entire 42-atom system contains a single ring-connected graphene structure. This graphene unit contains a Y-dislocation, the intersection of which has a cubic diamond-shaped seam, highlighted in yellow in Figure 7D.

[0145] VI. Measurement and Characterization Notes A number of different instruments were used to characterize the materials synthesized in this disclosure, and the following description provides information about these instruments and context for how the associated data was analyzed.

[0146] All Raman spectroscopic characterization was performed using a ThermoFisher DXR Raman microscope equipped with a 532 nm excitation laser and Omnic profile fitting software. Specific laser powers were used and specified where applicable.

[0147] Raman spectroscopy is commonly used to characterize the molecular structure of carbon, and there is a large body of literature on the subject. Two main spectral features are usually sp 2 Photoexcitation of hybridized carbon: G band (usually graphite sp 2 Carbon is approximately 1580 cm -1 ~1585cm -1 The peak intensity values ​​are shown in the figure) and the D band (approximately 1350 cm under photoexcitation). -1 In addition, a "2D" band representing a secondary D band is observed in some graphitic carbons, and its peak intensity is usually around 2700 cm -1 The G band is located in sp 2 -sp 2 The D band is assigned to the vibration of the sp 2 This is assigned to the radial breathing mode of the hybridized carbon atoms, and for Raman observation this requires backscattering of electrons at the defect sites.

[0148] Researchers have described an amorphization pathway in the spectrum of graphitic carbon, showing the progression of disorder from graphite to amorphous carbon, which is useful for understanding the dynamics of the D band. In graphite, the D peak is absent because there are no defects to activate it. In carbons containing smaller graphene domains, the density of edge states increases, and as the edge states increase, the D peak is activated by backscattering at the edge defects. The D peak intensity increases toward a maximum, corresponding to nanocrystalline graphite. Further amorphization in the form of ring disorder decreases the intensity of the D peak. Finally, further amorphization leads to the formation of polycyclic sp 2 The D peak disappears due to the complete disappearance of the hybridized structure.

[0149] sp 3 The Raman spectrum peak associated with hybridized carbon is 1306 cm -1 peak (related to hexagonal diamond), 1325 cm -1 peak (related to hexagonal diamond), 1332 cm -1 (associated with cubic diamond). Cubic diamond contains 100% chair conformations, whereas hexagonal diamond contains both chair and boat conformations, resulting in lower Raman frequencies and less thermodynamic stability.

[0150] Raman-active phonons are known to be strain-dependent. Strain in the lattice shifts the vibrational frequency of the lattice, and Raman spectroscopy can be used to understand the strain state in the lattice. However, strain can also move the spectral peaks from their usual identified positions to new positions, making their identification more ambiguous. The main indicators of strain in ring-ordered graphene structures are the positions of the G peak and the 2D peak, both of which are sensitive to tension and compression. The G peak is a peak of the sp 2 -sp 2 It has been shown that when the bonds are stretched they shift to lower frequencies (i.e., "red-shifted") and when they are compressed they shift to higher frequencies (i.e., "blue-shifted"). In graphene structures with inhomogeneous strain fields, multiple modes of the G band can exist.

[0151] In disordered carbon, several peaks in the Raman spectrum are observed in addition to the D peak. 2 1500 cm of hybridized carbon -1 ~1550cm -1 The broad Raman peak (sometimes called "D") often found between sp and sp has generally been observed to increase with ring disorder. 2 Extended and weakened sp s that expand with increasing ring disorder and lattice distortion in hybridized graphene structures 2 -sp 2 This is due to a low correlation red-shifted mode of the G band associated with bond bonding. Ferrari and Robertson showed that the G peak red-shifts to this range in stage II of the amorphization pathway. In graphene oxide, this red-shifted mode of the G peak can be seen simultaneously with the normal G peak, which is due to the presence of normal sp 2 Bonding and weak sp 2 This indicates the presence of ring-ordered bonds, which is in good agreement with the conventional interpretation that graphene oxide is a heterogeneous lattice with both ring-disordered and ring-ordered regions.

[0152] Another feature observed in disordered carbon (called the D' peak) can appear as a shoulder to the G peak at 1620 cm -1 This feature is consistent with the high density of edge states, sp 2 It is often observed in hybridized carbons in association with the D peak, and it has been shown that the intensity of the D peak increases near the lattice edge.

[0153] D * Another feature observed in disordered carbon, sometimes called the 1100 cm peak, is -1 ~1200cm -1 This is a broad band that fits between 1175 cm -1 The peak intensity value of sp 2 Network and SP 3 Transition between networks 2Atoms and sp 3 sp formed between atoms 2 -sp 3 It is due to the sp bonding. It is also due to hexagonal diamond. Some researchers attribute this peak to the sp bonding of nanodiamonds and diamond-shaped materials. 3 carbon, but Ferrari and Robertson dispute this. They attribute it to about 1240 cm -1 The protonated aliphatic sp s undoubtedly present at these carbons, along with the broad peaks of 2 We provide evidence that the chain should be assigned to trans-polyacetylene.

[0154] In this disclosure, Raman spectral analysis may include reference to unfitted or fitted spectral features. "Unfitted" spectral features refer to spectral features that are evident before deconvolution by the profile fitting software. Thus, unfitted features may represent the convolution of multiple underlying features, but their location is not subjective. "Fitted" spectral features refer to spectral features that are assigned by the profile fitting software. An incomplete profile fit may indicate the presence of other underlying features that have not been deconvoluted.

[0155] For clarity, features related to unfitted Raman distributions are marked with the subscript "u" - e.g., "G u " band. In this disclosure, OMNIC peak separation software is used to perform profile fitting and deconvolute the features that contribute to the overall spectral profile. These fitted features are annotated with "f" - e.g., "D f " bands. The software's Gaussian-Lorentzian linear setting is used by default, allowing the fitted bands to adopt a Gaussian-Lorentzian profile, with the Gaussian profile of the fraction determined by the software to optimize the fit. Other profile fitting methods may alter the position, intensity, and trend of the fitted peaks.

[0156] An additional unmatched feature defined within this disclosure is the trough ("Tr"), which is the D u Band and G u The region of low Raman intensity located between the bands. D u Peak and G u The minimum intensity value occurring between peaks is called Tr u The trough intensity is a useful feature in practice because it indicates the underlying spectral dynamics, such as the redshift of the G band, which corresponds to ring disorder and lattice distortion, and can be analyzed without relying on subjective judgments of profile fitting.

[0157] An averaged Raman spectrum represents the average of multi-point spectral measurements made on a sample on a rectangular grid. The spectra from different points are normalized and averaged to create a composite spectrum.

[0158] X-ray diffraction of carbon powders was performed at EAG Laboratories. XRD data were collected by coupled Theta:2-Theta scan on a Rigaku Ultima-III diffractometer equipped with a copper X-ray tube with a Ni beta filter, focusing optics, computer-controlled slits, and a D / teX Ultra 1D strip detector. Peak positions and widths were determined using profile fitting software.

[0159] Thermogravimetric (TGA) analysis of the carbon powder was performed using a TA Instruments Q600 TGA / DSC. Thermal oxidation experiments were performed by heating the powder samples in air.

[0160] Transmission electron microscopy (TEM) was performed using an FEI Tecnai F20 operated at 200 kV. A 300-mesh copper grid with lacey carbon was used. All samples were prepared in ethanol and allowed to dry at room temperature.

[0161] Gas sorption data may be collected on a Micromeritics Tristar II Plus.

number

number

number

[0162] Pore ​​size distribution (PSD) and cumulative pore volume are other methods that can be implemented from gas sorption data to understand particle sintering behavior. Data were collected on a Micromeritics Tristar II Plus.

number

number

number

[0163] Using Micromeritics MicroActive software, the Barrett, Joyner, and Halenda (BJH) method can be applied to calculate adsorption / desorption PSD and cumulative pore volume. This method provides a comparative assessment of mesopore size distribution for gas adsorption data. For all BJH data, Faas corrections and Harkins and Jura thickness curves can be applied. Cumulative pore volumes can be measured for both the adsorption and desorption portions of the isotherm.

[0164] VII. Procedure The following discussion summarizes the procedures used to complete each experiment (i.e., Experiment A-Experiment G). Applicant generally strives to label samples according to the most relevant experiment—i.e., Experiment A-Experiment G. Sample A1 is the first sample associated with Experiment A. Within an experiment, multiple samples may be evaluated and multiple procedures may be performed to create the samples. Procedures and samples are labeled the same—e.g., "Sample B2" is made via "Procedure B2."

[0165] This disclosure uses exemplary procedures. Other procedures, including those utilizing pyrolysis of alternative solid or liquid state carbonaceous precursor materials, the use of alternative substrates or catalysts, or other fundamental parameters, may be substituted for those described herein without departing from the concept of the present invention. Many exemplary x carbon synthesis procedures have been performed to establish the versatility of the method, the mechanism of synthesis, and certain observable trends that may be utilized.

[0166] Procedure - Experiment A Procedures A1, A2, and A3 may use a rotary tube furnace equipped with a quartz tube. The quartz tube may be a 60 mm OD quartz tube with a central 12-inch section ("body") of a 100 mm OD tube placed within the furnace's heating zone, as shown in Figure 8A. A quartz baffle within the body may facilitate powder agitation. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted into both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool may be used to secure the ceramic block in place. The powder sample may be placed in the tube without a ceramic boat. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0167] Procedures A4 and A5 may use a tube furnace equipped with a quartz tube. The quartz tube may be a 60 mm OD tube. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted on both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). The powder sample may be placed in an open ceramic boat inside the tube. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0168] Using the furnace configuration described above, five carbon samples can be synthesized using the following procedure.

[0169] Procedure A1: A 500 g sample of magnesium oxide template precursor powder "Elastomag 170" (commercially available magnesia powder from Akrochem) can be placed in a quartz tube in the heating zone of a tube furnace. The rotary tube furnace can be set to non-rotating mode. The furnace can be heated from room temperature to a set temperature of 1,050 °C over 50 min with argon (Ar) gas flowing at 500 sccm. The furnace can be cooled to 750 °C over an additional 30 min with argon gas flow continuing. During this time, the morphology of the MgO template precursor may change as it is calcined to the desired template morphology. After this condition is maintained for an additional 30 min, propylene (C3H6) gas can be introduced at 250 sccm without changing the Ar flow, and this condition can be maintained for 60 min. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature with the Ar flow continuing. At this point, the synthesized C@MgO exoskeleton mineral composite powder can be analyzed by Raman spectroscopy or thermogravimetric analysis (TGA). The MgO template can then be selectively extracted from the C@MgO encapsulated mineral complex powder by acid etching with hydrochloric acid (HCl) under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample A1."

[0170] Procedure A2: A 500 g sample of magnesium oxide (MgO) template precursor powder, Elastomag 170 (a commercially available magnesia powder from Akrochem), can be placed in a quartz tube in the heating zone of a tube furnace. The rotary tube furnace can be set to non-rotating mode. With Ar gas flowing at 500 sccm, the furnace can be heated from room temperature to a set temperature of 1,050 °C over 50 minutes, and then maintained in this state for 30 minutes. During this time, the morphology of the MgO template precursor may change as it is calcined to the desired template morphology. Next, without changing the Ar flow rate, a methane (CH4) gas flow can be initiated at 500 sccm, and this state can be maintained for 30 minutes. The CH4 flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow is maintained. At this point in the procedure, the synthesized C@MgO exoskeleton mineral composite powder can be analyzed by Raman spectroscopy or thermogravimetric analysis (TGA). The MgO template can then be selectively extracted from the C@MgO encapsulated mineral composite powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample A2."

[0171] Procedure A3: MgO powder can be produced by calcining light magnesium carbonate (hydromagnesite powder from Akrochem) at 1,050 °C for 2 hours. A 300 g sample of the uncalcined powder can be placed in a quartz tube within the heating zone of a tube furnace. The rotary tube furnace can be set to rotate at 2.5 RPM. The furnace can be heated from room temperature to a set temperature of 650 °C over 30 minutes with Ar gas flowing at 500 sccm, and then maintained at this temperature for 30 minutes. Next, without changing the Ar flow rate, C3H6 gas flow can be initiated at 270 sccm and maintained at this temperature for 60 minutes. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow is maintained. At this point in the procedure, the synthesized C@MgO exoskeleton mineral composite powder can be analyzed by Raman spectroscopy or thermogravimetric analysis (TGA). The MgO template can then be selectively extracted from the C@MgO encapsulated mineral composite powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample A3."

[0172] Procedure - Experiment B In steps B1-B3, MgO powder can be produced by calcining a template precursor powder containing rhombohedral magnesite (MgCO) crystals. The precursor powder can be calcined in a Vulcan 3-550 muffle furnace at 580°C for 1 hour, then at 1,050°C for 3 hours, with a heating rate of 5°C / min.

[0173] In step B4, MgO powder can be produced by calcining a template precursor powder containing light magnesium carbonate crystals. The precursor powder can be calcined in a Vulcan 3-550 muffle furnace at 750°C for 1 hour with a heating rate of 5°C / min.

[0174] Procedures B1-B3 may use an MTI rotary tube furnace equipped with a quartz tube. The quartz tube may be a 60 mm OD quartz tube containing the central 12-inch section ("body") of a 100 mm OD tube placed within the furnace's heating zone, as shown in Figure 8A. A quartz baffle within the tube can facilitate powder agitation. The furnace can be kept horizontal (i.e., not tilted). Ceramic blocks can be inserted into both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool can be used to secure the ceramic block in place. The powder sample can be placed in the tube without using a ceramic boat. The tube can be fitted with two stainless steel flanges. Gas can enter through the gas inlet on one flange and exit through the gas outlet on the other flange.

[0175] Procedure B4 may use a tube furnace equipped with a quartz tube. The quartz tube may be a 60 mm OD tube. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted on both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). The powder sample may be placed in an open ceramic boat inside the tube. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0176] Procedure B1: The CVD procedure can be carried out at 640 °C for 16 hours under flowing gas conditions. The flowing gas can contain 1,220 sccm of CO2 and 127 sccm of C3H6. The quartz tube can be rotated at 1 rpm. After the resulting C@MgO powder is cooled to room temperature under flowing CO2, the MgO template can be selectively extracted from the C@MgO encapsulated mineral complex powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample B1."

[0177] Procedure B2: The CVD procedure can be carried out at 580 °C for 20 hours under flowing gas conditions. The flowing gas can contain 1,220 sccm of CO and 127 sccm of C H . The quartz tube can be rotated at 1 rpm. After the resulting C@MgO powder is cooled to room temperature under flowing CO, the MgO template can be selectively extracted from the C@MgO encapsulated mineral complex powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample B2."

[0178] Procedure B3: The CVD procedure can be carried out at 540 °C for 32.5 hours under flowing gas conditions. The flowing gas can contain 1,220 sccm of CO2 and 127 sccm of C3H6. The quartz tube can be rotated at 1 rpm. After the resulting C@MgO powder is cooled to room temperature under flowing CO2, the MgO template can be selectively extracted from the C@MgO encapsulated mineral complex powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample B3."

[0179] Procedure B4: The CVD procedure can be carried out at 580 °C for 1 hour under flowing gas conditions. The flowing gas can include 1,138 sccm of CO and 276 sccm of CH. After the resulting C@MgO powder is cooled to room temperature under flowing CO, the MgO template can be selectively extracted from the C@MgO encapsulated mineral complex powder by acid etching with HCl under magnetic stirring conditions, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample B4."

[0180] Procedure - Experiment C In Procedures C1 and C2, MgO powder can be produced by processing a template precursor powder containing sodium-doped elongated nesquehonite template precursor crystals. The sodium-doped nesquehonite template precursor can be precipitated from a stock solution of magnesium bicarbonate in water. First, a 57-liter pressure vessel is filled with magnesium hydroxide (Akrochem Versamag) and deionized water at a concentration of 0.62 mol kg. -1 This mixture can be recycled while being carbonated with CO2 up to 60 psig to form a magnesium bicarbonate (Mg(HCO3)2) solution stock. After about 22 hours, the solution can be filtered to remove undissolved solids. The resulting solution stock is 0.29 mol kg -1 Then, sodium bicarbonate (NaHCO3) is added to bring the sodium concentration of the system to 1.7·10 -3 mole kg -1 The resulting mixture can be filtered, rinsed with deionized water and acetone, and dried in a forced-air oven at 45°C. The template precursor can be used directly in the CVD replication process, with in-situ conversion to MgO during the temperature ramp.

[0181] Procedures C1 and C2 may use a tube furnace equipped with a quartz tube. The quartz tube may be a 60 mm OD tube. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted on both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). The powder sample may be placed in an open ceramic boat inside the tube. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0182] Step C1 A 1.6 g sample of sodium-doped elongated nesquehonite template precursor can be placed in a quartz tube in the heating zone of a tubular furnace. The furnace can be heated from room temperature to a set temperature of 460 °C over 20 minutes while flowing Ar gas at 1271 sccm, and then maintained at this temperature for 15 minutes to allow equilibration. Next, without changing the Ar flow rate, C2H2 gas flow can be initiated at 42 sccm, and this condition can be maintained for 3 hours. The C2H2 flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow is continued, and the resulting C@MgO powder can be recovered. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral complex powder, resulting in the carbon being mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample C1."

[0183] Step C2 A 1.9 g sample of sodium-doped elongated nesquehonite template precursor can be placed in a quartz tube in the heating zone of a tubular furnace. The furnace can be heated from room temperature to a set temperature of 400 °C over 20 minutes while flowing Ar gas at 1,271 sccm, and then maintained at this temperature for 15 minutes to allow equilibration. Next, without changing the Ar flow rate, a CH gas flow can be initiated at 105 sccm, and this condition can be maintained for 3 hours. The CH flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow is maintained. The resulting C@MgO powder can be recovered. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral complex powder, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample C2."

[0184] Procedure - Experiment D In Steps D1 and D2, MgO powder can be produced by calcining a template precursor powder containing light magnesium carbonate crystals in a Vulcan 3-550 muffle furnace at 750°C for 1 hour with a heating rate of 5°C / min.

[0185] In Procedure D1 and Procedure D2, a tube furnace equipped with a quartz tube can be used. The quartz tube can be a tube with an OD of 60 mm. The furnace can be kept horizontal (i.e., not tilted). Ceramic blocks can be inserted on both sides of the heating zone of the furnace (the powder sample is placed between the block and the heating zone). The powder sample can be placed in an open ceramic boat inside the tube. The tube can be fitted with two stainless steel flanges. Gas can enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0186] Step D1 A 0.9 g sample of magnesium oxide template precursor can be placed in a quartz tube in the heating zone of a tubular furnace. The furnace can be heated from room temperature to a set temperature of 700 °C over 30 minutes while flowing Ar gas at 1,271 sccm, and then maintained at this temperature for 15 minutes to allow equilibration. Next, without changing the Ar flow rate, C3H6 gas flow can be initiated at 20 sccm and maintained at this temperature for 30 minutes. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow continues. The resulting C@MgO powder can then be recovered. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral complex powder, resulting in the carbon being mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample D1."

[0187] Step D2 A 0.9 g sample of magnesium oxide template precursor can be placed in a quartz tube in the heating zone of a tubular furnace. The furnace can be heated from room temperature to a set temperature of 700 °C over 30 minutes while flowing argon (Ar) gas at 1,271 sccm, and then maintained at this temperature for 15 minutes to allow equilibration. Next, a combined propylene (C3H6) gas flow of 20 sccm and hydrogen (H2) gas flow of 60 sccm can be initiated without changing the Ar flow rate, and this condition can be maintained for 30 minutes. The C3H6 flow can then be stopped, and the furnace can be cooled to 150 °C while continuing the Ar and H2 flows. The H2 flow can be stopped below 150 °C, the furnace can be cooled to room temperature, and the resulting C@MgO powder can be recovered. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral complex powder, allowing carbon to be mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder, which is referred to herein as "Sample D2."

[0188] Procedure - Experiment E In steps E1 and E2, MgO powder can be produced by calcining light magnesium carbonate (commercially available hydromagnesite powder from Akrochem) in a rotary kiln in an air atmosphere in two stages, as shown in Figure 8A. The first stage heat treatment can be performed at 400°C with a powder residence time of 9 minutes, followed by a second stage heat treatment at 750°C with a powder residence time of 3 minutes.

[0189] Procedures E1A and E2A may use a tube furnace equipped with a quartz tube. CVD may be performed using an MTI rotary tube furnace equipped with a 60 mm OD quartz tube. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted into both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool may be used to secure the ceramic block in place. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange. The powder sample may be placed in a ceramic boat, which may be placed in the heating zone before starting the procedure. Procedures E2 and E4 may utilize a similar setup with minor modifications to allow for rapid heating and / or cooling of the sample. These modifications are described in each exemplary procedure.

[0190] Step E1: 62 g of this pre-calcined MgO powder can be placed in a 50 mm OD quartz tube serving as a boat. After starting Ar gas flow at 2,000 sccm, the furnace can be heated from room temperature to a set temperature of 700 °C over 20 minutes and maintained at this temperature for 15 minutes. Next, while maintaining the Ar flow, C3H6 gas flow can be started at 1,274 sccm and maintained at this temperature for 30 minutes. After that, the C3H6 flow can be stopped, and the furnace can be cooled to room temperature while the Ar flow is maintained. The C@MgO exoskeleton mineral composite powder can be collected.

[0191] Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample E1."

[0192] Procedure E1A: This procedure involves rapidly heating and cooling the encased mineral composite material from room temperature to a desired set temperature. A 3.0 g quantity of the encased mineral composite powder described in Procedure E1 can be placed in a ceramic boat and placed in a quartz tube outside the heating zone of the furnace. After starting the flow of Ar gas at 4,000 sccm, the furnace can be heated from room temperature to a set temperature of 900 °C over 45 minutes and maintained at this temperature for 15 minutes. The sample can be left outside the heating zone until the set temperature is reached. Once the desired temperature is reached, the boat is pushed in with minimal additional air introduction and left in the heating zone for 30 minutes before being returned to the quartz tube outside the heating zone. This can serve to briefly expose the sample to the desired temperature. The furnace can be cooled to room temperature while the Ar flow is continued. The C@MgO encased mineral composite powder can be collected at room temperature.

[0193] Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample E1A."

[0194] Step E2: 74 g of this pre-calcined MgO powder can be placed in a 50 mm OD quartz tube serving as a boat. After starting Ar gas flow at 2,000 sccm, the furnace can be heated from room temperature to a set temperature of 580 °C over 20 minutes and maintained at this temperature for 15 minutes. Next, while maintaining the Ar flow, C3H6 gas flow can be started at 1,274 sccm and maintained at this temperature for 3 hours. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature while the Ar flow is maintained. The C@MgO exoskeleton mineral composite powder can be recovered.

[0195] Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, resulting in the carbon being mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample E2."

[0196] Procedure E2A: This procedure involves gradually heating the encapsulated mineral composite material from room temperature to the desired set temperature and then rapidly cooling it back down to room temperature. A 3.0 g quantity of the encapsulated mineral composite powder described in Procedure E3 can be placed in a ceramic boat and placed in a quartz tube in the heating zone of a furnace. After starting the flow of Ar gas at 4,000 sccm, the furnace can be heated from room temperature to a set temperature of 1,050 °C over 50 minutes and maintained at this temperature for 15 minutes. The furnace can be maintained at this temperature for 1 hour. After that, the furnace can be cooled with the Ar flow continuously, and the heater can be turned off and the ceramic boat can be withdrawn from the heating zone. The C@MgO encapsulated mineral composite powder post can be collected at room temperature.

[0197] Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, allowing the carbon to be mixed in an aqueous MgCl solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, and dried to form a carbon powder. The carbon powder produced by this procedure is referred to herein as "Sample E2A."

[0198] Procedure - Experiment F In step F1, MgO powder can be produced by calcining a template precursor powder containing light magnesium carbonate crystals. The precursor powder can be calcined in a Vulcan 3-550 muffle furnace at 750°C for 1 hour with a heating rate of 5°C / min.

[0199] Procedure F1 may use a Thermcraft tube furnace modified with a quartz tube. The quartz tube may be a 60 mm OD quartz tube with a bulged central 577 mm section ("body") of 130 mm OD tube placed within the furnace's heating zone. A quartz baffle within the body may facilitate powder agitation. The furnace may be kept horizontal (i.e., not tilted). The template sample may be placed within the body within the heating zone, and ceramic blocks may be inserted outside the body on either side of the furnace's heating zone. Glass wool may be used to secure the ceramic blocks in place. The template sample may be placed within the tube without the use of a ceramic boat and allowed to rotate freely within the body. The tube may be fitted with two stainless steel flanges. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange.

[0200] Procedures F2, F3, F4, F5, F6, and F7 may use a tube furnace equipped with a quartz tube. CVD may be performed using an MTI rotary tube furnace equipped with a 60 mm OD quartz tube. The furnace may be kept horizontal (i.e., not tilted). Ceramic blocks may be inserted into both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool may be used to secure the ceramic block in place. Two stainless steel flanges may be attached to the tube. Gas may enter through a gas inlet on one flange and exit through a gas outlet on the other flange. The powder sample may be placed in a ceramic boat, which may be placed in the heating zone before starting the procedure.

[0201] Procedures F1 and F2: A 150 g quantity of magnesium oxide template powder can be placed in the body of a quartz tube. After starting CO gas flow at 1,379 sccm and rotating the tube at 1 RPM, the furnace can be heated from room temperature to a set temperature of 580 °C at a rate of 20 °C / min and maintained at this temperature for 15 minutes. Next, while maintaining the CO flow, C2H2 gas flow can be initiated at 276 sccm and maintained at this temperature for 180 minutes. The C2H2 flow can then be stopped and the furnace can be cooled to room temperature with the CO2 flow continuing. The powder can be recovered. The C@MgO encapsulated mineral composite powder can be further processed to produce carbon powder. The MgO template can be selectively extracted from the C@MgO encapsulated mineral composite powder by acid etching with HCl under magnetic stirring conditions, and the carbon can be mixed in an aqueous MgCl2 solution. The carbon can then be filtered from the solution, rinsed three times with deionized water, rinsed three times with ethanol, and dried to yield a carbon powder referred to herein as "Sample F1."

[0202] A 50 mg quantity of carbon powder from Sample F1 can be compressed under 105 ksi oil pressure in a 7 mm die set (Pike Technologies 161-1010). Upon compression, the carbon can form a pellet, referred to herein as "Sample F2," which can be stable enough for handling.

[0203] Procedure F3: Sample F2 can be placed in a ceramic boat and placed in the quartz tube of a furnace. After starting the flow of Ar gas at 4,000 sccm, the furnace can be heated from room temperature to a set temperature of 1,050°C over 50 minutes and maintained at this temperature for 30 minutes. The furnace can then be cooled to room temperature with the Ar flow continuing. The pellet can be recovered at room temperature and referred to herein as "Sample F3."

[0204] Procedure F4: A 100 mg quantity of sample F1 powder can be placed in a ceramic boat and placed in the quartz tube of a furnace. After starting the flow of Ar gas at 4,000 sccm, the furnace can be heated from room temperature to a set temperature of 1,050 °C over 50 minutes and maintained at this temperature for 30 minutes. The furnace can then be cooled to room temperature while the Ar flow is continued. The powder can then be collected at room temperature.

[0205] A 50 mg quantity of this powder can then be compressed under 105 ksi hydraulic pressure in a 7 mm die set (Pike Technologies 161-1010). Under pressure, the encased mineral carbon framework does not form a pellet but remains as a powder, referred to herein as Sample F4.

[0206] Procedure F5: Potassium carbonate (K2CO3) template precursor can be spray dried using a Sinoped LPG-5 spray dryer. A room temperature solution consisting of 250.35 g of K2CO3 and 1,667.2 g of deionized water (DI) was pumped into the rotary atomizer set at 24,000 RPM at a rate of 23 mL / min. The inlet temperature of the spray dryer was set at 195°C, and the outlet temperature was 139°C. The powder recovered after spray drying was the K2CO3 template precursor.

[0207] A 100 g quantity of this K2CO3 template precursor powder can be placed in a ceramic boat, placed in a quartz tube, and used in an MTI tube furnace to produce an encased mineral complex powder. After starting CO2 gas flow at 1,220 sccm, the furnace can be heated from room temperature to a set temperature of 640 °C at a rate of 20 °C / min and maintained at this temperature for 15 minutes. Next, while maintaining the CO2 flow, C3H6 gas flow can be started at 162 sccm and maintained at this temperature for 2 minutes. The C3H6 flow can then be stopped, and the furnace can be purged with Ar at a flow rate of 2,000 sccm for 30 minutes to remove any CO2 present in the tube. The furnace can then be cooled to room temperature while the Ar flow is continued. The powder can be recovered. The C@K2CO3 encased mineral complex powder can be further processed to produce carbon powder. The K2CO3 template can be selectively extracted from the C@K2CO3 encapsulated mineral complex powder by acid etching with HCl under magnetic stirring conditions, and the carbon can be mixed in a KCl2 aqueous solution. The carbon can then be filtered from the solution and rinsed three times with deionized water to obtain an aqueous paste. This paste can then be rinsed three times with ethanol to obtain an ethanol paste.

[0208] This carbon ethanol paste can be further diluted with ethanol to create an ultra-dilute mixture of 0.003 wt% carbon. This mixture can be stirred for 5 minutes at 12,000 RPM using an IKA T-25 Digital Ultra-Turrax (UT) high-shear rotor-stator homogenizer. The stirred mixture is immediately poured into a glass-fritted vacuum filtration apparatus with a 47 mm diameter nylon filter (0.45 μm pore size) as the filtration medium. Vacuum filtration can be continued without interruption until all the liquid has been drained. The vacuum is turned off, and the filter containing the carbon is allowed to air dry in the vacuum filtration apparatus. After drying, the soft vdW aggregate can be removed from the filter. This vdW aggregate is referred to herein as "Sample F5."

[0209] Procedure F6: Sample F5 can be placed in a ceramic boat and placed in the quartz tube of a furnace. After starting the flow of Ar gas at 4,000 sccm, the furnace can be heated from room temperature to a set temperature of 1,050°C over 50 minutes and maintained at this temperature for 30 minutes. The furnace can then be cooled to room temperature with the Ar flow continuing. The assembly can be recovered at room temperature and referred to herein as "Sample F6."

[0210] Procedure F7: Neskenite (MgCO3·3H2O) can be precipitated from lansholderite (MgCO3·5H2O) to produce elongated particles. A magnesium bicarbonate (Mg(HCO3)2) solution equivalent to 45 g / L MgO can be prepared by high-pressure dissolving magnesium hydroxide (Akrochem Versamag) in carbonic acid at 720 psig. Lansholderite can be precipitated from this magnesium bicarbonate solution in a continuous stirred tank reactor (CSTR). The solution can be cooled to approximately 14°C and agitated at approximately 700 RPM with a down-pumping marine impeller while depressurizing from 720 psig to 0 psig over 5 minutes. 4 SCFM of air can be removed from the headspace while cooling to approximately 12°C for 8 hours. 空気 The solution can be continuously purged with hexane. The solution can be stirred at about 350 RPM for an additional 18.5 hours. The CSTR can then be heated to 34.5°C while stirring at about 720 RPM for 82 minutes. The solution can then be diluted with about 5 L of deionized water while heating to 43.8°C for an additional 61 minutes. The contents of the CSTR are then removed, filtered, and dried in a forced air oven at 40°C. The resulting powder, identified herein as N2, is nectocrystalline nesquehonite.

[0211] MgO powder can be produced by firing in an MTI tube furnace equipped with a 60 mm diameter quartz tube at 640 °C for 2 hours with a N2 gas flow rate of 2000 sccm and a heating rate of 5 °C / min. A 2.4 g quantity of this MgO powder can be placed in a ceramic boat, placed in the quartz tube, and used in an MTI tube furnace to produce C@MgO. After starting CO2 gas flow at 815 sccm, the furnace can be heated from room temperature to a set temperature of 540 °C at a heating rate of 5 °C / min and held at this temperature for 15 minutes. Next, while maintaining the CO2 flow, CH2 gas flow can be started at 812 sccm and held at this temperature for 2 minutes. The CH2 flow can then be stopped, and the furnace can be purged with Ar at a flow rate of 1698 sccm for 30 minutes to remove any CO2 present in the tube. The furnace can then be heated to 900 °C at a heating rate of 20 °C / min and held at this temperature for 30 minutes. The furnace can then be cooled to room temperature with Ar flow continuing. The powder can be recovered. The C@MgO encapsulated mineral composite powder can be further processed to produce carbon powder. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, allowing the carbon to mix in an aqueous MgCl solution. The carbon can then be filtered from the solution and rinsed three times with deionized water to obtain an aqueous paste. This paste can then be rinsed three times with ethanol to obtain an ethanol paste.

[0212] This carbon ethanol paste can be further diluted with ethanol to create an ultra-dilute mixture of 0.003 wt% carbon. This mixture can be stirred for 5 minutes at 12,000 RPM using an IKA T-25 Digital Ultra-Turrax (UT) high-shear rotor-stator homogenizer. The stirred mixture is immediately poured into a glass-fritted vacuum filtration apparatus with a 47 mm diameter nylon filter (0.45 μm pore size) as the filtration medium. Vacuum filtration can be continued without interruption until all the liquid has been drained. The vacuum is turned off, and the filter containing the carbon is allowed to air dry in the vacuum filtration apparatus. Once dry, a flocculated soft buckypaper, referred to herein as "Sample F7," can be removed from the filter.

[0213] Procedure - Experiment G Procedure G1: Magnesite (MgCO3) particles can be crystallized from a solution of magnesium bicarbonate to obtain a powder of equiaxed template precursor particles.

[0214] An MTI rotary tube furnace equipped with a quartz tube can be used. The quartz tube can be a 60 mm OD quartz tube with a central 12-inch section of a 100 mm OD tube placed within the furnace's heating zone, as shown in Figure 8A. A quartz baffle within the tube can promote powder agitation. The furnace can be kept horizontal (i.e., not tilted). Ceramic blocks can be inserted on both sides of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool can be used to secure the ceramic block in place. The tube can be fitted with two stainless steel flanges. Gas can enter through the gas inlet on one flange and exit through the gas outlet on the other flange.

[0215] A quantity of 177 g of precipitated magnesite powder was placed in an Ar flow rate of 5 ft 3 MgO can be produced by firing at 640°C for 10 minutes at a heating rate of 20°C / min under a 1000 kJ / hr heating rate. Using MgO powder already present in a quartz tube, the furnace described above can be used to produce C@MgO. After starting CO2 gas flow at 1,918 sccm and rotating the tube at 1 RPM, the furnace can be heated from room temperature to a set temperature of 640°C at a heating rate of 20°C / min and held at this temperature for 15 minutes. Next, while maintaining the CO2 flow, C3H6 gas flow can be started at 127 sccm and held at this temperature for 360 minutes. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature while the CO2 flow is continued.

[0216] The C@MgO encased mineral composite powder can be returned to the tube in the same furnace / tube configuration for a second growth cycle. After starting CO gas flow at 1,918 sccm and rotating the tube at 1 RPM, the furnace can be heated from room temperature to a set temperature of 640 °C at a rate of 20 °C / min and held at this temperature for 15 minutes. Next, while maintaining the CO flow, C3H6 gas flow can be started at 127 sccm and held at this temperature for 120 minutes. The C3H6 flow can then be stopped and the furnace can be cooled to room temperature while continuing the CO2 flow.

[0217] The C@MgO encased mineral composite powder can be returned to the tube in the same furnace / tube configuration for a third growth cycle. After starting CO gas flow at 1,918 sccm and rotating the tube at 1 RPM, the furnace can be heated from room temperature to a set temperature of 640 °C at a rate of 20 °C / min and held at this temperature for 15 minutes. Next, while maintaining the CO flow, C3H6 gas flow can be started at 127 sccm and held at this temperature for 180 minutes. The C3H6 flow can then be stopped, and the furnace can be cooled to room temperature while continuing the CO2 flow.

[0218] The powder can be recovered. The C@MgO encapsulated mineral composite powder can be further processed to produce carbon powder. Acid etching with HCl under magnetic stirring conditions can selectively extract the MgO template from the C@MgO encapsulated mineral composite powder, allowing the carbon to mix in an aqueous MgCl solution. The carbon can then be filtered from the solution and rinsed three times with deionized water, followed by three rinses with ethanol, to produce an ethanol paste. This paste can be dried to form a carbon powder.

[0219] This carbon powder can then be used for further CVD growth. An MTI rotary tube furnace equipped with a quartz tube can be used. The quartz tube can be a 60 mm OD quartz tube with a central 12-inch section of a 100 mm OD tube placed within the furnace's heating zone. A quartz baffle within the tube can facilitate agitation of the carbon powder. The furnace can be kept horizontal (i.e., not tilted). Ceramic blocks can be inserted on either side of the furnace's heating zone (with the powder sample placed between the block and the heating zone). Glass wool can be used to secure the ceramic block in place. Two stainless steel flanges can be attached to the tube. Gas can enter through a gas inlet on one flange and exit through a gas outlet on the other flange. This assembly is shown in Figure 8A.

[0220] After CO gas flow at 1,918 sccm and tube rotation at 1 RPM, the furnace can be heated from room temperature to a set temperature of 640°C at a rate of 20°C / min and maintained at this temperature for 15 minutes. Next, while maintaining the CO flow, C3H6 gas flow can be initiated at 127 sccm and maintained at this temperature for 180 minutes. The C3H6 flow can then be stopped and the furnace can be cooled to room temperature with the CO2 flow continuing. The final carbon powder mass, minus losses due to migration to the glass wool, can be approximately 43.2 g. The carbon powder produced by this procedure is referred to herein as "Sample G1."

[0221] Procedure - Experiment H Procedure H: In a pressure vessel equipped with an overhead stirring system and gas-injection impeller, 16 kg of deionized water and 1.39 kg of commercially available MgO powder (Versamag) can be mixed to produce an aqueous Mg(HCO) solution. The mixture can be mixed at 700 RPM and cooled to 5°C while supplying CO gas at up to 850 psi for 2 hours. The resulting solution can be removed from the pressure vessel at atmospheric pressure and supplied to a BETE XA air atomizing nozzle containing an FC7 liquid cap and an AC1802 air cap at a rate of 56 mL / min. Compressed air for droplet atomization can be supplied into the nozzle at 54 psi with an air flow rate of 5 SCFH. The inlet temperature of the spray dryer can be set to 200°C, and the outlet temperature can range between 108°C and 109°C. The environmental conditions during the spray drying process can be 28.4°C and 48% RH. Approximately 1400 mL of the solution was sprayed, and 208 g of spray-dried hydrous magnesium carbonate (Mg(CO3) xH2O) template precursor powder with a hollow spherical morphology was collected via a cyclone separator.

[0222] The template precursor powder can then be converted into a template by heat treatment using a muffle furnace (Vulcan 3-550 model, maximum 1440 W). Approximately 10 g of the template precursor powder can be placed in a ceramic boat and heated to 580 °C, then held at this temperature for 13.5 hours, followed by heating to 1050 °C and holding for an additional hour, yielding approximately 3.9 g of MgO powder. The heating rate for both steps can be 5 °C / min, and cooling is allowed to continue overnight over an 8-hour period. Approximately 0.47 g of MgO powder can be pelletized by uniaxial compression at 7.8 ksi in a 15.7 mm ID hydraulic press for 1 minute. The resulting disk-shaped template can have a diameter of 15.7 mm and a thickness of 2.5 mm.

[0223] A Thermcraft tube furnace equipped with a 60 mm OD quartz tube can then be utilized for the template-dependent CVD procedure. The furnace can be kept horizontal (i.e., not tilted), and a 0.47 g pelletized template sample can be placed in a ceramic boat in the heating zone before the procedure begins. Ceramic blocks can be inserted outside both sides of the furnace's heating zone, and glass wool can be used to secure the ceramic blocks in place. Two stainless steel flanges can be attached to the tube. Gas can enter through the gas inlet on one flange and exit through the gas outlet on the other flange. After starting the CO2 gas flow at 815 sccm, the furnace can be heated from room temperature to a set temperature of 540 °C at a rate of 20 °C / min and maintained at this temperature for 5 minutes. Next, while maintaining the CO2 flow, a CH2 gas flow can be initiated at 144 sccm and maintained at this temperature for 90 minutes. The CH2 flow can then be stopped, and the furnace can be cooled to room temperature while the CO2 flow continues. During cooling, the lid of the clamshell furnace can be fully opened, exposing the quartz tube to the outside air. The resulting encapsulated mineral composite pellet can then be characterized. Finally, the pellet is cooled again, and the same CVD growth procedure is repeated two more times, for a total of three CVD growth steps, with the pellet cooled between each step. The resulting encapsulated mineral composite pellet contains macroscopic encapsulated mineral carbon that can be tested for room-temperature superconductivity.

[0224] A vacuum chamber similar to that associated with the Cober-Muegge microwave system used in Experiment G (Figure 8C) may be used, but without microwave irradiation. The vacuum chamber may be equipped with a four-point probe (Lucas / Signatone SP4-40045TFJ) for measuring leadless sheet resistance and contact resistance. The probe specifications may be 40 mil tungsten carbide tip spacing, 5 mil tip radius, and 45 g spring pressure. The four-point probe may be installed inside the vacuum chamber and wired to a Keithley 2400 Series Source Meter located outside the vacuum chamber. The Keithley Source Meter may be set to four-wire mode with the Autoohm method selected, operating as a conventional constant current source ohmmeter with a starting current of 10 mA. The auto-range function was selected, and the current was stepped to 100 mA when the measured resistance fell below 20 ohms / square. A convection-enhanced Pirani vacuum gauge module (CVM201 Super Bee), capable of reading down to 0.1 mTorr with a resolution of 0.1 mTorr and a repeatability of 2% of the reading, can be used to measure the chamber pressure simultaneously with the sample sheet resistance. Finally, the chamber can be equipped with a vacuum pump. This setup should allow the vacuum chamber to be pumped down while simultaneously reading the chamber pressure and sheet resistance.

[0225] The points of the four-point probe are brought into static contact with the flat surface of the macrofoam as lightly and delicately as possible to obtain a stable and continuous sheet resistance reading. This delicate placement must be done so as not to compress the surface of the macrofoam with the probe tips, which is essential for the tested surface. xThis may be necessary because the macrofoam is apparently sensitive to pressure. This pressure sensitivity is believed to be due to local mechanical compression that reduces the interlayer distance and thereby induces interlayer electronic coupling near the voltage detection contact point. Additionally, a soft, non-conductive backing can be used under the carbon macrofoam to minimize local compression. To achieve contact, the source meter can be activated to obtain an initial reading at ambient conditions, after which the chamber can be closed and evacuated. While the chamber is evacuated, readings of the chamber pressure and the sample's sheet resistance can be recorded.

[0226] VIII. Experiment A - Analysis SEM images of sample A1 confirm the presence of an exo-mineral framework. Figure 9 shows an SEM micrograph of sample A1 after removal of the endohedral mineral phase of the exo-mineral composite powder. It is unclear from this SEM micrograph whether one or more distinct exo-mineral frameworks are present. The morphology appears to consist of connected macroporous subunits (as shown in Figure 9). This reflects a partially sintered powder template. Unlike the framework discussed in sample A2, which appeared fragmented and distorted after liquid-phase processing and evaporative drying (as shown in Figures 21-22), the framework in Figure 9 appears largely intact and unaffected by the processing and drying. This indicates that the exo-mineral walls of sample A1 are able to withstand the stresses generated during processing.

[0227] TEM analysis was also performed to enhance transparency and examine the microstructure of the exclusivity mineral walls of sample A1. Figure 10A is a TEM micrograph in which a typical framework can be observed against a background lattice of lacy carbon (this lattice is used to support the TEM sample and is not the carbon of interest). The framework in this micrograph appears to contain at least nine macropore subunits, numbered in Figure 10A. The cavities are both in size and shape consistent with the morphology of displaced endocrine minerals (not shown). No signs of distortion or wrinkling are apparent within the walls.

[0228] A higher magnification, shown in Figure 10B, allows for a more detailed examination of the exoskeleton mineral walls. This image shows a cross section of the wall. The few walls observed in sample A1 were consistently about 12 nm thick (or about 30–35 layers), indicating that the growth of the graphene structure was terminated by CVD cessation rather than by occlusion of the catalyst template surface. This is evidence of the contribution of an autocatalytic growth mechanism; without this mechanism, we would not expect to grow so many layers, no matter how long the CVD was continued. N2 gas adsorption was performed and a BET surface area of ​​142 m was obtained. 2 g -1 and BJH porosity 0.35 cm 3 g -1 This BJH porosity value is undoubtedly smaller than the actual relative porosity, given that large macropores cannot be measured using the N2 adsorption method.

[0229] At the highest magnification, shown in Figure 10C, the layered structure of the enveloping mineral wall can be discerned. It comprises a multilayer stack of overlapping z-neighboring graphene domains, as evidenced by the alternating dark and light edges. Each edge line represents a two-dimensional graphene domain, or the z-spacing between two z-neighboring domains.

[0230] During HRTEM analysis, care must be taken not to confuse the edge lines corresponding to the actual positions of graphene layers with those corresponding to the z-spacings between these layers. Depending on the defocus value, the edges corresponding to the actual atomic positions can be dark or light. For any color, the lines related to the z-spacings will be the opposite color. In the literature, examples can be found where either dark or light edges are associated with graphene layers. Confidently determining the exact atomic positions in HRTEM images requires supporting information about the actual molecular structure.

[0231] The presence of edge lines indicates that this exoskeleton mineral wall fragment of sample A1 contains a stacked arrangement of z-adjacent graphene domains. In the main frame of Figure 10C, a few dark edge lines are traced in yellow. As shown by the yellow trace, the z-adjacent edge lines appear to be roughly aligned in xy at distances of up to a few nanometers, but the edge lines are not parallel throughout the exoskeleton mineral wall. However, due to the local xy alignment of z-adjacent graphene domains, the wall of Figure 10C exhibits nematic alignment. All layers of the imaged wall fragment of Figure 10C exhibited nematic alignment.

[0232] The xy ordering between z-adjacent graphene domains allows for smaller z-spacing and denser arrangement, resulting in enhanced interlayer bonding and vdW aggregation. We believe this is a desirable feature of layered graphene systems, in contrast to the low-density, non-layered network structure exhibited by schwarzite. If density reduction is desired, this can be achieved by introducing larger-scale porosity modes (such as macropores in sample A1) while maintaining dense layered organization at smaller scales.

[0233] Another useful example of nematic alignment is shown in Figure 11. This is an HRTEM image (from a different sample) of an exoskeleton mineral wall with layers of nematic alignment. The rim lines were sharper in the HRTEM image taken of this sample, so this example is shown here. Different sections of the wall are highlighted in yellow. In each highlighted area, the rim pattern indicates nematic alignment with that portion of the wall. This is thought to result from the graphene structures growing conformally on the template surface and also on top of each other.

[0234] Although the layers throughout sample A1 are nematically aligned, it is visually difficult to trace the dark edge lines in Figure 10C for more than a few nanometers. An exemplary portion of the outer membrane wall is shown as a white square in Figure 10C, which is magnified in the inset of Figure 10C. Although the diffraction contrast and focus in this image are not sharp, the edge lines can be recognized and traced. The dark edge lines from the micrograph are traced with red lines. The light edge lines from the micrograph are traced with blue lines in the bright areas with high contrast and with dotted blue lines in the bright areas with low contrast.

[0235] In addition to the z-spacing between the red segments, the magnified inset in Figure 10C appears to show lateral discontinuities—i.e., blue traces—separating the red segments. This pattern can be observed throughout the HRTEM image of sample A1. If the red traces in the magnified inset represent the locations of graphene domains, each lateral discontinuity in the red traces indicates an edge. If this interpretation is correct (which proves incorrect), the ubiquitous presence of this edge pattern throughout the exoskeleton mineral wall suggests that the wall contains a vdW assembly of small graphene domains—these lateral discontinuities are frequent, likely averaging less than 3 nm. Furthermore, if this interpretation is correct, one would have to conclude that the graphene edges of z-neighboring layers are aligned. This could be explained if the edges were caused by fracture, but the lateral pattern is present throughout the entire wall, making such an explanation impossible.

[0236] An alternative (and correct) explanation is that the light-colored edge (corresponding to the blue trace in the enlarged inset of Figure 10C) represents actual atomic positions. The solid blue line in the center of the inset forms a distinct reclined "Y" shape, as indicated by the reclined Y in Figure 10C. This light-colored Y indicates that the bilayer at the branch end of the Y and the graphene monolayer at the stem end of the Y are different regions of the same ring-connected graphene structure. Furthermore, in this scenario, the light-colored edge traced with the dotted blue line has lower diffraction contrast than the solid blue line trace, but still indicates the presence of several atoms. The solid and dotted blue traces indicate that the entire enlarged region is ring-connected—opposite to the separateness indicated by the red trace.

[0237] This observation has precedent in the anthracite literature. HRTEM rimming of anthracite was analyzed to develop a model of structural dislocations in anthracite. Figures 12A-D are borrowed from this HRTEM analysis. Each figure includes a model representing the structural dislocations seen in anthracite and, below the model, a simulation of the associated HRTEM rim pattern. These simulated rim patterns match the rim patterns actually observed in anthracite, validating the dislocation model. In each simulated rim pattern, the light rims represent graphene regions, and the dark rims represent interlayer spaces.

[0238] Figure 12A shows an edge dislocation diagram taken from the anthracite literature, in which a graphene region is sandwiched between two z-neighboring regions—one above and one below. The edges of the sandwiched region represent local terminations of several graphene structures, members of which are sp 2 In van der Waals aggregates formed primarily by subduction events (typical of carbon formed by template-dependent CVD methods), the edges of the subducted region—and the z-neighboring regions between the pinched regions—together contain edge dislocations. A simulated HRTEM edge pattern formed by edge dislocations is also shown in Figure 12A. The pattern is characterized by light edge lines representing the locations of pinched regions terminating between dark Y-shaped edge lines representing the interlayer spacing.

[0239] Figure 12B is a diagram, taken from the Anthracite literature, of a Y-dislocation, which can be thought of as a reclined Y-structure that would form if the edge atom of the sandwiched graphene region of Figure 12A were covalently bonded to one of its z-neighbors. The geological transformation of an edge dislocation (e.g., Figure 12A) into a Y-dislocation (e.g., Figure 12B) reduces the dislocation energy. This is because the junction between the three layers of the Y-dislocation contains sp 3 This occurs through a radical addition reaction, which creates a row of atoms, and researchers suggest that the Y rearrangement in anthracite evolved in this way.

[0240] The simulated HRTEM rim pattern formed by the Y dislocation is shown below the dislocation in Figure 12B. The pattern is the inverse of the simulated pattern in Figure 12A—i.e., the dark rim lines end between the light Y-shaped rim lines. The light Y-shaped rim lines indicate the location of the Y-shaped graphene structure and are a smaller version of those shown by the molecular model in Figure 7D. The simulated rim pattern closely resembles the Y shape traced in the enlarged inset in Figure 10C.

[0241] The geologically formed anthracite network naturally illustrates how structural rearrangements can create three-dimensional graphene networks. Virtually all of anthracite's carbon atoms are members of the graphene network resulting from these cross-linking rearrangements, except for the occasional ring-bonded CH, CH2, or CH3 groups (only small amounts of solid-state C, as shown by NMR, are present). It is this cross-linking of the graphene network that increases anthracite's hardness and prevents it from exfoliating or solubilizing. Using NMR spectroscopy, we show that dodecylation of anthracite affects only the edge atoms of this unit, "making the graphene layers appear to fuse together."

[0242] Returning to the edge pattern shown in the magnified inset in Figure 10C, we can conclude that this pattern is associated with bridging dislocations. The solid blue lines indicate Y-type dislocations. The low-contrast edges traced by the dotted blue lines likely indicate out-of-focus or disordered Y-type dislocations. The red line segments represent the spaces between graphene layers. Because the Y-type dislocations consist of diamond-shaped seams that maintain lateral and vertical ring connections, we can conclude that the magnified inset in Figure 10C indicates ring-connected regions within the exclusivity mineral wall. Furthermore, the presence of these Y-type dislocations throughout the wall indicates that the exclusivity mineral framework of sample A1 contains an anthracite network.

[0243] This finding is further reinforced by a comparative analysis of samples A2 and A3. Specifically, when the exoskeleton mineral framework of sample A1 contains vdW aggregates, the significantly superior robustness of the less crystalline particles of sample A1 compared to the more crystalline particles of sample A2 (relative crystallinity as determined by HRTEM, Raman, and XRD analyses) contradicts findings reported in the literature. The researchers demonstrate that vdW aggregates of small graphene domains are more fragile (i.e., less robust) than those of larger crystalline domains. For example, "amorphous graphene nanocages" (often less than 10 nm in size) with similar morphology to the particles of sample A1 and containing aggregates of small, overlapping graphene domains are easily broken and deformed. This fragility is explained by the weak vdW interactions between the small graphene domains in these aggregates, which are easily sheared. The researchers demonstrate that amorphous graphene nanocages have superior cohesion to crystalline graphene nanocages composed of larger domains. However, in fact, all particles throughout sample A1 show a dramatic improvement in mechanical robustness compared to the fragile nanocrystalline particles found in sample A2.

[0244] From this, it can be said that the outer mineral framework in Figure 10A contains an average of about 18.5 layers of anthracite network (the theoretical specific surface area of ​​graphene is 2630 m2 g -1 The BET specific surface area of ​​sample A1 is 142 m 2 g -1 The observable portion of the anthracite network in Figure 10A contains nine spherical macropore subunits. Overall, this represents a graphene network with a significant amount of lattice area in vdW contacts. A conservative estimate of this area is 48 μm 2 and is calculated based on the following reasons. First, our estimate ignores the 8th and 9th subunits, which are only partially visible in Figure 10A. The average radius of the remaining subunits is difficult to calculate precisely, but it is certainly larger than 200 nm (for reference, the radius of sphere #4 in Figure 10A is approximately 200 nm, as shown by the black dotted line). However, we use this radius as a conservative estimate. The theoretical surface area of ​​seven spheres with a radius of 200 nm is approximately 3.5 × 10 6 nm 2 (i.e. 7×4πr 2 where r = 200 nm). Note that this decreases when the spheres are joined together as in Figure 10A, reducing the theoretical surface area by 25%, to 2.6 × 10 6 nm 2 Finally, based on the estimated average wall thickness of 18.5 layers, the total lattice area of ​​the entire wall is approximately 4.8 × 10 7 nm 2 (i.e., 18.5 layers x 2.64 x 10 6 nm 2 ), i.e., 48 μm 2 It is estimated that...

[0245] Because all of this networked lattice region is composed of nematically aligned layers, virtually all of this lattice region undergoes interlayer vdW interactions. For the same reason that crystalline graphene nanocages constructed from large-area domains exhibit superior vdW cohesion to amorphous graphene nanocages constructed from small-area domains, we can infer that gradually enlarging an anthracite network will result in a significant vdW contribution to the system's cohesion. This is one reason why anthracite networks are more attractive than Schwarzite-like graphene networks, such as those synthesized in zeolite templates (shown in Figure 2). Shorter, more consistent z-spacings and superior vdW cohesion can be achieved with a denser layered structure. The resulting local density increase can then be offset by the introduction of larger-scale porous modes, such as template pores in the exoskeleton mineral framework.

[0246] More detailed information about the bonds within the framework of sample A1 can be obtained from the sample's Raman spectrum. Figure 13 shows a single-point Raman spectrum taken with a 532 nm laser at 2 mW power. No smoothing was performed. For reference, the full spectrum is shown in the inset of Figure 13. u The band is 1345cm -1 and 1350cm -1 This is typical for 532 nm (approximately 2.33 eV) excitation. u The band is usually 1585cm -1 Compared to 1590cm -1 and 1595cm -1 There is a center between sp 2 It can be seen that there is some compressive strain in the bond. u Band and G u High Tr between the bands u There is a peak, I Tru / I Gu The peak intensity ratio corresponds to approximately 0.50, indicating the possible presence of an underlying peak that should be investigated via profile fitting. Du / I GuThe peak intensity ratio is less than 1.0.

[0247] Another unfitted peak evident in Figure 13 is at 1100 cm -1 and 1200cm -1 D located between u This appears as a weak shoulder on the band. The location of this feature is between 1150 and 1200 cm -1 D seen in the area * This peak corresponds to the sp peak of soot-like carbon. 2 Area and sp 3 Transition sp between regions 2 -sp 3 Researchers in this field believe that this is due to the bonding. Therefore, such an assignment is the sp that makes up the diamond-shaped seam. x It matches the ring well.

[0248] To elucidate the underlying features of the Raman profile in Figure 13, OMNIC Peak Isolation software was used. Initially, the software was limited to using only two peaks. Figure 14 shows the two fitted peaks, the fitted profile, the actual profile, and the residual, which represents the difference between the fitted and actual profiles. The residual at the bottom of the graph indicates the extent to which the fitted profile deviates from the actual profile and the magnitude of that deviation. If the residual is flat (taking into account that the residual also reflects unsmoothed actual noise), it indicates a good fitted profile that matches the actual profile. If there are only two peaks, the fitted profile is still poor, with a peak at approximately 1150 cm. -1 and 1650cm -1 There is a large residual between the peak and valley regions, especially between 1150 cm and 1150 cm. -1 It can be seen that the shoulder area nearby does not fit well.

[0249] The OMNIC Peak Separation software then performed a peak separation at 1500 cm before re-running the profile fitting procedure. -1A third peak was manually placed at the start of 1566 cm. Figure 15 shows the three fitted peaks, the fitted profile, the actual profile, and the residuals representing the difference between the fitted and actual profiles. -1 This fitted profile, incorporating a broad fitted peak at 1150 cm, appears to be much better than the profile with only two fitted peaks. -1 and 1200cm -1 There is still a large residual between

[0250] The OMNIC Peak Separation software then performed a fitting procedure at 1150 cm -1 A fourth peak was manually placed at the start of the 1185 cm fit. Figure 16 shows the fourth fitted peak (labeled f-1 to f-4). -1 This fitted profile, which further incorporates a broad fitted peak at 1185 cm, appears to be much better than fitted profiles that yielded two or three fitted peaks. -1 The f-1 peak in reduces the residuals associated with the shoulder feature in this region. These four peaks provide a satisfactory fitting profile.

[0251] The analysis of the four matched bands is as follows: G band (undistorted sp 2 The grid is usually about 1585cm -1 (as seen in the photo) is 1596 cm -1 f-4 peak and 1514 cm -1 The f-4 band represents a blue-shifted mode of the G band. The increase in frequency of these blue-shifted phonons is due to the presence of several sp 2 -sp 2 This is due to the compressive strain of the bond. 1514cm -1 The broader f-3 peak at σ coincides with the "D" peak seen in graphene oxide and represents a redshifted mode of the G band. The lower frequency of these redshifted phonons is due to the sp 2 -sp 2This is due to the stretching and weakening of bonds. In addition to the induction of tensile strain, the ring disorder in this region does not allow for a uniform strain field, which leads to the broadening of the f-3 band. The splitting of the G band into the f-3 and f-4 peaks indicates that the sp 2 -sp 2 Specific regions where bonds are compressed and sp 2 -sp 2 The presence of specific ring disordered regions where bonds are stretched can be discerned.

[0252] In graphene oxide, no blue-shifted band like f-4 is observed, and the G peak also appears at 1585 cm -1 In addition to the normal mode, a red-shifted mode (called the "D" peak, characterized herein by its trough height) is also present. This, together with the absence of oxygen sites in sample A1 (evident from the near-zero mass loss below 400 °C in Figure 20) and its graphene-based layered structure, demonstrates that its Raman spectrum arises from a structure different from that of graphene oxide.

[0253] The f-2 peak in Figure 17 is at 1343 cm -1 The slightly red-shifted D f Represents the peak. 2 The D band of carbon is dispersive and the D peak position can vary based on excitation, but is located at 1343 cm -1 is sp under 532 nm excitation. 2 The D peak position normally associated with carbon (approximately 1350 cm -1 ) is somewhat lower than the redshift of sp 2 Vibrational density of states (VDOS) and sp 3 This indicates that there is some underlying interpolation between the low frequency bands seen in VDOS.

[0254] Interpolation of the VDOS of alloy structures occurs when the interphases are strongly bonded. 2 Interpolation between the high-frequency band (related to hybridization) and the low-frequency band is performed by sp 3 The sp of the state and its immediate neighbors2 These strongly coupled regions are the sp 2 It activates the radial breathing mode (RBM) phonons found throughout the ring structure. 3 Even if the carbon state is present in trace amounts, the larger sp 2 The RBM phonon of the grafted unit can be seen in the Raman spectrum due to the activation of the RBM phonon observed throughout the entire unit. 2 Phase and sp 3 The phase is strongly bonded sp x Ring sp 3 states, and thus the D band associated with the RBM phonons is interpolated. Conversely, the sp 2 Layer containing sp 2 The majority of the states are sp 3 are not in the immediate vicinity of the states or strongly coupled to them, and therefore sp 2 -sp 2 The G band, which is related to vibration, is not interpolated. From this analysis, f-2 in Figure 17 (i.e., D f The red-shifted position of the Y dislocations (peak) supports the observation that they are present throughout the anthracite network, including sample A1.

[0255] The degree of D-band interpolation is determined by the sp 3 sp, not the proportion of states 3 Fraction of RBM phonons activated by the state vs. sp 2 is the fraction of RBM phonons activated by edge states. 3 Even in the state, sp 2 A small number of edge states can activate a large proportion of RBM phonons, which may result in the D band being interpolated, resulting in sp 3 There are more states, and sp 2 With fewer edge states, one can expect a greater degree of interpolation. x Ring is sp 2 From the edge state to sp2 Internal state or sp 3 Because they are formed by transformation into states, the prevalence of each of these two states is negatively correlated.

[0256] Therefore, interpolating the D band of sample A1 is sp 2 sp whose edge states are related to diamond-shaped seams 3 This can be seen as evidence that the state has been transformed. 2 sp whose edge states are related to diamond-shaped seams 3 The transformation of the tensile strength to the tensile strength state suggests a structural mechanism behind the seam formation, and this causal relationship will be further explored in relation to sample A3 and the samples from experiment B.

[0257] Other than the f-2 peak position, sp 3 Another possibility for the existence of the state is D u The shoulder associated with the peak at 1100 cm in Figure 13 is characteristic. -1 and 1200cm -1 This shoulder, which appears between 1185 cm and 1185 cm, is fitted by the broad f-1 peak in Figure 16. -1 Centered on 1150cm -1 and 1200cm -1 The broad peak between 2 -sp 3 This feature has been assigned to a bond and is therefore consistent with a transition occurring at the diamond-shaped seam. To demonstrate that this feature is not related to trans-PA, sample A1 was annealed at 1050 °C for 30 min. For comparison, the fitted Raman spectrum of the annealed sample is shown in Figure 17. The shoulder feature has a decrease in intensity and appears at 1185 cm. -1 From 1180cm -1 The peak area of ​​the f-1 peak (the ratio of its area to the sum of the areas of the four fitted peaks) is slightly shifted to 0.16 but not eliminated. This indicates that it is not trans-PA. However, the area ratio of the f-1 peak (the ratio of its area to the sum of the areas of the four fitted peaks) is reduced from 0.16 to 0.11 by annealing. This reduction is due to the sp 2 -sp 3 Showing reduced binding, possibly sp3 Therefore, the f-1 peak may also be evidence of the diamond-shaped seam in sample A1.

[0258] A review of the anthracite literature reveals that the D band in the optical Raman spectra of some grades of natural anthracite is red-shifted—the unfitted D peak is at 1340 cm -1 D bands can sometimes be found at lower levels, whereas in other less mature or more mature grades, the D bands appear to be uninterpolated. This can be inferred from the fact that in the less mature grades, the diamond-shaped seams have not yet formed geologically. In more mature grades (e.g., meta-anthracite), the diamond-shaped seams form and then destabilize, resulting in sp 3 It can be inferred that the condition has been eliminated and the screw dislocation has progressed.

[0259] To our knowledge, the basis for the occasional redshift of the D peak has not been investigated, nor has it been assigned to a diamond-shaped seam. Du / I Gu The ratio tends to be below 1.0, as in sample A1. -1 and 1605cm- -1 The blue-shifted G peak located between 1500 cm -1 From 1550cm -1 , which is consistent with the red-shifted mode of the G peak. Furthermore, some grades of anthracite exhibit a broad underlying peak that can be fitted between 1100 cm -1 From 1200cm -1 The spectrum of sample A1, together with its HRTEM rim pattern, is therefore consistent with a synthetic anthracite network.

[0260] Further characterization of the anthracite network of sample A1 was performed using XRD analysis. XRD analysis was performed on a sample synthesized from magnesium carbonate raw powder using a procedure similar to procedure A1. This raw powder was calcined to obtain MgO powder with template particles indistinguishable from those of sample A1. Therefore, the XRD results of this carbon were analyzed to understand the crystalline structure of an anthracite network like sample A1. Figure 18 shows the overall XRD profile. Table 2 below contains values ​​for the XRD peak angle, d-spacing, area, area fraction (normalized to the area of ​​the main peak at 2θ = 25.044°), and full width at half maximum (not corrected for instrument broadening). [Table 2]

[0261] Three peaks were fitted across a range of interlayer spacings. The three fitted peaks are referred to as Peaks I, II, and III and are displayed in Figure 18. Figure 18 also includes reference lines indicating the 2θ values ​​associated with the refractive index of graphite. For sample A1, the largest fitted peak, as measured by the area under the peak, is Peak II. Peak II achieves its maximum height at 2θ = 25.044°, corresponding to a d-spacing of 3.55 Å. The area under Peak II is set to 100% for comparison with the other peak areas. The FWHM value of Peak II is 5.237°, indicating a relatively wide range of interlayer spacings. The d-spacing and FWHM values ​​of Peak II indicate a more diverse and larger interlayer spacing within sample A1 than that of graphitic carbon.

[0262] Peak I has a maximum height at 2θ = 20.995°, corresponding to a d-spacing of 4.23 Å. Like Peak II, Peak I is broad with a FWHM value of 4.865°. The area under Peak I is 32% of the area under Peak II, indicating a significant phase in the interlayer spacing. The d-spacing of 4.23 Å ​​is too large to be associated with the interlayer phase of graphitic carbon. This peak may reflect the presence of z-neighboring curved graphite domains, where the curvature is not a phase. The out-of-phase z-deflection disrupts the uniformity of the interlayer spacing and expands the space between the curved domains. This curvature is consistent with an anthracite network.

[0263] Peak III also indicates the presence of a phase with a small interlayer spacing. It has a maximum height at 2θ=30.401°, corresponding to a d-spacing of 2.93 Å, and the interlayer spacing represented by peak III is smaller than that of any interlayer phase in graphitic carbon. Peak III is as broad as peaks I and II, with a FWHM value of 8.304°. The area under peak III is 80% of the area under peak II, indicating that the interlayer spacings are approximately equivalent. In graphitic carbon, no d-spacings are observed in the 2.93 Å range, and <002> The d-spacing value of is 3.36 Å, which is the same as that of graphite. <100> There is no d-spacing larger than the d-spacing value of 2.13 Å. When glassy carbon is heated and compressed, sp 2 Area distortion, sp 2 From sp 3 rehybridization to sp with interlayer spacing between 2.8 Å and 3 Å 2 / sp 3 The peak III of sample A1, which has a d-spacing of 2.93 Å, coincides with this, and the sp 3 This further confirms that the condition exists.

[0264] This corresponds to the blue-shifted mode of the G peak of sample A1, and its XRD profile is <100> This reflects compression. In the intralayer peak region, <100> The fitted peak has a maximum height of 2θ=30.401°, corresponding to a d-spacing of 2.09 Å. This peak is broad and <100> This indicates a wide range of d-spacing values. <100> The d-spacing of 2.09 Å in , compared with the d-spacing of 2.13 Å in graphite, indicates a compressive strain of approximately 2% in the xy plane.

[0265] The thermal oxidation profile of sample A1 is shown in Figure 19. It plots the derivative of the sample's mass loss versus temperature. The onset of thermal oxidation for sample A1 occurs between 450 and 500 °C, higher than for sample A3 and similar to that for sample A2. This indicates that sample A1 contains a non-negligible amount of unstable mass compared to carbon oxides such as graphene oxide. The peak mass loss temperature is approximately 608 °C, lower than for sample A2 but higher than for sample A3. Overall, these results are consistent with the temperatures at which CVD was performed. High-temperature pyrolysis processes typically result in carbon formation at higher onset temperatures of thermal oxidation and peak mass loss due to increased crystallinity. The only exception to this trend is the earlier onset of thermal oxidation for sample A2, which may be due to the slight presence of soot observed in certain regions of the sample. This soot-like phase is incompatible with the substrate and is presumed to have formed via gas-phase pyrolysis in free space due to the high-temperature pyrolysis of procedure A2. The remainder of sample A2 had greater thermo-oxidative stability than the other samples and exhibited the highest peak temperature of mass loss among all three samples.

[0266] Figure 20 shows an SEM image of sample A2. Analysis of the image confirmed the presence of carbon particles that appear to be fragmented exosporium mineral frameworks. Similar to sample A1, the templated morphology of the framework is evident, with the exosporium mineral walls appearing to encapsulate and replicate the templated surface. However, unlike sample A1, the framework is often fractured and deformed. This loss of original morphology clearly indicates that the exosporium mineral walls were no longer able to withstand the mechanical stresses encountered during liquid-phase template extraction and drying. This fracture, in light of the mild extraction procedure involving gentle agitation and subsequent drying, suggests that the exosporium mineral framework does not contain an intact anthracite network but instead contains vdW aggregates that are easily fractured and deformed by shear fracture.

[0267] TEM analysis of sample A2 confirms the deformed and fragmented framework seen in the SEM images. Figure 21A shows a TEM image that reveals the extent of damage that occurred during template extraction. It is very different in appearance compared to the nearly intact, undeformed particles observed in sample A1 (as shown in Figure 10A). Figure 21B reveals that the encrusted mineral walls are comparable in thickness to the walls of sample A1. The BET specific surface area of ​​sample A2 is 127 m 2 g -1 It was measured at 142 2 g -1 ), suggesting that the average wall thickness of sample A2 is between 20 and 21 layers—slightly thicker than sample A1. The BJH specific porosity of sample A2 is 0.37 cm 3 g -1 and sample A1 (0.35 cm 3 g -1 ), but it should again be noted that this measurement underestimates the contribution of larger macropores.

[0268] In Figure 21C, edge lines associated with layered structures can be observed. Despite the long-range curvature of the exclusivity mineral walls, both the dark and light edge lines are generally straight. This indicates a reduction in ring disorder and Gaussian curvature in these graphene regions compared to the regions observed in sample A1. As shown by the red trace in Figure 21C, the edge lines are substantially parallel, and therefore the layers can be described as nematically aligned. Several possible examples of edge patterns associated with bridging dislocations can be identified, but these are significantly less common than in sample A1. While occasional bridging dislocations are present in these exclusivity minerals, they are insufficient to form an anthracite network.

[0269] More detailed information about the bonding structure of sample A2 can be obtained from its Raman spectrum. Figure 22 shows a single-point Raman spectrum taken with a 532 nm laser at 2 mW power. No smoothing was performed. The three main features of the profile are the peaks at approximately 1349 cm -1 D u Peak: approx. 1587cm -1 G u Peak and approximately 2700 cm -1 2D u It's the peak.

[0270] Compared with sample A1, sample A2 had a Tr u The feature intensity becomes very low, and I Tru / I Gu The ratio is less than 0.15, which is consistent with the small contribution from the redshifted modes underlying the G peak and the absence of tensile strain due to ring disorder. The absence of ring disorder and associated stretching is in good agreement with the observation of the small Gaussian curvature of C in Figure 21. Furthermore, the 1587 cm -1 G in u The peaks are in their natural positions, indicating that the compressed region present in sample A1 is not present. u The prominent peak indicates that sample A2 exhibits a turbostratic stacking arrangement of hexagonal tiling layers.

[0271] Average D of sample A1u Compared to the peak, the average D of sample A2 u The peaks show high intensity and the average I Du / I Gu The ratio is greater than 1.0. This means that the 2D u Appearance of peaks (average I 2Du / I Gu The D-band intensity, together with the D-band ratio of 0.265, reflects increased crystalline ordering in sample A2 compared to sample A1. While an increase in D-band intensity in the spectrum of crystalline carbon corresponds to a decrease in crystallinity (e.g., amorphization of graphite to nanocrystalline graphite), sample A1 is nanocrystalline, so its high D-band intensity indicates increased crystalline ordering compared to sample A2.

[0272] G u The peak is at about 1620 cm -1 This is because there are shoulders at 1620cm. -1 The sp of sample A2 is attributed to the underlying D' peak at 2 This is evident due to the high density of edge states. -1 Narrow D centered on u The peak is sp 2 This D band is not a good candidate for any low-frequency sp 3 The bands also appear to be poorly interpolated, with most RBM phonons being sp 3 Not state, sp 2 This indicates that the electrons are activated by the edge states. * The peaks are either absent or negligible.

[0273] Table 3 below contains the XRD peak angles, d-spacings, areas, area fractions (normalized to the area under the major peak at 2θ = 25.8319°), and FWHM values ​​(not corrected for instrument broadening) for a sample synthesized using a procedure similar to Procedure A2, but from magnesium carbonate raw powder. Calcination of this powder yielded an MgO powder with template particles indistinguishable from those of Sample A2. Therefore, the XRD results for this carbon were analyzed to understand the crystal structure of aggregates like Sample A2. [Table 3]

[0274] Three peaks were fitted in the range of the interlayer periodicity. The three fits are referred to as Peaks I, II, and III, with the ascending numbers corresponding to the ascending 2θ values ​​at which the peaks achieve their maximum intensity values. The largest fitted peak, as measured by the area under the peak, was Peak II, which had a maximum height at 2θ = 25.8319° and a corresponding d-spacing of 3.45 Å. The area under Peak II was set to a value of 100%. The d-spacing value of Peak II is consistent with that of turbostratic graphitic carbon. <002> Consistent with the d-spacing, the peak is significantly sharper than peak II of sample A1.

[0275] The maximum height of Peak I is 2θ = 22.9703°, corresponding to a d-spacing of 3.87 Å - a reduction from the corresponding d-spacing of 4.23 Å ​​for Peak I in sample A1. The area under Peak I is only 13% of the area under Peak II, making it a significant but minor phase. On the other hand, the Peak I phase in sample A1 was 32% of the area of ​​Peak II. The presence of Peak I may reflect larger z-spacings of edge dislocations or the presence of non-hexagonal rings, which are reduced but not eliminated. Large irregular <002> The reduced presence of d-spacing is again consistent with the appearance of more aligned and planar edge lines in sample A2, as shown in FIG. 21C.

[0276] Peak III indicates the slight presence of a contracted interlayer spacing phase. With a maximum height at 2θ = 31.2063°, corresponding to a d-spacing of 2.86 Å, the interlayer spacing represented by Peak III is significantly smaller than any interlayer spacing in graphitic carbon. Peak III is also exceptionally broad, with a FWHM value of 10.33°. The area under Peak III is only 5.1% of the area under Peak II, making it a significantly less significant phase. This is consistent with the low abundance of Y dislocations observed in sample A2.

[0277] Finally, the intralayer periodicity at 2θ=42.6906° is <100> This corresponds to a d-spacing of 2.12 Å, which is close to the d-spacing of 2.13 Å in graphite. -1 G u The natural position of the peaks confirms the absence of compressive strain, which may indicate that compressive strain has some relation to the formation of bridging dislocations and the xy spacing where they occur.

[0278] The thermal oxidation profile of sample A2 is shown in Figure 19. It plots the derivative of the sample's mass loss versus temperature. The onset of thermal oxidation for sample A2 is between 450°C and 500°C, higher than for sample A3 and similar to that for sample A1. The peak mass loss temperature of sample A2 at 650°C is higher than for samples A1 and A3, reflecting the improved stability of the nanocrystalline graphite structure. The wider temperature range over which sample A2 is thermally oxidized corresponds to the presence of easily oxidizable soot and is due to the earlier onset of thermal oxidation.

[0279] Further practical demonstration of the degraded mechanical properties of sample A2 relative to sample A1 was obtained by uniaxial compression tests, in which powders from sample A1 and sample A2 were each uniaxially compressed at the same pressure. After compression, sample A1 maintained its powder shape, suggesting insufficient compression, while the powder from sample A2 was compressed into a solid, single pellet.

[0280] To better understand the powder under compression, SEM was performed. Figure 23 shows an SEM image of the exosporium framework of sample A1 after compression. It can be seen that the framework retains its porous morphology. While fracture of the exosporium walls is observed in many particles, other exosporium walls exhibit linear features not present before compression. These linear features are shown in Figure 23 and magnified in the inset. In this image, the exosporium walls are observed to have distorted inward, resulting in internal creases and linear surface features. Many of the compressed particles in sample A1 exhibit localized distortion, indicating that the exosporium walls were able to locally flex. The porous morphology of the framework indicates that the walls can withstand inelastic shear yielding, store elastic potential energy, and rebound upon release of uniaxial compression. This elasticity, provided by the anthracite network within the walls, prevents the framework from irreversibly compressing into a paper-like pellet.

[0281] In contrast, Figure 24 shows an SEM image of the exoskeleton mineral framework of sample A2 after compression. The porous morphology of the framework of sample A2 is destroyed. The resulting paper-like aggregate of the sheet is consistent with the observation that these frameworks undergo plastic deformation and become more prone to fragmentation during liquid-phase processing and drying. During compression, the layers within the exoskeleton mineral walls are able to shear due to the absence of an anthracite network. The framework loses its porosity and compresses into a layered structure, forming a pellet, but lacking stored elastic potential energy, it is unable to rebound upon release of uniaxial compression. Therefore, the absence of an anthracite network in the walls prevents the exoskeleton mineral framework of sample A1 from rebounding.

[0282] Figure 25A is an SEM image of sample A3. The exosporium mineral framework of sample A3, like the particles of sample A1, is not significantly deformed and retains its original pore and wall morphology. This morphology reflects a template containing a partially sintered powder of bonded polyhedral MgO crystals, as shown in Figure 26. The bonded subunits of the exosporium mineral framework possess large, flat facets and appear more polyhedral than those of sample A1. In the SEM micrograph of Figure 25A, it is unclear where the individual frameworks begin and end, or how many different frameworks are present in this image.

[0283] In contrast to the exoskeleton walls of samples A1 and A2, which exhibited a consistent appearance, the walls of sample A3 contain transparent and opaque regions. The transparent regions are found within the flat facets of the framework and at first glance appear as holes in the exoskeleton walls. Figure 25B shows a close-up of the polyhedral exoskeleton present in Figure 25A. Two transparent regions ("windows") are circled and shaded yellow. The windows, as shown in Figure 25B, are located in the central region of the flat facet and are surrounded by narrow, more electron-opaque strips running around the periphery of the facet. These strips, as shown in Figure 25B, give the window a framed appearance and are referred to herein as "framing." The framing on the facets is typically along the edges of the facets, although occasionally, more electron-opaque tendrils extending inward can be observed.

[0284] As shown by the yellow arrow in Figure 25C, the framing around the window generally faces across the window toward the framing on the opposite side, so that the framing is in intimate contact with the transparent surface. In the facet shown in Figure 25C, and many other readily identifiable examples, the gentle inward curvature of the framing (i.e., toward the interior of the hole) can be extrapolated to span a slightly concave transparent surface. This slight concavity is indicated by the curvature of the yellow arrow. This is the first indication that the window is not a physical hole in the encasing mineral wall.

[0285] If there were no transparent surface to guide the framing, the mechanical stresses of template removal and drying would be expected to cause it to bend, wear, or twist irregularly. However, if the framing were supported, like connective tissue, by transparent regions of the wall extending across the facets, such irregularities would not be expected. Rather, it would exhibit the shape of a transparent surface, and slight depressions would be expected as the receding water was pulled inward as the framework evaporated and dried. In fact, this was the appearance of all the framing. SEM analysis concluded that the windows observed in sample A3 were not holes but rather electron-transparent phases in the wall.

[0286] A phase change of carbon from the edge of a flat facet to its center has been observed by previous researchers. CVD growth of exo-mineral frameworks on NaCl cubes revealed distinct wall phases at the edges and corners of the NaCl facets (nucleation occurred in these regions due to localized melting of NaCl). Based on Raman analysis, these regions contained multilayer vdW aggregates of small graphene domains. In the central region of each facet—i.e., areas of reduced melting and nucleation—a second phase of large, more crystalline domains was observed within the exo-mineral walls. These exo-mineral walls broke down during template decomposition and drying, creating platelet-like fragments. This framework transformation contrasts with the intact exo-mineral framework of sample A3, where no platelet-like fragments were observed in the dried carbon powder. The observation that the windows in sample A3 did not separate into independent platelet-like particles strongly indicates that the walls of sample A3 contain an anthracite network rather than vdW aggregates.

[0287] Figure 27A is an HRTEM image of sample A3 showing its overall microstructure. The macropore subunits of the exosporous mineral framework shown in Figure 27A are cubic, and yellow dotted lines are used to help visualize their cubic shape. The more electron-transparent windows on the flat facets of the subunits are outlined in Figure 27A by solid yellow lines. Upon template displacement, sintering of the MgO template crystals imparts the pore passages observed between the subunits.

[0288] The mineral wall of sample A3 is slightly thinner than the walls of samples A1 and A2. 2 g -1 The BET measurement shows that the average wall thickness is about 8 layers (2630 m 2 g -1 / 328m 2 g -1 = 8.0). Cross sections of the encrusting mineral walls reveal that they are of fairly uniform thickness and show no discontinuities, even in the central regions of the flat facets. This is shown in Figure 27C, where cross sections of the pore walls across several flat facets (indicated by the yellow dotted rectangles) are uniformly thick and discontinuous. This is confirmed by observing many different facets from various angles, and is another indication that the fenestrae are not holes, but simply transparent areas of the encrusting mineral walls.

[0289] Similar to sample A1, sample A3 exhibits numerous Y dislocations. A typical rim pattern associated with Y dislocations, depicted from sample A3, is shown in the enlarged inset of Figure 27B. The ubiquitous presence of Y dislocations also indicates that the anthracite network contributes to the robustness of the A3 sample framework. Furthermore, the layers within the walls of sample A3 exhibit nematic ordering, similar to the layers in the walls of sample A1. However, the distinct rim lines of sample A3 are more difficult to visually trace for any distance greater than 1-2 nm, suggesting a more cross-linked anthracite network.

[0290] These observations are supported by the Raman spectrum of sample A3. Figure 28 shows a single-point Raman spectrum taken with a 532 nm laser at 2 mW power. No smoothing was performed. For reference, the full spectrum is shown in the inset of Figure 28. The overall Raman profile of sample A3 appears similar to that of sample A1 and anthracite. 2D u No peaks present. D u The center of the peak is about 1340 cm -1 , reflecting an interpolation of the D band from that observed in sample A1 (D u Peak is 1345-1350cm -1 The reason for this increase in D-band interpolation is that 2 For edge states, sp 3 This reflects the fact that more RBM phonons are activated by the 1150 cm state. -1 and 1200cm -1 There is a shoulder between the x The underlying D coincides with the transition occurring at the diamond-shaped seam. * This shoulder is shown in Figure 28.

[0291] Also, like sample A1, sample A3 exhibits a relatively sharp blue-shifted G u The peak is shown (in Figure 28, 1585 cm -1 The normal G peak position is indicated by the dotted line. This blue-shifted mode indicates compressive strain. Compared to sample A1, sample A2 has a slightly lower valley (I Tru / I Gu peak = 0.40), but the valley is still high enough to indicate the presence of an underlying broad peak, which is again inferred to be a redshifted mode in the G band associated with the presence of ring disordered regions.

[0292] I Du / I Gu The peak intensity ratio is about 0.77, and sample A3 has a D u This indicates that the peak intensity is low. uThe decreasing trend of peak intensity (A2>A1>A3) is positively correlated with the CVD temperature (1050°C>750°C>650°C), and the D-band interpolation (i.e., sp 3 This shows a positive correlation with the increase in RBM phonons activated by carbon. u The decrease in peak intensity is due to the sp 2 This is because the ring structure is gradually lost. In the case of sample A3, sp 2 Ring is sp x This occurs because the diamond-shaped seams are replaced by rings. The D-band intensity decreases with increasing density of diamond-shaped seams. This is therefore consistent with the appearance of a cross-linked anthracite network in the HRTEM image of sample A3.

[0293] From the characterization of samples A1, A2, and A3, we can infer the structural pathway by which diamond-shaped seams form during growth. This discussion begins with the observation that window regions of the enveloping mineral walls are electron-transparent, whereas the surrounding framing and curved regions of the enveloping mineral walls are electron-opaque. We then link this to an analysis of the nucleation and growth of primordial domains on the template surface. Finally, we model the structural encounters between these primordial domains and show how, under appropriate circumstances, diamond-shaped seams can evolve from these encounters.

[0294] As shown in Figure 25, the heterogeneity in electron transparency for sample A3 is due to different charging behavior in different regions of the exoskeleton mineral wall. When imaged, more electrically insulating regions of the exoskeleton mineral wall generate more charging. This charging behavior is clearly linked to the template surface topography. More conductive windows are associated with atomically flat template surfaces, such as the facets displayed in Figure 26, where nucleation of primordial domains was minimal or nonexistent. The less conductive framing and rounded regions of the exoskeleton mineral wall are associated with more defective regions of the templated surface, where nucleation of primordial domains was relatively dense.

[0295] Next, D of sample A3 uBased on the peak interpolation, a significant portion of the RBM phonons in sample A3 can be associated with diamond-shaped seams throughout the anthracite network. 3 The diamond-shaped seams are dense and therefore sp 3 In the region of the wall where the density of states is higher, we expect the conduction to increase due to the discontinuity of the π cloud where conduction occurs. 3 We expect that charging will be less prevalent in regions of the wall where the density of states is lower. Taking these observations together, regions of the enveloping mineral wall with higher nucleation density appear to be more prevalent, which is due to the sp associated with the diamond-shaped seam. 3 This is thought to be due to the high density of states. 3 The high density of diamond-shaped seams and nuclei is believed to be due to grafting occurring at the structural interfaces of primordial domains growing on a common substrate surface. Dense and localized nucleation leads to proliferation of primordial domains, increasing structural interactions and resulting in more grafting, resulting in sp 3 The texture and diamond shaped seams become more prevalent.

[0296] Next, we analyze the structural encounters between these primordial domains. The ring disorder has a non-zero Gaussian curvature, and its edges have undulating shapes determined by the local lattice curvature. The ring disorder of the primordial domains grown via pyrolysis at temperatures below 900 °C is similar to that of single-crystal MgO. <100> Wafers and single crystal germanium <100> This has been demonstrated by several examples in the prior art, including the growth of ring-disordered domains on wafers. When two such primordial domains grow on a common substrate surface, a structural encounter can occur between their edges. Because the local lattice curvature and undulating edges of the domains are not in phase, this structural encounter forms a stochastic, incoherent structural interface between nearby edge segments. Adding to this complexity, the edges of the primordial domains can be conceptualized as a constantly self-rearranging fluid of free radicals. The incoherence of the interface, where the edge atoms of one primordial domain are above, below, or horizontally mismatched with the edge atoms of the other domain, can be expressed as simple subduction or sp 2 This prevents deformation due to grafting.

[0297] In Figures 29 to 36, the sp 2 and sp 3 Grafting leads to local charging in the enveloping mineral regions associated with dense structural activity, as observed in sample A3. 3The diagrams show step-by-step how the state and diamond-shaped seam are derived. Referring to the molecular models shown in these figures, and all others that follow throughout the remainder of this disclosure, a few comments are in order. First, while these systems must be represented statically, our molecular models should be understood as static representations of dynamic, self-rearranging structures. Second, all of these figures, created using molecular models constructed using Avogadro 1.2.0 software, should be considered to represent only rough geometric approximations of the actual systems. They are intended to provide useful visual illustrations of the phenomena described herein. Third, while a substrate is not shown, the pyrolytic growth process of primary interest in this disclosure is specified by the substrate, and the absence of a substrate in a system does not imply its absence. Fourth, because our primary focus is on the evolution of the graphene structure, these figures do not depict hydrogen atoms. This is because, by definition, hydrogen is excluded. However, we understand that theoretical understanding indicates that, in fact, the hydrogenation and dehydrogenation of these graphene structures occurs dynamically during the formation of pyrolytic carbon. Fifth, multiple perspective views are provided to facilitate visual inspection and understanding of these systems in three dimensions. Sixth, for illustrative purposes, the continuum of the systems under consideration is depicted, but the continuum as depicted is not meant to be strict or universal. Seventh, we wish to show that diamond-shaped seams, chiral columns, and screw dislocations are the catalysts for sp-transfer across structural interfaces. 2 Graphing and sp 3 Here's how it all derives from grafting. We'll try to model how this happens using as simple a model as possible to convey the basic concepts.

[0298] The diagram in Figure 29 shows an incoherent structural interface. The interface is formed by a structural encounter between two edge segments (E1 and E2), each of which belongs to a different ring-disordered graphene structure (G1 and G2, respectively). These edge segments and graphene structures are displayed in Figure 29. The structural interface between them is described as the E1-E2 interface. G1 and G2 can be considered as primordial domains nucleated on a common substrate surface.

[0299] The E1-E2 structural interface in Figure 29 includes a zigzag-zigzag interface—i.e., an interface in which the participating edge segments are both zigzag-oriented. This configuration can arise when the growing graphene structure undergoes self-rearrangement, similar to the growth of free-radical condensates. From the H2 perspective in Figure 29, we can see that the primordial domain regions G1 and G2 are both curved. Thus, their edges have an undulating shape. The incoherence of the edge z-displacements at the structural interface results in three interface zones—two offset zones, labeled "Offset Zone I" and "Offset Zone II," located on either side of the E1-E2 structural interface, and a horizontal zone between them. These structural zones are labeled in Figure 29.

[0300] The vertical offset within the offset zone allows the opposite edge atoms to have sp 2 -sp 2 In the offset zone, under the appropriate pyrolysis conditions, the edge atoms are sp 2 From sp 3 Rehybridization to sp 3 -sp 3 The bond line can be formed, and the grafting of the original domain is end-to-end. 3 The formation of the state is referred to herein as "sp 3 This is referred to as "grafting."

[0301] In the horizontal zone, the vertical offset between the two ends is small enough that the opposing sp 2 Edge atom 2p z The orbitals are sufficiently aligned that π bonds can form between the edge atoms. In these zones, under appropriate pyrolysis conditions, the edge atoms are sp 2 -sp 2 This is similar to the sp 2 bond observed between ring-ordered domains in the prior art. 2 Similar to grafting, but with sp at a non-interfering interface. 2 Except that the grafting is localized in the horizontal zone.

[0302] In Figure 30, the opposing sp 2 The minimum vertical offset between atomic members and their 2p z sp in the horizontal zone, assuming sufficient alignment of orbitals 2 The system was modified by grafting. The two sp 2 -sp 2 The line of bond forms a new six-membered ring connecting the primitive domains E1 and E2, thereby coalescing into a new graphene structure designated G3. The new graphene structure G3 is shown in vertical perspective in Figure 30. As shown in Figure 30, the new sp 2 The formation of the ring induces some alignment distortions of the resulting G3 domains. It is noteworthy that in some cases the grafting event may distort the original interface, dynamically stretching and contracting the interfacial zone.

[0303] In the illustration of FIG. 31, the graphene structure G3 shown in FIG. 30 is composed of sp 3 Structurally modified by grafting, which assumes a substantially perpendicular offset between the edge atoms in these zones, due to the sp 2 From sp 3 rehybridization to two different sp. 3 -sp 3 Organized in a join line, with 5 sp 3-sp 3 The formation of bonds (highlighted in red in Figure 31) is involved. From a vertical perspective, five sp 3 -sp 3 The bond formation leads to the formation of five new sp x It can be seen that a ring is formed. From the H1 perspective, two sp 3 -sp 3 It can be seen that the coupling lines (coupling line I corresponding to offset zone I and coupling line II corresponding to offset zone II) point in opposite directions.

[0304] sp 2 Grafting and sp 3 The six rings formed via grafting are displayed in Figure 31. The six-membered sp 2 On each side of the ring (designated R3), there is a six-membered sp x Ring (R 2-C and R 4-C R 2-C and R 4-C In both cases, the six-membered sp x The ring contains a chiral chain. The chiral chain is sp x 4 sp of the ring 2 containing atoms and two sp 3 These sp 3 The part is sp 3 -sp 3 The R bond connects them together to close the ring. This is shown in the H2 perspective view of Figure 31, where R 2-C The chiral chains are highlighted by blue arrows, and the direction of the blue arrows corresponds to the direction of increasing height in the z direction. 2 The atoms are black circles, and the sp 3 The atoms are represented by black and white circles. These two terminal sp 2 sp between atoms 3 -sp 3 The bond is highlighted in red. These two sp x The ring represents a chiral ring, and in Figure 31, R 2-C and R 4-CIt is written as follows.

[0305] The chiral shape imparted by the chiral chain results in sp x Ring R 2-C and R 4-C represents a chiral ring. Both of these chiral rings in Figure 31 form at the transition between a horizontal zone and a laterally adjacent offset zone. It is this structural zone transition and the associated change in edge height that creates the chiral chain. As a result, chiral rings form at interfacial zone transitions, and their chirality is determined by the zone transition at which they form.

[0306] In Figure 31, the remaining three sp x The rings (R1, R5, and R6) are in chair conformations. As shown in the H1 perspective view of Figure 31, they show two different directions. Each direction represents a point symmetry of the other direction in the xy plane. These directions are predetermined based on the shape of the offset zones in which R1, R5, and R6 are formed. R1 was formed by grafting across offset zone I, where E2 is higher than E1. Therefore, R1 is elevated where E2 would have been. On the other hand, R5 and R6 were formed by grafting across offset zone II, where E1 is higher than E2. Therefore, R5 and R6 are elevated where E1 would have been. This reversal of edge heights is due to the shape of these sp x The direction of the point symmetry of the ring (and the two sp 3 -sp 3 This is the reason why the bonding lines are in the opposite direction.

[0307] Furthermore, the chiral ring R formed at the zone transition on both sides of the horizontal zone is formed by the inversion of the edge height between the two offset zones. 2-C and R 4-C If the edge heights are not reversed between offset zone I and offset zone II, R 2-C and R 4-C would have had the opposite chirality. This alternative scenario is shown in Frame II of Figure 60.

[0308] SP in offset zone 3 With grafting, the sp in Figure 31 3 The atom is only tricoordinated, representing a tertiary radical. 3 -sp 3 Related to the bond are five sp radicals representing higher tertiary radicals. 3 These higher order tertiary radicals are shown as circles in the H1 perspective and as black and white circles in the H2 perspective in Figure 31. Each of these five higher order radicals has an unpaired electron extending upward into z-space.

[0309] The graphene structure G3 shown in Figure 31 represents the "base" - i.e., the underlying layer formed by grafting of the primordial domain during pyrolytic growth. After grafting, the base can exhibit tertiary radical sites extending in z-space as shown in Figure 31. By forming the base, the sp 2 The edge states are removed. In the region of the base corresponding to the offset zone, the sp 2 Edge atom is sp 3 In the region of the base corresponding to the horizontal zone, sp 2 Edge atom is sp 2 These substitutions change the Raman spectrum of the base—specifically, the sp 2 The edge atoms become fewer and sp 3 There will be more conditions.

[0310] In Figure 32, radical addition reactions occur with five higher tertiary radicals of the base G3, resulting in five z-adjacent sp 3 In Figure 32, five z-adjacent sp 3 The atoms are represented by black and white circles. By adding these, a second layer of sp 3 -sp 3 Bond lines (i.e., bond lines I and II) are created. These new sp 3 -sp 3The bond is highlighted in red in Figure 32.

[0311] In Figure 33, the radical addition reaction on the base was continued, resulting in nine sp 3 atoms (shown as nine black and white circles in the perspective view of V and H2 in Figure 33) and three sp 2 atoms (shown as three filled circles in the perspective view of V and H2 in Figure 33). The addition of these atoms results in the formation of the second layer of sp 3 -sp 3 The third layer of sp on the bond line 3 -sp 3 A bond line (highlighted in red in the perspective view of V and H2 in Figure 33) is formed, where sp 3 -sp 3 Note that the orientation of each successive layer of bond lines is a point mirror image of the orientation of the layer above or below.

[0312] Addition reaction gives three sp x Three additional six-membered sp rings located adjacent to the rings R1, R5, and R6, respectively x A new sp ring (labeled R7, R8, and R9 in Figure 33) is also formed. x Each ring has a sp in the base below it. x Since they share one or more atomic members, these sp x Each ring has the sp x The rings are adjacent to each other. These three sp x By adding rings vertically, a new extended graphene structure is created, which we can name G4.

[0313] The sp located below x Rings R1, R5 and R6 are sp x Rings R7, R8 and R9 are in chair conformation, and each has the sp x The orientation represents the point symmetry of the ring. x Rings R1 and R7 comprise the first diamond-shaped seam, and the other four sp xThe rings (R5, R6, R8, and R9) contain a second distinct diamond-shaped seam, and the two diamond-shaped seams (separated in the enlarged inset of the H1 perspective of Figure 33) form an initial Y transition oriented in opposite directions (as indicated by the gray shading in the enlarged inset of the H1 perspective). The diamond-shaped seam terminates internally in a chiral ring (or as a chiral column if the seam extends vertically). In the H2 perspective of Figure 33, the chiral ring R 2-C and R 4-C It can be seen that the diamond-shaped seam is located at the inner end of the diamond-shaped seam.

[0314] In Figure 34, the radical addition reaction on the base was continued, resulting in nine sp 3 atoms (shown as nine black and white circles in the perspective view of V and H2 in Figure 34) and 18 sp 2 atoms (shown as 22 filled circles in the perspective view of V and H2 in Figure 34) were added, while some primary carbon atoms in the previous step were replaced by three-coordinated sp 2 In this figure, the radical addition reaction continues, and the vertical sp 3 Growth and lateral sp 2 We are beginning to see that both growth and productivity are being promoted. 3 -sp 3 The fourth layer of sp 3 -sp 3 The bond lines are highlighted in red in the V and H2 perspective views of FIG.

[0315] The three sp in Figure 34 x Located directly above and adjacent to rings R7, R8, and R9 are R 10 , R 13 and R 14 Three new six-member sp x It is a chiral ring R 2-C Located at the top of 11-C This new chiral ring is labeled in the H2 perspective. The z-neighboring chiral ring R 2-C and R 11-CFor easier visual identification, the R is separated by an enlarged inset in the H2 perspective view. 2-C and R 11-C The atomic members of are denoted as 1, 2, 3, …, 6 and 7, 8, 9, …, 12, respectively, and sp 2 Members are in black numbers, sp 3 Members are shown as grey numbers. From this, R 2-C Similarly, R 11-C It can be seen that R2-c also contains chiral chains. The chiral chains of both rings are highlighted by blue arrows in the enlarged inset of the H2 perspective view in Figure 34, and the direction of the blue arrows corresponds to the increasing height in the z direction. The chiral chain of R2-c includes atoms 1 to 6, with atoms 1 and 6 being sp 3 -sp 3 sp connected to each other via bonds 3 Contains atoms. 11-C The chiral chain contains atoms 7 to 12, and atoms 7 and 12 are sp 3 -sp 3 sp connected to each other via bonds 3 Contains atoms.

[0316] The two z-adjacent chiral rings are sp 3 -sp 3 (Sp labeled 1, 6, 7 and 12 3 The chiral rings are connected through a z-chain of atoms (including the member atoms). 3 -sp 3 The z-directed chains of bonds contain chiral columns. Chiral columns, like chiral rings, are found at the inner ends of the diamond-shaped seams of the anthracite network. The basic structure of a chiral column is R 2-C -R 11-C This can be elucidated by comparing the enlarged inset of the H2 perspective view of Figure 34, in which the chiral column is isolated, with the view of the chiral column in Figure 37B. Within the chiral column, there are sp 2 and sp 3 A helical one-dimensional chain of atoms (i.e., "sp x There is a "spiral" in Figure 37. x The basic structure of the helix is ​​shown.

[0317] In Figure 35, continuing growth above the base produces 32 new sp. 2 atoms were added (shown as 32 filled circles in the V and H perspectives in Figure 35), while some primary carbon atoms in the previous step were replaced by three-coordinated sp 2 In this view, the ring above the base can be seen to have coalesced into a second-layer nucleus with zigzag edge segments that are substantially xy-aligned with the base and substantially parallel to the original structural interface. From this higher-layer nucleus, further sp 2 Growth can proceed laterally. Looking vertically at Figure 35, it can be seen that the second layer is slightly twisted relative to the first layer. This is called an Eshelby twist and is produced by chiral defects such as chiral columns.

[0318] The continuous growth reflected in Figure 35 results in the base layer chiral ring R 4-C On top of this, another chiral ring R 12-C As shown in the enlarged inset of the H2 perspective view in Figure 35, these two z-adjacent chiral rings are sp 3 -sp 3 A second chiral column (and a second sp x Form a spiral. Base layer ring R 2-C and R 4-C Since the chirality of the chiral chains is common, R 2-C and R 4-C The two chiral columns formed on top of this also share chirality. The shared chirality of these two chiral columns increases the angle of the Eshelby twist.

[0319] The multilayer graphene system shown in Figure 35 is classified herein as an anthracite network. x The entire anthracite network, laterally and vertically cross-linked by chiral columns constructed from rings, comprises a single ring-connected graphene structure, herein referred to as "sp x It is described as a "network." x As the network grows, sp3 You can begin to see the state growing continuously.

[0320] In Figure 36, by continuing to grow on the original G3 base, sp x A third layer is added to the network. In vertical view, the third layer exhibits the same Eshelby twist as the second layer. As the chiral column continues to propagate vertically, each higher layer that forms will be rotationally misaligned with the z-neighboring layer above or below it. In Figure 37A, a close-up of the H2 perspective view from Figure 37, it can be seen that each higher layer region continues the chiral column. In Figure 37A, the chiral chains within the chiral rings are highlighted in blue, and the sp 3 -sp 3 The z-direction chain of bonds is highlighted in red. A simplified representation of each chiral column of the z-adjacent chiral ring is shown in Figure 37B. In Figure 37C, the sp x The helix is ​​isolated.

[0321] In Figure 36, we can see that continuing growth above the original G3 base creates two distinct diamond-shaped seams. x One of these seams, comprising a two-dimensional ribbon of rings, is shown in bold in the enlarged inset of the H1 perspective view. x Other seams containing two-dimensional sheets of rings are highlighted in yellow in the other enlarged inset of Figure 36. Each of these seams contains two-dimensional cubic diamond surfaces running transverse to the layers. The seams represent the lateral and perpendicular ring-connecting interfaces between adjacent layers. x The diamond-shaped seams of the network are colored red (i.e., sp 3 -sp 3 In Figure 37A, both chiral columns from Figure 36 are shown, where sp 3 -sp 3The bonds are again highlighted in red, and the chiral chains are highlighted in blue. In Figure 37B, the chiral columns are illustrated, and in Figure 37C, the sp x The spiral is shown.

[0322] The sp shown in Figure 36 x The network represents a simplex graphene system. The only atoms that do not belong to a simplex are the five primary carbon atoms in z-space above the third layer. These atoms are not members of a ring and therefore cannot be members of a graphene structure or graphene system.

[0323] The pyrolytic growth sequence modeled in Figures 29-36 connects all the observations made in Experiment A. First, the non-uniform charging observed in the encrusting minerals of sample A3 (see Figures 25 and 27) is due to the presence of sp 3 This is attributed to the localization of grafting and the formation of diamond-shaped seams at structural interfaces. These interfaces are most dense in regions of intense nucleation, corresponding to rounded regions and regions close to defects on the template surface. On the other hand, in regions of the enveloping mineral wall formed on flatter template surfaces, sp 3 Second, the sp 2 and sp 3 Grafting is done on many sp 2 Since edge states are eliminated, as well as sp 3 Grafting is sp 2 Strong sp at the defect site activates RBM phonons throughout the ring 2 -sp 3 This leads to coupling, so sp 3 Grafting is sp 2 leading to the interpolation of the Raman D band. Finally, the grafted base is sp 3 Due to the inclusion of higher-order radicals in the grafted region, even if the template / substrate is inaccessible, the growth is not terminated and higher-order layers can easily nucleate. This is the case for multilayer sp x The resulting network exhibits superior mechanical robustness compared to the vdW aggregate.

[0324] In experiment A, we observed that the interpolation of the Raman D band increases with decreasing pyrolysis temperature. This is consistent with slower hydrogen release at lower temperatures, allowing more time for the dynamic self-rearrangement condensate at the interface to relax to an energy-minimizing configuration. 2 sp eliminating edge states 2 or sp 3 Grafting is accelerated at low temperatures.

[0325] In step A1, the CVD temperature is 750 °C, which allows for gentle dehydrogenation and carbonization of the condensate. Therefore, sp 2 and 3 Grafting is easy to occur, and sp 2 When the edge state disappears, 1345 cm -1 Above average D u Peak and 1343cm -1 Average D f As evidenced by the difference between the peaks, the fundamental interpolated modes begin to appear in the D band, which indicates that the exoskeleton mineral framework of sample A1 is composed of minimally grafted z-sp x It is classified as a network.

[0326] In step A2, the CVD temperature is 1050°C, which accelerates dehydrogenation and carbonization. High-energy edge dislocations are pinned and vdW aggregates are formed. RBM phonons are generated by these sp 2 The D band of sample A2 is activated by edge states and therefore not interpolated, which leads to the classification of the exoskeleton mineral framework of sample A1 as a vdW aggregate.

[0327] In step A3, the temperature is further lowered to 650 °C, and the grown condensate is rearranged to form sp 2 This allows more time for relaxation to the energy-minimum grafted conformation, eliminating the edge states. As a result, -1 D of sample A3 locatedu The peak is interpolated to the most D band in any of the samples in experiment A, at approximately 1350 cm -1 SP 2 Edge activation D band and 1332 cm -1 This indicates that the exoskeleton mineral framework of sample A3 is composed of partially grafted z-sp x It is classified as a network.

[0328] IX. Experiment B - Analysis The samples produced and evaluated in Experiment B contain an encrusted mineral framework synthesized by surface replication on mesoporous or macroporous MgO templates. These samples, like Samples A1 and A3, exhibit excellent mechanical properties and contain an anthracite network.

[0329] Figure 38A is an SEM image of the exoskeleton mineral composite material associated with step B1 prior to extraction of the MgO template. Here, the endoskeleton mineral template is still visible beneath the exoskeleton mineral framework. The template comprises equiaxed grains with a porous substructure of linked nanocrystalline subunits formed by thermal decomposition of the template precursor compound (magnesite, i.e., MgCO). Figure 38B is an SEM image of the exoskeleton mineral framework from sample B1, demonstrating both the absence of displaced template and that the framework retains its original templated morphology. The framework appearance shown in Figure 38B is representative of the framework appearance found in samples B2 and B3, both of which were fabricated with similar template particles.

[0330] Figure 38C shows an SEM image of the exoskeleton mineral framework from sample B4. Sample B4 was synthesized by surface replication on a different template than samples B1-B3. The template contains flat platelet-like particles with a porous substructure of connected nanocrystalline subunits obtained from the pyrolysis of a hydromagnesite template precursor. Thus, the exoskeleton mineral framework of sample B4 exhibits a "sheet-pore" morphology—similar to the frameworks of samples B1-B3 in terms of porous substructure, but not in terms of overall shape.

[0331] In experiment B, a lower pyrolysis temperature was explored to demonstrate the effect of slowing the dehydrogenation reaction of the free radical condensates, which was thought to potentially promote the ability of the condensates to relax into energy-minimizing grafting configurations at the structural interfaces. Based on experiment A, the gradual interpolation of the D bands revealed spectroscopically distinguishable sp 2 This was expected to lead to a reduction in edge states. The temperature setting of the CVD furnace was varied between 640°C and 540°C.

[0332] Table 4 below lists the samples, pyrolysis temperatures (i.e., the set temperatures of the CVD furnace), carbon source gases, and average I Du / I Gu and I Tru / I Gu Peak ratio, average Gu and D u Peak position and G u and D u The spacing between peaks is shown. [Table 4]

[0333] The average values ​​in Table 4 were obtained from the average spectrum representing a composite of nine point spectra. To calculate the average values, we first measured the raw data of each point spectrum by ±5 cm. -1 The spectra were smoothed using a moving average method at wavenumber intervals of 1000 to minimize noise. After smoothing, the intensity values ​​of each point spectrum were normalized to a common scale, and then the normalized intensity values ​​were averaged to create an average intensity value for each wavenumber.

[0334] A in FIG. 39 shows the average Raman spectra of samples B1 to B4. B in FIG. 39 shows the averaged D u ,Tr u and G u The black arrows in Figure 39B indicate the direction of the corresponding spectral trend when the CVD temperature is decreased in steps B1 to B3. u The enlarged view of the peak is shown in Figure 39. u FIG.

[0335] By evaluating the Raman spectra of samples B1 to B3, it was found that the thermal decomposition temperature decreased with increasing D u It was shown that the peak intensity (and peak area) tended to decrease. The FWHM of the peaks did not appear to change significantly. This tendency for the peak intensity and area to decrease is due to the sp 2 This means that the RBM phonons associated with the rings are reduced overall, which means that the sp 3 It is known that this occurs when the content of -sp 2 In diamond-shaped carbon, which does not have rings, the D feature disappears completely. Therefore, the D observed in experiment B u The decrease in peak intensity is due to sp 3 sp accompanying grafting 2 From sp 3 Rehybridization to sp x Varies between sp 2 This may be due to the gradual decrease in the presence of rings. As the pyrolysis temperature decreases, the condensate forms lower energy sp 3 Not only does it have more time to relax into the grafted configuration, but it also increases the ring disorder of the pristine domain, which favors the offset zone at the expense of the horizontal zone. Both of these are sp 3 Grafting and sp x This should increase the number of rings.

[0336] The evaluation of samples B1 to B3 also showed that when the CVD temperature was lowered in experiment B, u Peak and low frequency sp 3This shows that the bands are gradually interpolated. 2 This indicates that the prevalence of edge states is decreasing. As discussed in Experiment A, this is due to the 2 This demonstrates that the edges are increasingly excluded at the structural interface, consistent with the adoption of lower-energy grafting configurations. Interestingly, the interpolated trend observed for samples B1–B3 coincides with the cubic diamond-shaped peak position at 1332 cm. -1 It doesn't stop there, but continues to go down to even lower frequencies.

[0337] Surprisingly, as the temperature decreases and grafting progresses, sp 2 There also appears to be an overall reduction in the level of lattice distortion in the clusters. This is also evident from the trend in valley heights for samples B1-B3—a trend not seen in experiment A, where samples A1 and A3 were found to exhibit higher valleys despite being synthesized at lower temperatures than sample A2. This trend in experiment B is due to the presence of sp 3 The increasing prevalence of grafting has led to the formation of more distorted sp x This may be explained by compression caused by an increased prevalence of ring conformations.

[0338] In samples B1 to B3, the thermal decomposition temperature decreased and the G u The peak position is the usual 1585 cm -1 ~1596.6cm -1 Another trend was observed, which is a gradual blue shift up to sp 2 -sp 2 This indicates an overall increase in compressive strain of the bonds, which is also due to increased grafting. Furthermore, the G band narrows, indicating less dispersion in the strain state. Thus, experiment B confirms the correlation between grafting and compression observed in experiment A. This compression also helps explain the decrease in valley height. From Figure 39, it can be seen that the G u As the peak position of I Tru / I Gu The ratio is decreasing, and sp xIt can be seen that as the network compression progresses, the tensile strain state becomes smaller.

[0339] Another spectral observation in experiment B was D under 532 nm excitation. u The peak position is 1328.6 cm -1 The following (sample B3) is gradually interpolated: D of sample B3 u Peak position: 1328.6 cm -1 is the peak position of cubic diamond, 1332 cm -1 The anthracite network is known to be susceptible to beam induction heating, and D u Sample B4 was evaluated at a lower laser power setting of 0.5 mW due to the effect on peak position. The Raman spectrum of sample B4 collected at 0.5 mW laser power showed that the D band was located at 1332 cm -1 It was clearly shown that the peak position of this 1332 nm cubic diamond is red-shifted below the peak position of this cubic diamond. -1 The interpolation below shows that the hexagonal diamond array contains sp x Some researchers have suggested that hexagonal diamonds have a diameter of 1324.4 cm -1 While other examples have shown a strong Raman peak at 1318 cm -1 and 1325cm -1 Therefore, the average D of sample B4 u Peak position: 1324.5cm -1 , and 1318 cm -1 and 1320cm -1 D between u The multiple point spectrum with peak positions indicates sp of non-chair conformation. x This is strong evidence of a ring.

[0340] In addition to the large degree of interpolation, D of sample B4 u The bands are also D in samples B1 to B3. u This is because a high proportion of RBM phonons are sp x Activated by backscattering at the interface, sp 2This indicates that the RBM phonons activated by backscattering at the edge states are eliminated. 2 As the edge atoms are removed, x The more highly grafted the network, the narrower this peak should be. This enhanced grafting in sample B4 can be attributed to three factors: (i) the strained sp ‐like structure required for grafting at specific structural interfaces; x (ii) the dehydrogenation is slower at lower pyrolysis temperatures, meaning the condensate takes longer to find the grafted configuration; and (iii) smaller, less sterically hindered C2H2 gas molecules are used.

[0341] First, we start from the premise that certain structural interfaces do not allow chair conformations, i.e., cubic diamond. This premise is consistent with previous published studies on graphene-diamond bonding. In this study, in order for the edges of graphene domains to bond to the diamond surface, the atomic positions of the dangling bonds of graphene must be located at the sp -type atoms present on the diamond surface. 3 It turns out that for certain graphene edge configurations, the lonsdaleite (hexagonal diamond) surface has a higher sp -like orientation than the cubic diamond surface. 3 The atomic arrangement matches well.

[0342] In the consideration of Figures 29 to 36, the sp x The graphene-diamond bond exhibits a diamond-shaped seam containing rings, i.e., a cubic diamond-shaped seam. The graphene-diamond bond is characterized by the shape of the graphene edge and the sp 3 Based on the logic of the prior art, which required the matching of atomic columns, it is assumed that the two graphene edges at the structural interface are sp 3 To be grafted, each must have a matching sp 3 grafted to the atomic row, and then these two sp 3 The atomic rows are sufficiently consistent to form sp 3 -sp3 They theorize that bond lines must form, which is why the non-cubic polymorph of diamond is needed.

[0343] At a hypothetical zigzag-zigzag interface where the edges are close enough to be directly bonded, such as the E1-E2 interface shown in Figure 29, the sp 2 From sp 3 via rehybridization to sp 3 Two rows of atoms are created that are close enough to bond directly to each other, making each of the two graphene structures sp 3 effectively matching a row of atoms, so that there are sp 3 -sp 3 Bond lines can be formed to create two-dimensional cubic diamond shaped seams.

[0344] However, because the spacing of the edge atoms involved in a structural interface is inherently stochastic, we must consider the possibility that at some interfaces, opposing edge atoms are too far apart to bond directly to each other. To illustrate this, in Frame I of Figure 40, E * and E ** We model the offset zone of the zigzag-zigzag structure interface, which includes two edges, where E ** is E * For simplicity, the hydrogen atoms are not shown. 2 The spacing between the edge atoms is too large, so sp 3 No grafting occurs, but there is still room between the ends for interstitial atom insertion by continued radical addition.

[0345] In Frame II of Figure 40, the high end E ** sp 3 Insert a row of interstitial atoms (circled in Figure 40). 3 The row of interstitial atoms is E ** Match the end, E * SP 2Although close enough to bond with the edge atom, the vertical offset causes sp 2 Grafting is inhibited.

[0346] In Frame III, E * SP 2 Opposite rows of edge atoms are sp 2 From sp 3 Following rehybridization to sp 3 form a row of atoms, which are sp 3 -sp 3 bond to a row of interstitials (highlighted in red in Frame III of Figure 40). 3 -sp 3 Rows of bonds connect the graphene structure. ** Higher order SP on the side 3 The radical allows the radical addition to continue, resulting in a boat conformation of sp x Rings form (because chair conformations are not geometrically possible). Continued growth can result in seams, as shown in Frame IV of Figure 40. Such seams no longer contain cubic diamond but instead contain amorphous hexagonal polymorphs, which can be expected to have low-frequency Raman spectral peaks.

[0347] Therefore, the lateral spacing of the structural interface is sp 3 sp generated by grafting x It plays an important role in determining the ring conformation. When the spacing between the zigzag edges is close enough, the opposite sp 2 The edge atoms rehybridize and form sp 3 grafted and in a chair conformation sp x If the spacing between the zigzag edges is too wide, an interstitial row can be inserted, resulting in sp 2 Rehybridize the edge atoms and sp 3 -sp 3 sp that can form bond lines 3This results in a thermodynamically unstable conformation that may not be stable at high temperatures, i.e., complete grafting of the structural interface may not be possible at high temperatures. The necessity of such an interface configuration and the sp of the boat conformation are discussed. x Based on the necessity of the ring, sp x Network is 1332cm -1 Lower sp 3 If it does not show a D peak interpolation with the mode, it can be confidently concluded that it is incomplete grafting.

[0348] As modeled in Figure 40, the insertion of interstitials increases the local atomic packing density - at many interfaces, the interstitials are packed or wedged into the interface, increasing the sp 2 The fine spacing and the need for molecular rearrangement during dissociative adsorption suggest that small gas-phase species such as C2H2 offer less steric hindrance to reactions and atomic insertion at these interfaces, making grafting and compression easier. Despite being prepared at the same temperature of 580 °C, sample B4 (prepared by pyrolysis of C2H2) exhibited a higher D than sample B2 (prepared by pyrolysis of C3H6). u It is assumed that this is the main reason why the peak position is significantly low.

[0349] The logic of dense atomic "packing" at the structural interface is sp 3 Not only the offset zone where grafting occurs, but also the sp 2 This also applies to the horizontal zones where grafting occurs. Interstitial atom insertion at the structural interface explains the gradually higher G peak position observed in experiment B, while sample B4 has an average position of 1603.3 cm -1 , point position 1604.2cm -1 In the procedure using C2H2 feed gas at pyrolysis temperatures below 580 °C, the -1 Average G exceeding u Peak position and 1610cm -1 Point positions up to have been observed.

[0350] Other structural interfaces formed stochastically can be easily imagined, and sp 3 Grafting is done on other sp x These may include five-membered rings, seven-membered rings, nine-membered rings, and possibly others, all of which connect the participating graphene structures. x Ring-forming sp 3 The grafting events may further add up to form diamond shaped seams.

[0351] As an example of this, Frame I of Figure 41 shows the structural interface formed by a zigzag end segment and an armchair end segment (i.e., the "zigzag-armchair" interface). For simplicity, only the offset region of the zigzag-armchair interface is shown, and hydrogen atoms are again omitted. In Frame I of Figure 41, the interfacial spacing is 2 The end atoms are such that they are close enough to be directly grafted.

[0352] Therefore, Sp 3 Grafting is performed by grafting these opposing sp 2 sp at edge atom 2 From sp 3 The sp 3 -sp 3 sp with atom positions that can form bond lines 3 A row of atoms is formed, which is shown in frame II of Figure 41, with the enlarged inset showing sp 2 Atoms are filled circles, sp 3 Atoms are represented by black and white circles. 3 -sp 3 The bond lines are formed by alternating five- and seven-membered sp x Ring (R a , R b and R c and highlighted in yellow in the enlarged inset of Frame II in Figure 41).

[0353] As shown in Frame III of Figure 41, continued pyrolytic growth from the tertiary radical leads to the formation of second z-neighboring lines (R in Figure 41) of five- and seven-membered rings. d , R e and R f (written as) and sp 3 A third line of atoms (shown as a black and white circle in the enlarged inset of Frame III) can be generated. 3 The atom position within the line of atoms is determined by the z-neighboring sp 3 As well as the atomic lines, the encircled sp in the enlarged inset of Frame III in Figure 41 2 Atoms and sp 3 They can incorporate into the zigzag edges of atoms, thus forming a diamond-shaped seam at the zigzag-armchair interface.

[0354] If the spacing of the zigzag-armchair interface is too large to allow for bonds to form between the opposing edge atoms, an interstitial atom may need to be inserted. In such cases, sp 3 Grafting can lead to the formation of boat and half-chair conformations—like zigzag-zigzag interfaces with interstitial atoms. In Frame I of Figure 42, the edge atoms of the two domains are not close enough for direct grafting, and the interstitial sp 3 The row of atoms is bonded at the armchair edge. 3 The row of atoms has enough opposing sp 2 near the edge of the atom, but due to the vertical offset 2 Grafting is inhibited.

[0355] In Frame II of Figure 42, sp 2 sp at edge atom 2 From sp 3 via rehybridization to sp 3 Grafting proceeds, and sp 3 A second row of atoms is created, and sp 3 -sp 3 A bond line is formed. In the enlarged inset of Frame II in Figure 42, Sp 2 Atoms are filled circles, sp 3Atoms are represented by black and white circles. 3 -sp 3 The bond is formed by alternating seven- and nine-membered sp x Ring (R I , R II and R III and highlighted in yellow in the enlarged inset of Frame II in Figure 42).

[0356] As shown in Frame III of Figure 42, continuing pyrolytic growth leads to a row of six-membered rings in the boat conformation (R IV , R V and R VI and highlighted in yellow in the enlarged inset in Frame III). Further growth leads to the formation of a half-chair conformation sp x A sequence of rings (R VII , R VIII and R IX and labeled in yellow in the enlarged inset of Frame IV of Figure 42), creating a Y dislocation. In this way, the Y dislocation and the hexagonal diamond-shaped seam are formed from the zigzag-armchair interface with interstitials.

[0357] The stochastic nature of this process allows for a variety of structural interface configurations, sp x While the presence of rings and diamond-shaped seams is inevitable, the exemplary model detailed here is sufficient to explain the governing principles underlying these diverse specific scenarios, and also explains the observation of Raman spectral features consistent with cubic and hexagonal diamond motifs.

[0358] We next consider the structural interactions and pyrolytic growth of larger populations of primordial domains more broadly, which give rise to higher-order structural activity not yet considered by the applicant. To illustrate this, Figure 43 shows the sp x Illustrating network formation. The diagram is drawn from a horizontal perspective. Growth can be divided into three stages.

[0359] In Stage I of Figure 43, independently nucleated protodomains grow toward each other on a common substrate. The substrate is displayed in blue, and the black lines represent growing domains. The arrows indicate that the protodomains grow radially outward based on radical addition at their edges. If growth terminates during the previous Stage I when grafting has not progressed significantly, sp 2 The radial breathing mode is sp associated with these isolated ring-cleaved domains 2 It will be mainly activated by edge states.

[0360] In Stage II of Figure 43, domains are grafted to form a base and begin to nucleate higher layers on top of the base. Diamond-shaped seams (each seam is represented by an "X" in Stage II of Figure 43) form, and associated with them are anthracite sp. x A network is formed. Structural interfaces are stochastic and dynamic in nature, with hydrogenated aggregates self-rearranging and relaxing to energy-minimizing grafting configurations. Some structural interfaces allow opposing edge atoms to graft directly to each other, while others require the insertion of interstitials (as shown in Figures 40 and 42) to allow grafting. This increases atomic packing and allows for sp x If the growth terminates during stage II, the activation of RBM phonons is similar to that of sp 2 Edge states (which remain after growth has finished) and sp 3 This will occur through some coordination of states. Therefore, one can expect the D band to be interpolated and different modes to appear in the D band.

[0361] In stage III of Figure 43, sp xThe steady state of vertical and horizontal network growth promotes the structural encounter and subsequent grafting of higher-order layers. Similar to the structural activity between primordial domains, this proceeds stochastically. Dislocations tend to replicate z-periodically, creating diamond-shaped seams laterally, but this z-periodicity is not deterministic. On the other hand, new seams can nucleate from the structural encounter of higher-order layers, which is also expected to create incoherent interfaces. This allows for the formation of sp x This may allow for a more even distribution of dislocations throughout the network. If growth terminates at stage III in Figure 43, the activation of RBM phonons is sp 3 The growth can be characterized by the state (depending on the efficiency of grafting at the interface) and the interpolation of the D band can be seen rather than when the growth is terminated at stage I or stage II.

[0362] Although Figures 29 to 36 depict the vertical and lateral growth in stages, the lateral growth is expected to be much faster than the vertical growth mode. In other words, the nucleation of higher-order layers is likely to be rate-limiting. Since the nucleation of higher-order layers occurs at the structural interface, the overall growth is driven by the increase in structural activity and the sp 3 This can be accelerated by means of grafting. As long as the gas-phase species are abundant, rapid lateral growth allows for uniform coverage of the substrate, resulting in the formation of an envelope mineral wall of consistent thickness. This explains the uniform thickness of the envelope mineral wall observed in Figure 27C, even in "window" regions where nucleation of primordial domains would have been inhibited. Applicant has observed that for many substrates, the resulting carbon remains linear over long periods of time, indicating a steady state of high-layer nucleation. This "timeless" kinetic model is a fundamental advantage of anthracite networks over graphene networks, where the only growth mode is lateral.

[0363] G u Peak position (as a relative indicator of compressive strain), D u Peak position (sp 2 as a relative measure of the removal of edge states) and hence the spectral spacing between them (compressive distortion and sp2 (as both an indicator of edge state removal) across the various stochastically formed structural interfaces created during growth, and the different sp x This peak spacing - G can provide a useful indicator for characterizing the extent to which the network was able to form grafted bonds. u Peak position and D u VR0% - defined as the wavenumber distance between peak positions - is commonly used in the anthracite literature to determine vitrinite reflectance via Raman spectroscopy. Furthermore, vitrinite reflectance is an indicator of coal maturity. As coal matures, the spacing between peaks increases and vitrinite reflectance increases. For immature to mature coals, using 532 nm excitation, previous researchers calculated vitrinite reflectance as follows: vR0% = 0.0537(G u -D u )-11.21, where vR0% is the vitrinite reflectance (calculated using Raman parameters).

[0364] In sample B4, the peak spacing was 278.8 cm -1 This corresponds to a vitrinite reflectance of 3.76, which is typical for anthracite. Above this value, the peak-to-peak spacing is approximately 280 cm. -1 (which varies somewhat with excitation due to the dispersion of the D peak), and the spacing begins to decrease again as the anthracite matures from anthracite to meta-anthracite and finally to graphite. With this maturation, the I Du / I Gu The intensity ratio begins to increase and the spacing between peaks is no longer useful for calculating vitrinite reflectance. For mature anthracite or meta-anthracite, using 532 nm excitation, previous researchers have used the formula vR0% = 1.1659(I Du / I Gu )+2.7588, I Du / I Gu The peak intensity ratio was used to calculate the vitrinite reflectance.

[0365] Sample B4 was then characterized by XRD analysis. Figure 44 shows the overall XRD profile. Table 5 below contains the values ​​for the XRD peak angle, d-spacing, area, area fraction (normalized to the area of ​​the main peak at 2θ=24.489°), and full width at half maximum (uncorrected for instrument broadening). [Table 5]

[0366] The XRD profile of sample B4 contains broad peaks, indicating a range of interlayer and in-plane periodicity. In particular, <100> Note the broad fitted peak at 2θ = 43.138°, which is equivalent to a d-spacing of 2.095 Å. This is the same as that of graphite. <100> This reflects an average in-plane compressive strain of approximately 2% based on a d-spacing of 2.13 Å. <110> We can see the sign of in-plane compressive strain at 2θ=79.501°, which is equivalent to a d-spacing of 1.21 Å. This is again in line with the <110> This reflects a compressive strain of approximately 2% based on a d-spacing of 1.23 Å. This is due to the blue-shifted G u The peak positions are in good agreement.

[0367] The most prominent feature in the XRD profile of sample B4 is the main peak at 2θ = 24.489°, which is <002> This reflects the d-spacing of 3.63 Å, which is the same as that of AB-stacked graphite. <002> d spacing of 3.35 Å or turbostratic graphite <002> The d-spacing is significantly larger than 3.45 Å. This expansion is due to the x This contributes to the forced AA stacking at many of the cubic diamond-shaped seams distributed throughout the network. In the AA stacking region, the minimum interlayer spacing can be expected to increase due to the Pauli repulsion caused by the alignment of π-electron orbitals. Indeed, the interlayer spacing of the AA stacked layers is predicted to be 3.6-3.7 Å, which is in good agreement with the main interlayer peak at 2θ = 18.454°. Furthermore, there is an associated small peak at 2θ = 50.192°. <004> A peak was observed, which corresponds to a d-spacing of 1.82 Å- <002> This reflects half of the d-spacing of 3.63 Å.

[0368] The second interlayer peak was fitted at 2θ = 18.454°, reflecting an interlayer d-spacing of 4.80 Å. These values ​​and the width of the peak indicate the widespread presence of large interlayer spacings—larger than those observed in Experiment A. This is explained below. x In the network, the increased atomic packing as a result of grafting induces in-plane compressive strain beyond the critical buckling strain. Regions compressed beyond this critical buckling strain are forced to distort in the positive z direction, which represents the only degree of freedom. For this to occur, the vdW attraction to the underlying layer must be overcome. With sufficient strain, this occurs, and they bend away from the z-neighboring layer below, reaching a maximum amplitude of z deflection somewhere near the geometric center between the lateral seams that pin their periphery. This z deflection relaxes the in-plane compressive strain in these regions, but also increases the interlayer d-spacing. We expect the bending to form a broad continuum of interlayer d-spacings, exactly as observed in Table 4 and Figure 94, where the broad peak centered at 2θ = 18.454° reflects a significant phase of interlayer d-spacings greater than 7 Å. Therefore, we attribute this second interlayer peak at 2θ = 18.454° to the bending of xy-compressed graphene regions in the z direction between the diamond-shaped seams that sandwich them at their periphery.

[0369] From this established relationship, sample A1 (minimally grafted z-sp x Signs of curvature can also be seen in the interlayer d-spacings of sample A1 (vdW aggregate) and sample A2 (vdW network), which exhibit d-spacings below 2.13 Å. <100> It can also be seen that the in-plane compression state based on the peaks is observed. This indicates that the same phenomenon occurs in these low grafting systems. Specifically, in sample A2, local sp x Although a network is thought to have been constructed, it does not extend over the entire wall. x The network is insufficiently grafted to allow the ring-connected network to extend throughout the entire enveloping mineral wall.

[0370] Based on the findings from Experiments A and B, we investigated the sp 2 and sp 3 It is possible to speculate after the fact within the prior art where grafting may have occurred.

[0371] In one example, Cui performed a template-dependent CVD procedure at 950 °C using methane (CH4) and MgO template particles, which produced a 1322 cm -1 (under 633 nm excitation) u A single-layer graphene structure was produced that retained the peak position. Except for the interpolation of the D band, the D band of this graphene monolayer was observed under 633 nm excitation. u Peak height is 1332cm -1 As mentioned above, this is expected to be found near sp 3 sp in grafted and chair conformations x This is consistent with the formation of a ring. -1 The reported D peak position of may represent a redshift caused by interpolation.

[0372] However, there are a few points to note. First, in the Cui procedure, 3 We attempted to replicate the reported results to confirm whether a grafted system had been produced. We were pleased to find that the BET and TGA characteristics of the replicate samples we synthesized closely matched those of the samples reported by Cui. Furthermore, our Raman spectroscopy (performed under 532 nm excitation) revealed that I Du / I Gu The Raman spectra showed very similar peak intensity ratios, but no clear interpolation of the D peak position was observed. Our attempts to reproduce the interpolation of the D peak were unsuccessful.

[0373] Second, despite the D-band interpolation of the sample reported by Cui, the graphene particles produced are monolayer in nature as synthesized on the template, and therefore the cross-linking is lateral, which means that this sample is not an anthracite network or sp xThis is hardly a network. The case for this has been convincingly made in the prior art based on extensive BET, TGA, and XRD characterization. Therefore, because this rearrangement requires a natural multilayer structure, the vertical cross-linking between layers obtained in the anthracite network could not be realized. It is true that removal of the template has been reported to collapse the single-layer network into a bilayer structure. However, this bilayer does not undergo cross-linking via dislocations, sacrificing the important three-dimensionality of the molecular-level cross-linking present in the anthracite network. The absence of dislocations is also evident in HRTEM images of the bilayer, where edge lines are unbroken, visually distinct, and traceable over distances of more than 10 nm.

[0374] In another prior art study, Chung flame-synthesized carbon nano-onions at temperatures below 700°C (the temperature varied depending on the location). This procedure involved rapid chemical vapor deposition on metal catalyst nanoparticles, resulting in graphitic carbon nano-onions by precipitation. Post-mortem analysis revealed that the graphitic carbon nano-onions appeared to contain diamond-shaped seams. However, the cross-linking mechanism and pattern may be different, as the layers comprising the layered network are arranged in a graphitic arrangement (as evidenced by HRTEM analysis and reported in <002> (Also evidenced by the interlayer d-spacing of 3.45 Å.) Notably, these graphitic networks would have had significantly fewer chiral rings and columns due to fewer zone transitions at the structural interfaces between highly ring-ordered domains. These transitions are directly related to the undulating edge shapes associated with ring-disordered domains grown by the free-radical condensation growth mechanism. Furthermore, these carbon nano-onions offer less versatility and reduced control over important morphological attributes compared to the growth procedures demonstrated herein. However, it is foreseeable that certain aspects of this flame synthesis procedure, such as partial oxidation, could be utilized in tandem with the use of nonmetallic catalysts and free-radical condensation-based growth.

[0375] X. Experiment C - Analysis sp xWe investigated other pyrolysis methods that could synthesize the networks and found that by utilizing template-dependent CVD temperatures similar to those in Experiment B but at lower temperatures (325°C-500°C), we could synthesize carbons with an increased brownish color. Below 400°C, light brown carbons were obtained due to incomplete dehydrogenation of the growing condensates. At temperatures of 460°C, carbons were produced that appeared gray with a faint brownish tint.

[0376] A comparison of two samples (samples C1 and C2) synthesized at these temperatures is shown in Figure 45. These color differences are similar to the difference between highly mature coal (black color, low hydrogen) and less mature coal (brown color, high hydrogen). The residual hydrogen in the 400°C carbon sample shown in Figure 45 was confirmed by FTIR analysis, as shown in Figure 46.

[0377] Raman characterization of samples C1 and C2 was performed using a 532 nm laser with 0.5 mW of power under an Ar blanket. This low laser power was determined to be appropriate because the samples became thermally unstable at higher powers. Table 6 below lists the samples, CVD temperatures (i.e., CVD furnace set points), carbon source, and average I Du / I Gu and I Tru / I Gu Peak intensity ratio, average G u and D u Peak position and G u and D u The spacing between the peak positions is indicated. [Table 6]

[0378] The Raman spectral data in Table 6 are obtained from average spectra representing a composite of 16 point spectra. To calculate the average, the raw data for each point spectrum is first scaled ±5 cm. -1 The spectra were smoothed using a moving average method at intervals of 1. After smoothing, the intensity values ​​of each point spectrum were normalized to a common scale, and then the normalized intensity values ​​were averaged to create an average intensity value for each wavenumber.

[0379] Both Samples C1 and C2 show a decrease in the spacing between peaks compared to the sample in Test B, consistent with more hydrogenation and less grafting. Sample C1 exhibited a D u The peak was interpolated to 1332.7 cm -1 D u Based on the peak positions, the particles of sample C1 were partially grafted z-sp x In sample C2, D u The peaks do not show interpolation.

[0380] As shown in the averaged spectra of Figure 47, both sample C1 and sample C2 have a peak at 600 cm -1 A broad, weak peak appears at 600 cm -1 The peak at 1000 nm is attributed to dehydrogenated nanodiamond-type carbon and was also present in sample B4. Thus, in addition to the hydrogenated phases in samples C1 and C2 associated with the decomposition products of uncarbonized free radical condensates, there was also evidence of a non-hydrogenated nanoscale diamond phase.

[0381] The coexistence of hydrogenated and dehydrogenated phases can be considered to correspond to phases grown inside and outside the porous template, respectively. In other words, lower CVD temperatures increase the stability of C—H bonds, and the proportion of H2 is expected to increase inside the porous template, where gas exchange is diffusion-limited. Unable to release hydrogen molecules and therefore unable to carbonize, free radical condensates in these regions ultimately relax into neutral, low-molecular-weight hydrocarbon species. Researchers in the field of free radical condensation have demonstrated this phenomenon using time-of-flight mass spectrometry. To confirm this, sample C2 was immersed in ethanol under gentle stirring conditions. This produced a stable, amber-colored dispersion that passed through the filter, indicating the dissolution of the hydrocarbon oil phase.

[0382] XI. Experiment D - Analysis Experiment D was conducted to confirm the role of H2 gas in suppressing the release of hydrogen molecules during free radical condensate growth. Procedures D1 and D2 were essentially identical, except that in Procedure D1, only C3H6 and Ar were flowed into the reactor, while in Procedure D2, H2 was introduced at a low flow rate in addition to C3H6 and Ar. It was hypothesized that the presence of H2 should slow the carbonization process and promote relaxation of the condensates into grafted structures that minimize energy at the structure interfaces. Raman analysis was performed using a 532 nm laser at 5 mW power. Table 7 below lists the sample IDs, Raman D u The peak positions of the C@MgO-encapsulated mineral composite powders are shown in Fig. 1. [Table 7]

[0383] D of sample D2 u From the increase in peak position interpolation, the sp of procedure D increases with increasing the presence of H2. 2 It was confirmed that the removal of edge states was promoted. u Peak position: 1341.9 cm -1 Based on this, the exoskeleton mineral framework of sample D1 was partially grafted z-sp x Including the network. D of sample D2 u Peak position: 1329.5cm -1 Based on this, the exoskeleton mineral framework of sample D2 is composed of highly grafted x-sp x Including the network.

[0384] The carbon growth rate was reduced by approximately 50%, which suggests that slowing the carbonization of the condensate also slowed the carbon growth rate. Therefore, we found that H partial pressure can be used to slow carbonization and improve grafting, especially at higher temperatures that promote carbonization. From this, we can infer that in addition to pyrolysis temperature, the C:H ratio of the carbon source gas, the rate of H release and diffusion from the growing material, the presence of H feed gas, the morphology and pore structure of the substrate, the size of the template particles, the activity of the substrate surface, the presence of H scavenging species, and many other factors are important because they affect the dynamic equilibrium of hydrogenation and dehydrogenation in free radical condensates.

[0385] Understanding this, it may be possible to rationally balance these many factors to obtain faster kinetics. As a simple example, lower D is obtained when using a CVD temperature of 700 °C and a H2 feed rate of 30 sccm compared to when using a CVD temperature of 580 °C without H2 as the feed gas. u Peak position (sp 2 It has been confirmed that both high-temperature and high-speed carbon growth kinetics can be achieved simultaneously (consistent with good removal of edge states).

[0386] XII. Experiment E-Analysis Experiment E is sp x network (here "sp x This was done to demonstrate the formation of helical x- and z-networks from the precursor (referred to as the "precursor"). Samples E1 and E2 were prepared using the same template material, and sp x Samples E1A and E2A contained the sp precursors of samples E1 and E2, respectively. x This maturation, i.e., sp 3 From sp 2 The conversion by rehybridization to sp x It was obtained by annealing the precursor, i.e., the C@MgO inclusion mineral complex.

[0387] Figure 48 shows the equivalent masses of Sample E1 and Sample E1A side by side - Sample E1 on the left and Sample E2 on the right. Sample E1 consists of large, hard granules, while Sample E1A has a finer, softer consistency. The granules of Sample E1 occupy a much smaller volume than the Sample E1A powder, and when shaken they click against the glass wall of the vial, whereas the Sample E1A powder is silent when shaken. Sample E1A occupies a larger volume.

[0388] Figure 49A is an SEM image showing the granules of sample E1. As shown at higher magnification in Figure 49B and Figure 49C, individual encrusted minerals within the macroscopic granules of sample E1 exhibit a sheet-like pore morphology similar to that of sample B4. The templates used to prepare the samples of experiment E included flat platelet-like particles and stacks of platelet-like particles. The template particles contained a porous substructure of connected nanocrystalline subunits resulting from the pyrolysis of a hydromagnesite template precursor. These template particles (coated with iridium for imaging) are shown in the SEM image in Figure 51.

[0389] The flexibility of the exoskeleton mineral walls of sample E1 and the surface tension of water during drying cause the porous interior to collapse, resulting in only a sheet-like upper structure, clearly shown in Figure 49B, and a less clear lower structure, magnified in the inset of Figure 49C. The local flexibility of the exoskeleton mineral walls in sample E1 imparts flexibility to the particles, creating a wavy textured appearance, as shown in Figure 49B. When visually tracing the edges of the sheet-like particles in the SEM image, it is difficult to find a straight line. The flexibility of the exoskeleton mineral framework in sample E1 allows the particles to conform to each other, increasing the contact area and reducing the spacing between particles. This improved framework flexibility and packing results in dense, rigid granules upon evaporative drying.

[0390] Figure 49D is an SEM showing the finer hardness of the sample E1A powder compared to sample E1. While agglomerates are still present in sample E1A, they are not as dense or hard as the granules of sample E1, and there are many small agglomerates. Comparing Figure 49E, which shows the particles of sample E1A, with Figure 49B, which shows the particles of sample E1, a significant change is evident. The particles of sample E1A appear more linear than the wavy particles of sample E1, indicating stiffening. While the particles of sample E1 appear textured, the stiffened particles of sample E1A are buckled and more angular. This increased stiffness reduces the ability of the particles of sample E1A to flex and conform to one another, preventing the degree of densification exhibited by sample E1.

[0391] In the enlarged inset of Figure 49F, the stiffening of the sample E1A particle is also evident at the local level, where the porous subunits are preserved in their native morphology versus collapsed. This results in a clearly defined and recognizable porous substructure of sample E1A in Figure 49F—clearly more faithful to the native templated morphology than the relatively unclear substructure of sample E1 in Figure 49C.

[0392] Similar comparisons were made between Sample E2 and Sample E2A. Like Sample E1, Sample E2 densified into hard, macroscopic granules, as shown in Figure 50A. Under high magnification, Sample E2 particles can be seen within these granules. Like the particles of Sample E1, the particles of Sample E2 appear wavy and flexible, as shown in Figure 50B and Figure 50C.

[0393] Sample E2A occupied a significantly larger volume and was finer in hardness than the Sample E2 powder. Compared to the large, hard granules of Sample E2, the Sample E2A powder consisted of smaller, softer aggregates, as shown in Figure 50D. The annealed particles of Sample E2A again exhibited a stiffening effect—both at the particle level and locally. As shown in Figures 50E and 50F, the annealed particles of Sample E2A were stiffer and straighter than the unannealed particles of Sample E2. Furthermore, as shown in Figure 50F, the horizontal interplate stacking observed in the template powder was retained in the Sample E2A powder, likely indicating that the plate-like particles fused during annealing, so that they did not break apart during liquid-phase extraction of the endogenous minerals. The interparticle fusion effect will be discussed in more detail in connection with Experiment F.

[0394] To understand the changes in the bonding structure created by annealing, Raman analysis was performed using a 532 nm laser at 5 mW power. u and D u The average spectra for the range of peaks in the annealing range are shown, and the changes in the spectra with annealing are indicated by black arrows. Table 8 below shows the average I Du / I Gu and I Tru / I Gu Peak intensity ratio, average G u and D u Peak position and G u and D u The intervals between the peak positions are tabulated. [Table 8]

[0395] Interpolated D for samples E1 and E2 u The peak positions are sp related to the diamond-shaped seam 3 This indicates the existence of the state D of sample E1. u Peak position: 1335cm -1 Based on this, the exoskeleton mineral framework of sample E1 was partially grafted z-sp x Including the network. D of sample E2 uPeak position: 1328cm -1 Based on this, the exoskeleton mineral framework of sample E2 is composed of highly grafted x-sp x The network contains peaks whose spacing is typical for anthracite.

[0396] In contrast, the D of mature samples E1A and E2A u The peak positions are 1352 cm -1 and 1347 cm -1 These are sp 2 This is the normal range of the D band. Therefore, due to maturation, the sp in the exoskeleton mineral framework of sample E1A and sample E2A 2 Phase and sp 3 This indicates that the strong coupling of the phases was eliminated in samples E1A and E2A. 3 It can be seen that the condition has been significantly reduced or eliminated. Du / I Gu The increase in the peak intensity ratio and the decrease in the spacing between peaks reflect the maturation of the anthracite network. u Based on the peak positions, the framework contains highly mature helical z carbons, and D of sample E2A. u Based on the peak positions, the framework contains highly mature helical x carbons.

[0397] The sp of sample E1 and sample E2 x The rigidification of the grain and encasing mineral walls of the mature samples is surprising, given the absence of diamond-shaped seams that provide a bridging mechanism for the network. If these mature grains were not ring-connected, such thin-walled carbon would not be able to withstand template extraction, let alone sp x It is not significantly stiffened compared to the precursor, and we can therefore conclude that the mature particles are cross-linked via a bridge structure that is more rigid than the atomically thin, diamond-shaped seams of the precursor.

[0398] That D u Apart from the return of the peaks to the normal D-band range, samples E1A and E2A also exhibited a significant increase in their G u Increased D (relative to peak) u and Tr u Peak intensities are also shown. u The increase in peak intensity (and area) is due to the sp 2 This reflects the rapid increase in rings. u Inverse interpolation of peaks and sp 2 The increase in ring structure is sp x Ring sp 2 Converting sp to ring 3 From sp 2 The increase in the valley height of the G peak of the annealed sample is evidence of rehybridization to sp 2 We show redshifted modes consistent with the generation of lattice distortion. 3 The annihilation of the sp states, the distortion of the lattice, and the increase in the stiffness of the particle bridges 3 From sp 2 Rehybridization to the diamond-shaped seam results in sp 2 This is evidence of the formation of hybrid screw dislocations. These screw dislocations provide both vertical and horizontal crosslinks, giving the mature network a helical shape. This helical network structure can be conceptualized as a mesh formed by numerous screw dislocation loops, as shown in Figure 12D.

[0399] sp x To demonstrate that the precursor matures into a helicoid network, sp 3 From sp 2 We begin by modeling the effect of rehybridization to the cubic diamond-shaped sp. Frame I of Figure 53 shows a multilayered monolayer vertically intersected by a cubic diamond-shaped seam. The system shown in the figure is x This seam can be thought of as a small region in the precursor system. 2 -sp 3 Bonds and sp 3 -sp 3including the bond—the latter is highlighted in red in Frame I.

[0400] During annealing, the sp 3 Each member's SP 3 From sp 2 Rehybridization to β requires breaking one of the bonds. The two bonds are connected by high-energy sp 2 It cannot be cleaved unless a radical is generated. 3 -sp 3 The sp bonds are the least stable and are the first to destabilize during annealing (these broken bonds are shown by the gray dotted lines in Frame II of Figure 53). 3 Atoms and sp between them 3 -sp 3 The join line contains the horizontal line, so one sp 3 Atomic rehybridization and sp 3 -sp 3 The breaking of one of the bonds occurs between the xy-adjacent sp along the bond line. 3 -sp 3 Destabilizes the bond, causing linear dissociation. Dissociation of the entire line results in severing and maintaining the ABAB pattern -sp 3 -sp 3 When the bond line is broken, high energy sp 2 Two z-adjacent bond lines are kept so as not to form radicals.

[0401] In this way, the diamond-shaped seams due to lateral dissociation and the associated ring connections between z-adjacent layers are also eliminated. Thus, the simplex of Frame I in Figure 53 is decomposed into a vdW aggregate of strained, separated layers. This is shown in Frame III in Figure 53. This allows the sp x The role of diamond-shaped seams, which connect the network in both the lateral and vertical directions, becomes clear. As shown in Figure 53, during cutting, the lateral cross-linking modes are maintained, but the vertical cross-linking modes disappear. This indicates that sp xIt can be concluded that network maturation eliminates the vertical cross-linking associated with diamond-shaped seams. In the absence of other vertical cross-linking mechanisms, maturation leads to sp x The precursor transforms into a vdW aggregate that loses the vertical cross-links, and the vdW aggregate becomes less rigid than the three-dimensionally cross-linked precursor.

[0402] Next, sp x We will now explore the effect of adding a chiral ring and a chiral column to the precursor and aging it. The formation of such a system has already been modeled (see Figure 36), so we will apply this model to the exemplary sp x However, to improve visualization of its maturation, we consider only half of the system from Figure 36, shown from two perspectives (H1 and H2) vertically and horizontally in Frame I of Figure 54. Like the precursor modeled in Figure 53, this new precursor in Frame I of Figure 54 contains a diamond-shaped seam. However, unlike the precursor modeled in Figure 53, the diamond-shaped seam in this precursor terminates in a chiral column. The H2 perspective of Frame I of Figure 54 highlights the chiral column, the chiral chain is highlighted in blue, and the sp 3 -sp 3 The bonds are highlighted in red.

[0403] During maturation, sp 3 Part sp 3 From sp 3 Rehybridization of sp results in bond cleavage. 3 -sp 3 The sp bond between the two terminal atom members of each chiral chain is the least stable and is the first to be destabilized. 3 -sp 3 Each such bond is broken by a lateral sp 3 -sp 3 represents the end of the bond line, and its cleavage results in the remaining sp 3 -sp 3 The bond line becomes unstable. Therefore, sp 3 -sp 3Linear dissociation of bond lines (previously shown in Frame II of Figure 53) occurs in Frame II of Figure 54. These broken bonds are shown as gray dotted lines in Frame II of Figure 54. High energy sp 2 To avoid the formation of radicals, sp 3 -sp 3 An ABAB pattern of bond breaking and retention is formed.

[0404] In the H1 perspective of Frame II in Figure 54, this sp 3 -sp 3 The disconnection of the bond lines reveals the absence of diamond-shaped seams in the system. When they are removed, the vertical bridges associated with them are also removed, while the lateral bridges remain. In the absence of chiral rings or chiral columns, the disappearance of these vertical bridges would again result in a vdW assembly of separated z-adjacent layers, as was the case in the system shown in Figure 53. However, in this case, the chiral columns are present, and ABAB cleavage allows the sp s within the chiral columns to be separated. x The bonds that comprise the helix are left intact, which is the sp bond between the terminal atoms of each chiral chain. 3 -sp 3 When the bond is broken, the z-adjacent sp bonds between the chiral rings follow an ABAB pattern of breakage and retention. 3 -sp 3 These retained bonds are sp 3 From sp 2 Rehybridization to sp 2 -sp 2 This converts it into a one-dimensional sp x The spiral is sp 2 Atoms and sp 2 -sp 2 One-dimensional sp with bonds 2 These bonds are highlighted in blue in the H2 perspective of Frame II in Figure 54. Despite the loss of the vertical bridges associated with the diamond-shaped seams, the system retains the structure of these sp 2The retention of the helix preserves the vertical bridges associated with the chiral columns. Thus, both the lateral and vertical bridges are preserved during aging. The chiral rings (and the associated chiral columns of the connected chiral rings) are key to preserving the vertical bridges during aging.

[0405] This preservation of lateral and vertical crosslinks is shown in Frame III of Figure 54, which represents the relaxed system shown in Frame II. From Frame III, we can see that the ribbon-like helical graphene structure formed by ripening has a screw dislocation in the z-direction at its center. 3 From sp 2 Both before and after rehybridization of the central sp. 2 All atoms in the spiral are members of a ring. Therefore, during maturation, sp 2 The formation of the spiral is sp 2 The adjacent sp to which the spiral belongs as an edge 2 This involves the formation of a spiral pathway of rings. 2 From the formation of the spiral, sp 2 The formation of graphene helices, to which the helices belong, can be inferred, and sp 2 The retention of vertical bridges by the helix can be inferred from the retention of vertical ring connectivity.

[0406] From Frame III of Figure 54, it can be seen that the helical graphene structure needs to be distorted to maintain vertical ring connectivity. Graphene screw dislocations have been shown to exhibit twisting strain, and we expect to see a proliferation of low-frequency strained phonon states along with this twisting strain. The high valleys in Samples S1A and S2A are evidence of the lattice distortion caused by this helical geometry. Furthermore, from Frame III of Figure 54, it can be seen that the sp 3 The state is sp 2 It can be seen that the state is exchanged into the edge state. 3 State elimination and sp 2 The rapid increase in edge states is due to the D u This is reflected by the inverse interpolation of the peak positions. x Ring sp2 sp associated with transformation to a ring 2 The rapid increase in the number of rings is due to the increased D in samples E1A and E2A. u The formation of helices around chiral columns thus explains many of the spectral changes that occur with maturation.

[0407] sp 2 The helix-containing edge segment exhibits an interesting structure. It is unique in that every atomic member of the segment is bonded to three nearest carbon atoms, while the zigzag edge configuration is unique in that only half of the edge atoms are bonded to three carbon atoms, whereas in a regular zigzag edge configuration, only half of the edge atoms are bonded to three carbon atoms. This helix-zigzag feature results from the fact that it represents a chain of atoms formed by a broken polygon, where all interior angles of the broken polygon are less than 180°, thus allowing three carbon atoms to be adjacent at every edge position (including a reflective angle that prevents all edge positions from being bonded to three carbon atoms, as opposed to a regular zigzag edge). This novel edge configuration may result in novel electromagnetic and thermal properties that are known to depend on the edge configuration of graphene nanoribbons.

[0408] sp 2 The spiral is sp x To further clarify the process of evolving from the helix, the transformation is shown diagrammatically in Figure 55. In Frame I of Figure 55, a chiral column of three z-adjacent chiral rings is depicted. The blue lines in Figure 55 represent the chiral chain bonds, and the red lines represent the sp 3 -sp 3 The black circles in Figure 55 represent sp 2 The black and white circles represent sp atoms. 3 represents an atom.

[0409] As explained above in relation to Frame II of Figure 54, during ripening, sp 3 -sp 3 The bond is broken and sp 3 -sp 3 An ABAB pattern of bond breaking and retention is generated. The broken sp represents the "B" phase of the ABAB pattern. 3 -sp3 The bond is represented by a gray dotted line in Frame II of Figure 55 and labeled "B", while the retained sp 3 -sp 3 The bond is reconstituted by rehybridization to sp 2 -sp 2 These are therefore represented by blue lines in Frame II of Figure 55, labeled "A." This results in sp 2 -sp 2 sp connected via bonds 2 It becomes a one-dimensional helical chain of atoms. When relaxed, this sp 2 The curvature of the spiral becomes more uniform, as shown in Frame III of FIG.

[0410] Next, we consider the transformation of the two-dimensional graphene structure surrounding this one-dimensional helix. As mentioned above, 2 The formation of the spiral is sp 2 The helix entails the formation of graphene helices, which represent the end segments. The diagram in FIG. 56 mirrors the diagram in FIG. 55, but the sp in FIG. 56 has been removed to illustrate the formation of the helical geometry. x and sp 2 The difference is that we are attempting to represent the ring-connected structure around the helix. Frame I of Figure 56 shows a diamond-shaped seam (extending to the foreground, as indicated by the semi-transparent portion of the figure) terminating in the same chiral column shown in Frame I of Figure 55. The chiral chain of these rings is again represented by blue lines in Frame I of Figure 56, and is represented by sp 3 -sp 3 Bonds are again represented by red lines. Following established convention, the black circles in frame I of Figure 56 represent sp 2 The black and white circles represent sp atoms. 3 In Figure 56, however, blue and red regions are used to represent the ring-connected space. For example, the blue space surrounding the blue chiral chain is the ring-connected sp 2 The red space represents the ring-connected sp 3 Indicates space.

[0411] During maturation, the central sp in frame I of Figure 56 x The helix undergoes the same transformation as diagrammed in Figure 55, i.e., the sp 3 -sp 3 The bond is broken, followed by the associated sp 3 -sp 3 The bond line is dissociated, which allows the ring-connected sp 3 A fragment of space is removed. In Frame II of Figure 56, this removed space is shown in gray and labeled "B." This space can be imagined as extending to the foreground of the figure, like the diamond-shaped seam shown in Frame I. Meanwhile, the retained space, representing the "A" phase of the ABAB pattern, 3 -sp 3 The bond line is sp through rehybridization 2 -sp 2 This retained ring-connected space of the "A" phase is depicted in blue in Frame II of Figure 56 and labeled "A." It can also be imagined as extending to the foreground of the figure, like the diamond-shaped seam illustrated in Frame I.

[0412] When relaxed, as shown in Frame III of Figure 56, the same one-dimensional sp 2 A single helical graphene structure with a helix (i.e., a screw dislocation) is produced. The parametric equations that approximate this helix are x = u cos(v), y = u sin(v), z = cv, where the value of u is the central sp x One-dimensional sp evolved from a spiral 2 It is equal to or greater than the radius of the spiral.

[0413] These figures show sp 3 with diamond-shaped seams and chiral rings. xWe show how maturation of a network generates a mature network with both horizontal and vertical ring connections. To illustrate the principles of this transformation, we consider one diamond-shaped seam and one sp x Simple sp containing spirals x However, the precursor was a moderately large sp x The network can contain countless seams and chiral rings formed by structural interactions and grafting. In many cases, a single structural encounter between two end segments can lead to the development of multiple seams and chiral rings, as shown in Figure 36.

[0414] For this reason, a simple exemplary sp containing multiple seams and chiral rings is x It is desirable to model the transformation of the precursor. The formation of such a system in Experiment A has already been modeled (see Figure 36), so we will return to it for our purposes. The structural encounter and subsequent pyrolytic growth shown in Figures 29-36 suggest that this hypothetical sp x We derived a network. To facilitate visual evaluation of the transformation of the system, we show it from two perspectives (H1 and H2), vertical and horizontal, in Figure 57.

[0415] In frame I of Figure 57, sp x The precursors are then oriented to form two distinct diamond-shaped seams (each seam is circled in the perspective view of H2) and chiral chains representing the lateral ends of those seams (in the perspective view of H2, the chiral chains are highlighted in blue, and sp 3 -sp 3 During maturation, sp 3 From sp 2 Rehybridization to the system of Figure 54 allows the sp 3 -sp 3 This results in the breaking of a bond (which, as you may recall, is a subsystem of the system under consideration in Figure 57). This is shown in Frame II of Figure 57, where the broken sp 3 -sp 3Gray dotted lines are again used to represent bonds. 3 -sp 3 The ABAB pattern of bond line breaking and retention proceeds according to the sequence already described in connection with the transformation of the system in Figure 54. The retained bonds are sp 2 -sp 2 The only significant difference between the transformations shown in Figure 54 and Figure 57 is that the transformation in Figure 57 is a transformation of the larger sp x It extends across multiple seams and chiral rings of the precursor.

[0416] Relaxation of the system illustrated in Frame II of Figure 57 creates the helical network shown in Frame III of Figure 57. This simplex contains a network of two connected helical regions formed by two different screw dislocations in the system. The helical regions are ring-connected to each other, but the horizontal perspective of Figure 57 is not ideal for visually identifying the ring connections (a better perspective for identifying the ring connections is provided in Figure 58). In Frame III of Figure 57, two sps associated with the screw dislocations 2 The helix is ​​highlighted in blue. The two screw dislocations both contain loops. Both screws share a common chirality.

[0417] To better observe the ring connection between the two helices in Frame III of Figure 57, Figure 58 shows the simplex from an oblique angle, using a stick model visualization to aid depth perception. The yellow arrows highlight the common chirality of the two helices, and the black dotted arrows approximate the axes of the two helices—i.e., the dislocation lines. The entire loop shown in Figure 58 contains a ring-connected simplex similar to the graphene screw dislocation loops observed in the anthracite region (see Figure 12, D).

[0418] From these simple models, the spectral data of experiment E, and the changes in mechanical behavior observed in experiment E, it is clear that the changes in the bonding structure between samples E1 and E1A, and between samples E2 and E2A, are due to sp xThe sp network changes to a helical network 3 From sp 2 It can be concluded that this was due to re-hybridization to the

[0419] This is further supported by XRD analysis, which shows that x-sp x Sample B4A was created by annealing the network powder sample B4 at 1,050°C for 30 minutes while flowing Ar. x The network matured into a helical x-network. Figure 59 shows the overall XRD profile of sample B4A. Table 9 below contains the values ​​for the XRD peak angle, d-spacing, area, area fraction (normalized to the area of ​​the main peak at 2θ=23.535°), and full width at half maximum (uncorrected for instrument broadening). [Table 9]

[0420] The XRD profile of sample B4A contains significant changes. First, the broad peak fitted at 2θ = 18.454° in sample B4, which accounted for 30.4%, is not fitted in this range in the profile of sample B4A. This peak in sample B4 is believed to represent the phase of expanded interlayer spacing caused by bending of the graphene region in the z-direction due to intralayer compression beyond its critical buckling strain. At the same time, a broader fitted peak appears in sample B4A at 2θ = 29.489°, corresponding to a d-spacing of 3.03 Å and accounting for 33.2% of the peak area. These spectral changes suggest an overall shift toward smaller interlayer d-spacing, and the peak center at 2θ = 29.489° indicates potential interlayer compression.

[0421] Furthermore, when comparing sample B4 and sample B4A, <100> The peak shifts from 2θ=43.138° to 2θ=43.396°, respectively. <100> Notice that this corresponds to a decrease in the d-spacing from 2.10 Å to 2.08 Å. <002> It can be seen that the peak increases at 2θ=23.535°, which corresponds to an increase in the average interlayer d-spacing from 3.63 Å to 3.78 Å.

[0422] These changes are explained by changes in the cross-linking structure. <100> The cross section of an in-plane diamond-shaped seam is a line (i.e., one-dimensional), whereas <100> The cross section of an in-plane screw dislocation is a point (i.e., zero-dimensional). Therefore, when a one-dimensional pin is eliminated during ripening, only zero-dimensional pins remain that coincide with the endpoints of the eliminated one-dimensional pin. When the diamond-shaped seam is released, it only pins the curved layers at a point, rather than a full line, allowing them to relax more freely.

[0423] The lateral relaxation of these curved regions has the effect of reducing the amplitude of the z-deflection (thereby eliminating the broad peak at 2θ = 18.454° in sample B4 due to curvature) by more fully distributing the compressive and lattice strains within the layers. This increases the average interlayer d-spacing (mainly <002> The d-spacing associated with the peak increases from 3.78 Å to 3.63 Å. This is also reflected in the shift of the broad interlayer peak from 2θ = 18.454° to 2θ = 29.489°. Maturation reduces the d-spacing from 2.10 Å to 2.08 Å. <100> An increase in compressive strain is observed at the peak.

[0424] Unlike the other fitted peaks, which are broad and poorly correlated, the peaks at 2θ = 21.660° and 2θ = 35.944° are sharp and suggest highly periodic features, most likely due to the interlamellar periodicity consistently formed at the screw dislocation core of the helix.

[0425] sp xWe explore the formation of networks and their maturation into helical networks, understand the fundamental characteristics of these disordered networks, and then understand the structural zone transitions and their influence on the mature helical networks, and how the structural zone transitions affect sp x double helix, sp 2 This demonstrates how this can lead to the formation of structural variants including double helices and double helices.

[0426] First, returning to the helical network in Figure 58, the two connected helices and the resulting screw dislocations have the same chirality. This is due to the two base layer chiral rings (R 2-C and R 4-C ) reflects the preservation of the common chirality of the chiral chains within the E1-E2 interface. Applicants previously attributed the common chirality of these chiral rings to the inversion of edge heights between offset zone I and offset zone II at the E1-E2 interface modeled in FIG.

[0427] In an alternative scenario, where the edge heights between offset zone I and offset zone II are not reversed, the chiral rings of the two base layers have opposite chiralities. Figure 60 compares the original scenario with this alternative scenario. In Frame I, which corresponds to the original scenario, sp 2 and sp 3 In this scenario, the chiral ring R is inserted at the transition between each of the two offset zones and the horizontal zone between them. 2-C and R 4-C It has already been shown that the common chirality of the chiral chain is indicated by the blue arrow in the vertical perspective view of Frame I of Figure 60.

[0428] In Frame II of Figure 60, which corresponds to the new scenario, the sp crossing the interface where the edge height is not reversed between offset zone I and offset zone II 2 and sp 3In this alternative scenario, the chiral ring R is attached at the transition between each of the two offset zones and the horizontal zone between them. 2-C and R 4-C is still formed. However, because the ends do not cross and the end heights do not reverse, the chiral chain has the opposite chirality. This opposite chirality is indicated by the blue arrow in the vertical perspective view in Frame II of Figure 60.

[0429] sp x If the network subsequently grows on top of this base, sp x The helix will have opposite chirality and, associated with this, there will be less Eshelby twist between z-adjacent layers. Then, if this simplex becomes sp 3 From sp 2 When the helical network is transformed by rehybridization to 2 The screw dislocation loop formed by the screw is less distorted. The chiral ring of the base layer is formed first, and the dislocation is mixed sp x Chirality is maintained throughout the formation of intermediate networks, ultimately forming a helical network. Anthracite researchers have observed that screw dislocation loops often contain two adjacent xy screw dislocations of opposite chirality. Applicant has discovered that loops can also contain two adjacent screw dislocations of common chirality.

[0430] Another possible interface configuration is created when opposing end segments intersect without forming a horizontal zone between the two offset zones on either side. This configuration occurs even though the intersection is at the same height as the opposing segments. 2 Edge atom 2p z This can occur when the orbitals are misaligned and a π bond cannot be formed. The point where the edges intersect is called a "crossing point." The edge atoms at the crossing point are the high-energy sp 2 To eliminate edge states, sp 3 -sp 3 can form bonds, but sp2 -sp 2 Bond lines cannot be formed. At these intersections, sp 3 By grafting, sp x Chiral columns containing double helices are formed, and upon maturation, sp 2 A double helix is ​​formed.

[0431] sp on structural interfaces with intersections x The pyrolytic synthesis of the network is shown in Figure 61. In Figure 61, the sequence is divided into four stages. Stage I of Figure 61 shows the E1-E2 interface of Figure 29, but in this analysis, the edge crossing leads to sp 2 Let us assume that grafting is not possible - i.e., that there is an intersection between offset zone I and offset zone II. The interface in the diagram remains unchanged, but we will call it E1-E2 to show that we have assumed an intersection instead of a horizontal zone. c In stage I of Figure 61, E1-E2 c The interfacial zones associated with the interface are shown in the enlarged inset of the H2 perspective. Adjacent offset zones are separated by intersections indicated by Xs in the enlarged view.

[0432] Stage II in Figure 61 models the grafting of G1 and G2 and the nucleation of vertical growth via radical addition on the grafted base. The grafting and subsequent growth is consistent with the mechanism previously discussed in relation to pyrolytic growth modeled in Figures 29-36. However, in this analysis, edge misalignment leads to the sp 2 No grafting occurs. Instead, sp 3 Grafting of only E1-E2 occurs. c Two sp strands crossing the interface 3 -sp 3 The join lines are highlighted in red in the enlarged inset of stage II in Figure 61.

[0433] 2 sp 3 -sp 3 The bond line is formed by six laterally adjacent spx They form rings, each containing six atom members. x Five of the rings (R1, R2, R4, R5, and R6) are in chair conformations, and the orientation of R1 and R2 contains a point symmetry of the orientation of R4, R5, and R6. As established by the analysis of Figures 29-36, this point symmetry results from the reversal of edge heights between the two offset zones. Other sp x Ring (R 3-C ) is a chiral ring established at the intersection, similar to the applicant's previous discovery that chiral rings are formed at the transition of the interfacial zone. However, R 3-C We demonstrate that chiral rings formed at intersections such as these can contain two chiral chains, whereas chiral rings formed at transitions of structural zones involving horizontal zones contain only one chiral chain.

[0434] In stages III and IV of Figure 61, sp due to continuous vertical and horizontal growth x We model the formation of a network, which proceeds according to the same principles and mechanisms previously established in the discussion and analysis of Figures 29-36. Ring connectivity is extended laterally and vertically throughout higher layers via diamond-shaped seams. In vertical perspective views of both Stage III and Stage IV, Eshelby twists can be observed between each of the z-adjacent layers. The sp modeled in Stage IV x Network (G IV ) contains two different diamond-shaped seams.

[0435] In Figure 62, sp x Precursor G IV The double helix is ​​modeled after the maturation of G IV Two disconnected helical graphene structures G are created by the decomposition of G upon maturation. i and G ii Based on the composition of multiple members of different graphene structures, the double helix of Figure 62 comprises an aggregate-type system. This aggregate is shown in Figure 62 using two molecular visualizations from a vertical perspective and two vertical and horizontal perspectives. The cause of the collapse is sp3 From sp 2 As previously established, the sp 3 -sp 3 The bond is broken and the associated sp 3 -sp 3 The bond line dissociates laterally. At the center of the double helix is ​​a double screw dislocation. Double screw dislocations have been observed in protein crystals, and it has been found that the geometry of the interface junction can force their formation during maturation.

[0436] sp x The precursor G IV However, as it matures, its base becomes sp 2 Since there is no ring connection, decay occurs. G IV The base is the E1-E2, which is the origin of the base. c Horizontal zone and sp at the interface 2 Due to the absence of grafting, sp 2 Instead, E1-E2 c sp on the interface 3 Since only grafting occurred, the protodomains G1 and G2 were isolated from these sp 3 -sp 3 sp formed from bonds x Ring connection (R1, R2, R 3-C After its formation, the base layer was only connected by rings (R4, R5 and R6). 2 The ring remains broken, and G is placed on it. IV As a result, during maturation, G IV The base layer of this sp 3 The grafted interface is completely dissociated, and the primitive regions associated with G1 and G2 are again disconnected at the base. In a system that remains ring-connected, these two primitive regions at the base must be ring-connected via some pathway across the higher-order layers to adjacent rings. However, as each higher-order layer is completely dissociated, as well as the base, such pathways have been removed. As a result, sp x The precursor consists of two graphene structures, G i and G iiThe primitive domain G1 is completely decomposed into G i The primitive domain G2 is in G ii It's inside.

[0437] sp in Figure 61 2 The dissociation of the ring-cleaved base is analyzed in more detail in Figure 63. This is shown in Frame I of Figure 63. 3 sp formed via grafting x Ring connection (R1, R2, R 3-C , R4, R5 and R6). In Frame II of Figure 63, sp x The ring connection is made by isolating a portion of the base containing the primitive E1 and E2 edge atoms. These atoms contain a zigzag-zigzag interface and two sp 3 -sp 3 The six sp x Each ring has two sp 3 -sp 3 In Frame II, we can see the intersections where the edge heights are reversed, and the chiral ring R corresponding to the intersections 3-C The chiral ring R 3-C Except for the other sp in Figure 63 x The rings are in chair conformation. As shown in the enlarged view of Frame II, the rings in chair conformation each have four sp 3 atom (represented by a black and white circle) and two sp 2 atoms (represented by black circles). In each of these rings, two sp 3 -sp 3 The bonds have a common orientation.

[0438] sp 3 Other sp formed via grafting x Similarly to the ring, the chiral ring R 3-C , ...

Claims

1. Materials include synthetic anthracite.

2. The material of claim 1 , wherein the synthetic anthracite comprises a templated morphology.

3. 3. The material of claim 1, wherein the synthetic anthracite comprises an encrusted mineral framework.

4. The material of any one of claims 1 to 3, wherein the synthetic anthracite comprises at least one of a mesoporous structure and a macroporous structure.

5. The material of any one of claims 1 to 4, wherein the synthetic anthracite comprises at least one of a microscopic structure and a macroscopic structure.

6. 6. The material of any one of claims 1 to 5, wherein the synthetic anthracite comprises a layered graphene network cross-linked via structural rearrangements.

7. The material of any one of claims 1 to 6, wherein the synthetic anthracite comprises a room temperature superconductor.

8. 8. The material of claim 7, wherein the room temperature superconductor is macroscopic.

9. Materials including synthetic anthracite networks.

10. 10. The material of claim 9, wherein the synthetic anthracite network comprises a layered graphene network cross-linked via structural rearrangements.

11. The synthetic anthracite network is sp ｘ The material according to any one of claims 9 to 10, comprising a network.

12. The material of any one of claims 9 to 10, wherein the synthetic anthracite network comprises a spiral network.

13. 13. The material of any one of claims 9 to 12, wherein the synthetic anthracite network comprises x carbons.

14. 13. The material of any one of claims 9 to 12, wherein the synthetic anthracite network comprises z carbons.

15. The material according to any one of claims 9 to 14, wherein the structural dislocation comprises a Y dislocation.

16. The material according to any one of claims 9 to 14, wherein the structural dislocations comprise mixed dislocations.

17. 17. The material of claim 16, wherein the mixed rearrangement comprises a chiral column.

18. The material according to any one of claims 9 to 14, wherein the structural dislocation comprises a screw dislocation.

19. 18. The material of claim 17, wherein the structural dislocation comprises a double screw dislocation.

20. The synthetic anthracite network is sp ２ The material of any one of claims 9 to 19, comprising a hybridized region and a diamond-shaped region.

21. 21. The material of claim 20, wherein the diamond-shaped region comprises at least one of cubic diamond, hexagonal diamond, and amorphous diamond.

22. 21. The material of claim 20, wherein the diamond-shaped region comprises at least one of a chair conformation, a boat conformation, and a half-chair conformation.

23. The diamond-shaped region is sp ２ Hybridized atoms and sp ３ sp bearing hybridization atoms ｘ 21. The material of claim 20, comprising a ring.

24. 24. The material of any one of claims 9 to 23, wherein the synthetic anthracite network comprises ring-connected simplex members.

25. 25. The material of any one of claims 9 to 24, wherein the synthetic anthracite network comprises a multi-layer network.

26. The multi-layer anthracite network is ２ 2,300 m measured via adsorption ２ 26. The material of any one of claims 9 to 25, comprising a minimum average BET surface area of ​​less than 1 / g.

27. The multi-layer anthracite network is ２ 1,000 m measured via adsorption ２ / g and 2,300m ２ 27. The material of claim 26, comprising a minimum average BET surface area of ​​between 1 / g.

28. The multi-layer anthracite network is ２ 10 m measured via adsorption ２ / g and 1,000m ２ 27. The material of claim 26, comprising a minimum average BET surface area of ​​between 1 / g.

29. The multi-layer anthracite network is ２ 10.0 cm measured via adsorption ３ 29. The material of any one of claims 9 to 28, comprising an average BJH specific porosity of less than 1 / g.

30. The multi-layer anthracite network is ２ 7.5 cm measured via adsorption ３ / g and 10.0 cm ３ 30. The material of claim 29, comprising an average BJH specific porosity of between 1 / 2 and 1 / 2 g.

31. The multi-layer anthracite network is ２ 2.5 cm measured via adsorption ３ / g and 7.5 cm ３ 30. The material of claim 29, comprising an average BJH specific porosity of between 1 / 2 and 1 / 2 g.

32. The multi-layer anthracite network is ２ 2.5 cm measured via adsorption ３ / g and 7.5 cm ３ 30. The material of claim 29, comprising an average BJH specific porosity of between 1 / 2 and 1 / 2 g.

33. The average Raman spectrum obtained with 532 nm excitation is at 1342 cm －１ and 1375 cm －１ 33. The material of any one of claims 9 to 32, comprising an unfitted D band having a peak intensity between

34. The average Raman spectrum obtained with 532 nm excitation has a peak at 1332 cm －１ and 1342 cm －１ 33. The material of any one of claims 9 to 32, comprising an unfitted D band having a peak intensity between

35. The average Raman spectrum obtained with 532 nm excitation has a peak at 1318 cm －１ and 1332 cm －１ 33. The material of any one of claims 9 to 32, comprising an unfitted D band having a peak intensity between

36. The average Raman spectrum obtained with 532 nm excitation has a peak at 1300 cm －１ and 1318 cm －１ 33. The material of any one of claims 9 to 32, comprising an unfitted D band having a peak intensity between

37. The average Raman spectrum obtained with 532 nm excitation has a peak at 1580 cm －１ and 1595 cm －１ 37. The material of any one of claims 9 to 36, comprising an unmatched G band having a peak intensity between

38. The average Raman spectrum obtained with 532 nm excitation has a peak at 1595 cm －１ and 1610 cm －１ 37. The material of any one of claims 9 to 36, comprising an unmatched G band having a peak intensity between

39. The average Raman spectrum obtained with 532 nm excitation has a peak at 1610 cm －１ 37. The material of any one of claims 9 to 36, comprising an unmatched G band having a peak intensity greater than

40. The average Raman spectrum obtained with 532 nm excitation has a peak at 600 cm －１ and 750 cm －１ 40. The material of any one of claims 9 to 39, comprising an unfitted peak between

41. 41. The material of any one of claims 9 to 40, wherein the average Raman spectrum obtained with 532 nm excitation comprises a valley located between the unfitted G peak and the unfitted D peak, and the ratio of the height of the valley to the height of the unfitted G peak is between 0.60 and 0.

80.

42. 41. The material of any one of claims 9 to 40, wherein the average Raman spectrum obtained with 532 nm excitation comprises a valley located between the unfitted G peak and the unfitted D peak, and the ratio of the height of the valley to the height of the unfitted G peak is between 0.40 and 0.

60.

43. 41. The material of any one of claims 9 to 40, wherein the average Raman spectrum obtained with 532 nm excitation comprises a valley located between the unfitted G peak and the unfitted D peak, and the ratio of the height of the valley to the height of the unfitted G peak is between 0.20 and 0.

40.

44. 41. The material of any one of claims 9 to 40, wherein the average Raman spectrum obtained with 532 nm excitation comprises a valley located between the unfitted G peak and the unfitted D peak, and the ratio of the height of the valley to the height of the unfitted G peak is between 0.05 and 0.

20.

45. The average Raman spectrum obtained with 532 nm excitation has an I of less than 3.0 between its unfitted D peak and its unfitted G peak. Ｄ / I Ｇ The material of any one of claims 9 to 44, comprising a peak intensity ratio.

46. The average Raman spectrum obtained with 532 nm excitation has an I between 2.0 and 3.0 between its unfitted D peak and its unfitted G peak. Ｄ / I Ｇ 46. ​​The material of claim 45, comprising a peak intensity ratio.

47. The average Raman spectrum obtained with 532 nm excitation has an I between 1.0 and 2.0 between its unfitted D peak and its unfitted G peak. Ｄ / I Ｇ 46. ​​The material of claim 45, comprising a peak intensity ratio.

48. The average Raman spectrum obtained with 532 nm excitation has an I between 0.1 and 1.0 between its unfitted D peak and its unfitted G peak. Ｄ / I Ｇ 46. ​​The material of claim 45, comprising a peak intensity ratio.

49. The average Raman spectrum obtained with 532 nm excitation has an I of less than 0.50 between its unfitted 2D peak and its unfitted G peak. ２Ｄ / I Ｇ The material of any one of claims 9 to 48, comprising a peak intensity ratio.

50. The average Raman spectrum obtained with 532 nm excitation has an I between 0.25 and 0.50 between its unfitted 2D peak and its unfitted G peak. ２Ｄ / I Ｇ The material of any one of claims 9 to 48, comprising a peak intensity ratio.

51. The average Raman spectrum obtained with 532 nm excitation has an I between 0.05 and 0.25 between its unfitted 2D peak and its unfitted G peak. ２Ｄ / I Ｇ The material of any one of claims 9 to 48, comprising a peak intensity ratio.

52. 52. The material of any one of claims 9 to 51, wherein the XRD profile comprises a <002> peak position corresponding to an average interlayer d-spacing of 3.35 Å to 3.45 Å.

53. 52. The material of any one of claims 9 to 51, wherein the XRD profile comprises a <002> peak position corresponding to an average interlayer d-spacing greater than 3.45 Å.

54. 52. The material of any one of claims 9 to 51, wherein the XRD profile comprises a <002> peak position corresponding to an average interlayer d-spacing between 3.45 Å and 3.55 Å.

55. 52. The material of any one of claims 9 to 51, wherein the XRD profile comprises a <002> peak position corresponding to an average interlayer d-spacing between 3.55 Å and 3.65 Å.

56. 52. The material of any one of claims 9 to 51, wherein the XRD profile comprises a <002> peak position corresponding to an average interlayer d-spacing between 3.65 Å and 4.00 Å.

57. 57. The material of any one of claims 9 to 56, wherein the XRD profile comprises a broadened mode of the <002> peak with a peak position corresponding to an enlarged interlayer d-spacing of greater than 3.75 Å.

58. 58. The material of claim 57, wherein the XRD profile comprises a broadened mode of the <002> peak with a peak position corresponding to an expanded interlayer d-spacing of between 3.75 Å and 4.50 Å.

59. 58. The material of claim 57, wherein the XRD profile comprises a broadened mode of the <002> peak with a peak position corresponding to an expanded interlayer d-spacing of between 4.50 Å and 5.25 Å.

60. 58. The material of claim 57, wherein the XRD profile comprises a broadened mode of the <002> peak with a peak position corresponding to an expanded interlayer d-spacing of between 5.25 Å and 6.00 Å.

61. 61. The material of any one of claims 9 to 60, wherein the XRD profile comprises a <100> peak with a peak position corresponding to an average interlayer d-spacing of less than 2.13 Å.

62. 62. The material of claim 61, wherein the XRD profile comprises a <100> peak with a peak position corresponding to an average interlayer d-spacing between 2.11 Å and 2.13 Å.

63. 62. The material of claim 61, wherein the XRD profile comprises a <100> peak with a peak position corresponding to an average interlayer d-spacing between 2.09 Å and 2.11 Å.

64. 62. The material of claim 61, wherein the XRD profile comprises a <100> peak with a peak position corresponding to an average interlayer d-spacing between 2.00 Å and 2.09 Å.

65. 65. The material of any one of claims 9 to 64, wherein the synthetic anthracite network comprises an enveloping mineral framework.

66. 66. The material of claim 65, wherein the encasing mineral framework comprises microscopic particles comprising at least one of spherical particles, hollow spherical particles, fibrous particles, rosette particles, cubic particles, and prismatic particles.

67. 68. The material of any one of claims 9 to 67, wherein the synthetic anthracite network is a macrofoam comprising at least one of granules, pellets, fabrics, papers, filaments, and molded articles.

68. 69. The material of any one of claims 9 to 68, wherein the synthetic anthracite network comprises carbon structures grafted to one another by pyrolytic growth, the carbon structures comprising at least one of carbon black, glassy carbon, activated carbon, and carbon nanoparticles.

69. 69. The material of any one of claims 9 to 68, wherein the synthetic anthracite comprises a room temperature superconductor.

70. 70. The material of claim 69, wherein the room temperature superconductor comprises room temperature superconducting granules and the synthetic anthracite network comprises granular room temperature superconductor.

71. 71. The material of any one of claims 9 to 70, wherein the room temperature superconductor comprises a porous material evacuated to an internal pressure of less than 760 Torr.

72. 72. The material of claim 71, wherein the room temperature superconductor is evacuated to an internal pressure of between 1 Torr and 10 Torr.

73. 72. The material of claim 71, wherein the room temperature superconductor is evacuated to an internal pressure of between 100 mTorr and 1 Torr.

74. 72. The material of claim 71, wherein the room temperature superconductor is evacuated to an internal pressure of between 10 mTorr and 100 mTorr.

75. 72. The material of claim 71, wherein the room temperature superconductor is evacuated to an internal pressure of less than 10 mTorr.

76. The material according to any one of claims 9 to 75, wherein the room temperature superconductor comprises a gas-impermeable barrier phase for preventing the intrusion of external gas molecules.

77. The material according to any one of claims 9 to 75, wherein the room temperature superconductor comprises a gas-impermeable barrier phase for preventing the intrusion of external gas molecules.

78. 77. The material of claim 76, wherein the gas impermeable barrier phase comprises a metal.

79. The material according to any one of claims 9 to 77, wherein the room temperature superconductor becomes superconducting at a temperature of 20 ° C. and an external pressure of 1 atmosphere.

80. 78. The material of any one of claims 9 to 77, wherein the room temperature superconductor comprises a macroscopic article including a continuous filament, a sheet, or a shaped part.

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