Scalable Synthesis of Encapsulating Materials

Abstract

The present disclosure relates to the scalable synthesis of novel coating materials, including hierarchical coating frameworks, on recyclable templates and using recyclable process liquids. Using these methods, three-dimensional architectures constructed from two-dimensional molecular structures can be produced economically with reduced waste.

Description

[0001] Related Applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 086,760, filed Oct. 2, 2020, the entire disclosure of which is incorporated herein by reference.

[0003] The following applications are hereby incorporated by reference in their entirety for all purposes: PCT / US21 / 49195 (the ’49195 application); U.S. Provisional Patent Application 63 / 075,918 (the ’918 application); U.S. Provisional Patent No. 63 / 086,760 (the ’760 application); U.S. Provisional Patent Application 63 / 121,308 (the ’308 application); U.S. Utility Application 16 / 758,580 (the ’580 application); U.S. Utility Application 16 / 493,473 (the ’473 application); PCT / US17 / 17537 (the ’17537 application); PCT / US21 / 37435 (the ’37435 application); U.S. Provisional Patent Application 63 / 129,154 (the ’154 application); and U.S. Patent 10,717,843 B2 (the ’843B2 patent). TECHNICAL FIELD

[0004] The present disclosure relates to a method for the scalable production of diverse coating materials, including laminated coating materials having two or more coating layers. More specifically, the present disclosure relates to a low-cost, waste-reducing method for producing novel coating materials in which process materials can be recycled. BACKGROUND ART

[0005] Compared to bulk materials, nanostructured materials can have superior properties. A three-dimensional ordered architecture constructed from nanostructured building blocks can facilitate the realization of these superior properties in bulk material form. These “architectured” materials can be produced by synthesizing nano- or micro-scale building blocks and arranging them into elaborate assemblies. In particular, porous materials having an architectured pore structure are favored due to their low density, high specific surface area, and potential mechanical properties.

[0006] The ’49195 application teaches a scalable method (“general method”) for synthesizing carbon-coated frameworks using surface replication or conformal replication of a template surface to direct the formation of a coating architecture. By engineering the template material, carbon frameworks having a variety of rationally engineered substructural and superstructural features have been synthesized. In some variants of the general method, such as the “preferred method” taught in the ’49195 application, the template material employed includes magnesia (MgO) templates obtained from magnesium carbonate (MgCO3·xH2O) template precursor materials.

[0007] Although the applications of carbonaceous coated frameworks are numerous, it will be desirable to develop other coating materials through template-directed surface replication procedures similar to those described in the '49195 application. In particular, it will be desirable to synthesize coated frameworks constructed from a range of materials that are stable in atomic monolayer or few-layer configurations. Examples of potentially useful framework components include sp 2 hybrid boron nitride (BN), borophene (B), silicene (Si), boron carbonitride (BC x N), and various other ceramic compounds. In particular, it will be desirable to generate coated frameworks that include electrically insulating or semiconductive elements or compounds, and also compounds of these elements having a reasonable architected morphology that can be achieved through surface replication.

[0008] It will also be desirable to produce three-dimensional frameworks that include heterogeneous chemical compositions. In this way, different phases of the framework can achieve different functions. As an example, a carbonaceous framework can be shielded from thermal oxidation by sandwiching it between non-carbonaceous ceramic layers or encapsulating it within non-carbonaceous ceramic layers. As another example, a carbonaceous framework can be coated with a catalytic layer and used as a functional support for the catalytic layer. In particular, it will be desirable to include coated walls that include multiple different coating layers. Numerous useful heterostructured compositions have been identified in the graphene and graphene oxide literature, and it will be useful to be able to generate coated frameworks from these diverse compositions as well as compositions of new stratigraphic organizations that can be readily envisioned.

[0009] Additionally, it will be desirable to use methods that recycle both the template and the process liquid to produce coating materials, including coated frameworks. Additionally, in certain variants, it will be desirable to recycle process gases. As described in the '49195 application, conserving and reusing process materials can reduce the material inputs and outputs required to produce coating materials, thereby reducing costs and waste. If the general method or preferred methods can be more generally used to produce coating materials that are not entirely carbonaceous in composition, this will make the manufacture of these novel coating materials more scalable and efficient. SUMMARY OF THE INVENTION

[0010] The present disclosure presents a method for synthesizing novel coating materials of a variety of chemical compositions using surface replication techniques. The exemplary surface replication techniques presented herein can be incorporated into a general method. Thus, these surface replication techniques extend the applicability of the general method to include the scalable production of coated frameworks of different chemical compositions. These novel coating materials can be synthesized directly on an MgO template or synthesized onto other coating materials synthesized on an MgO template, and can be synthesized using preferred methods.

[0011] The present disclosure also presents a method for directly synthesizing two-dimensional materials or any chemical composition on non-metallic templates, porous templates, and reusable templates. In particular, a method for directly synthesizing two-dimensional materials on thermally stable metal oxide compounds such as MgO is disclosed so that these two-dimensional materials can be engineered in a variety of three-dimensional architectures. To demonstrate this, sp 2 hybrid BN and BC x N-coated frameworks are synthesized on porous MgO templates by template-directed CVD. The analysis presented herein shows that these coated frameworks include cross-linked hierarchical networks similar to the synthetic anthracite carbon networks described in the '37435 application. Other deposition methods including physical vapor deposition and other gases can be used to deposit other two-dimensional materials on these highly stable general templates. These other materials include mono-elementalenes (such as borophene, silicene, germanene, stannene, phosphorene, arsenene, antimonene, bismuthine, and tellurene) and compounds (such as various transition metal dichalcogenides) and doped variants.

[0012] The present disclosure also presents a method for encapsulating a coated framework by forming a gas-impermeable barrier phase around the coated framework. This barrier layer can be used to shield the encapsulated coated framework from external reactants (such as O2) or to seal the framework in a gas-evacuated internal state.

[0013] The present disclosure also presents examples of novel coated materials constructed from two-dimensional molecular structures such as sp 2 hybrid BN and BC x N. Thus, these two-dimensional materials can be fabricated into the same engineerable coated architectures previously demonstrated with graphene carbon, including coated architectures with controllable compact ordered substructures and elongated thin equiaxed hierarchical and hollow superstructures. Similar to the controllable flexible coated frameworks that can be generated from graphene carbon, controllable flexible coated frameworks can also be generated from these other two-dimensional materials.

[0014] The present disclosure also presents examples of novel coated materials constructed from two or more different coated layers to obtain new functions. These layers can include materials arranged in atomic monolayers (such as graphene carbon or sp 2 hybrid BN) or materials with three-dimensional bonding structures (such as silica or sp 3Hybrid BN). Combinations of carbon with other layers can also provide enhanced functionality. In particular, practical examples are shown in the present disclosure of shielding the graphene coating layer from thermal oxidation by adding one or more thermally inert coating layers. The supporting graphene layer can also be usefully combined with a catalytic layer (such as a metal or metal oxide adsorbent) to provide a high surface area catalyst, or to prevent charge carrier recombination (as in graphene / TiO2 composites). Numerous applications of the hierarchical coating framework of three-dimensional structures similar to two-dimensional / Van der Waals heterostructures will be apparent to those skilled in the art.

[0015] The present disclosure also shows examples of novel coating materials that are electrically insulating or semiconductive. Examples of electrically insulating coating materials include silica-like and sp 2 Hybrid BN coating framework. An example of a semiconductive coating material is BC x N coating framework, where the bandgap can be changed by varying the carbon content.

[0016] The present disclosure generally shows examples of ceramics that are lighter and have more diverse mechanical properties than their conventional bulk counterparts. In particular, these ceramics can be engineered to be flexible and even reversibly wrinkled or collapsed, as previously shown for carbon coating frameworks. A wide range of ceramic alloys can be designed by heat treating prefabricated ceramics.

[0017] The aim of the present disclosure is to make the generally and preferably previously disclosed methods more versatile. The ability to fabricate coating materials with diverse chemical characteristics while also preserving and reusing process materials makes these methods and their variants more powerful and applicable over a wider range. For example, there are various mesoporous silicas made by sol-gel procedures using cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), or other consumable template materials; the present disclosure provides an alternative route that allows the use of reusable template materials and process liquids to make mesoporous silica-like materials. In particular, an aim of the present disclosure is to provide a scalable way to produce non-carbonaceous or three-dimensional controllable compact architectures comprising multiple phases with different chemical characteristics.

[0018] Another aim of the present disclosure is to demonstrate how various elements and compounds, and hierarchical heterostructures of these elements and compounds, can be synthesized into templated porous morphologies that have hitherto only been demonstrated for carbon. This includes mesoporous and macroporous substructures with engineerable unit cell subunit geometries, as well as various superstructure geometries. In particular, microscopic superstructures with elongated, flattened, equiaxed, or hierarchical geometries can be synthesized.

[0019] Another aim of the present disclosure is to show how flexible coating frameworks can be constructed from non-carbonaceous two-dimensional materials. This is achieved by rationally designing the superstructure and compaction of the coating framework, as well as the thickness of the coating walls.

[0020] Another object of the present disclosure is to show how the graphene-coated framework can be modified by adding other coating layers. This can take the form of an overall encapsulation of the graphene-coated framework at the superstructural level or a more refined encapsulation of the coating walls at the substructural level. These modifications can be used to shield the graphene carbon from thermal oxidation, enabling them to resist combustion in high-temperature oxidation environments such as those encountered in the presence or near a flame or at high speeds in the atmosphere.

[0021] Another object of the present disclosure is to show how conventional and advanced ceramics (including ceramic alloys and composites) can be synthesized to have an engineered mesoporous or macroporous substructure and a variety of superstructural geometries. This may be useful for applications that benefit from weight reduction, rapid mass transfer, high surface area, or increased toughness, as these properties can all be achieved through engineered porosity. Description of the Drawings

[0022] Figure 1 A is a diagram of a layered coating framework including an AB stratigraphic arrangement. Figure 1 B is a diagram of a layered coating framework including a BAB stratigraphic arrangement, where the A layer is stratigraphically obscured. Figure 1 C is a diagram of a layered coating framework including an AB stratigraphic arrangement, where the B layer stratigraphically encapsulates the framework.

[0023] Figure 2 Shows how a layered coating framework can be synthesized using pre-extraction replication and post-extraction replication.

[0024] Figure 3 Is a diagram of a general method. The template cycle and the liquid cycle are marked.

[0025] Figure 4 Is a diagram of a general method with a gas cycle. Process gas is used for agent extraction in the separation stage and is recaptured in the precursor stage and / or the template stage.

[0026] Figure 5 Is a diagram of a preferred method. In the preferred method, the stock solution includes a Mg(HCO3)2 solution, the template precursor includes magnesium carbonate, the template includes MgO, and the coating material is carbonaceous.

[0027] Figure 6 Is a diagram of an AEAPTMS ((3-(2-aminoethylamino)propyl)trimethoxysilane)-functionalized carbon surface.

[0028] Figure 7 A is P 24 type layered coating material photograph, where the framework includes graphene layers and SiO x C y layers.Figure 7 B is P 25 Photograph of a P-type silica-like coating material.

[0029] Figure 8 A is P 25 SEM micrograph of a P-type silica-like coated framework. These frameworks were obtained by generating a BAB layered coated framework where A comprises a carbonaceous layer and B comprises an organosilane layer, and then removing the carbonaceous A layer and the carbon component of the B layer. Despite the deformation of the superstructure, the similarity to the prismatic isometric superstructure of the template precursor can still be discerned, as shown by the yellow dashed line. Figure 8 SEM micrograph of porous MgO template particles with a prismatic superstructure for B.

[0030] Figure 9 is a diagram showing P 23 type carbon, AEAPTMS-functionalized P 23 type carbon and P 25 Pore size distribution diagrams of different pore sizes of P-type silica-like materials.

[0031] Figure 10 SEM micrograph including elongated silica-like coating materials. As shown by the spectrum generated by energy dispersive x-ray spectroscopy, in some particles, the silica-like material stratigraphically encapsulates the carbon-coated material, thus preventing its thermal oxidation.

[0032] Figure 11 SEM micrograph including hollow spherical silica-like coating materials.

[0033] Figure 12 A includes P 26 Optical micrograph of a P-type coating material. This material includes a layered coated framework comprising a BAB stratigraphic arrangement of disordered BN (B phase) and carbon (A phase). P 26 The Raman spectrum of the P-type coating material is also shown in Figure 12 A. Figure 12 B includes P 27 Optical micrograph of a P-type coating material. This material includes a disordered BN coated framework. P 27 The Raman spectrum of the P-type coating material is also shown in Figure 12 B. Figure 12 C is the Raman spectrum of the P7-type carbon material used in Example P 26 and P 27 and P.

[0034] Figure 13 A is an image of a light brown powder including a P 28 type coating material. Figure 13 B is the elongated P obtained by content extraction of the N2T1-type template material28 Optical micrograph of the P-type framework. Figure 13 C shows the P 28 TEM micrograph of the 50 - 400 nm unit cell subunits of the P-type framework. Figure 13 D is a HR-TEM micrograph of a BN synthetic anthracite network including a coating wall. The Y dislocation is circled and traced in yellow. Figure 13 E is a HR-TEM micrograph of a BN synthetic anthracite network including a coating wall. The screw dislocation is circled and traced in yellow.

[0035] Figure 14 A is the P 28 superposition of the Raman spectra of the P-type BN framework and the P 27 type BN framework. Figure 14 B is the P 28 superposition of the Raman spectra of the P-type BN framework and the BN@MgO PC material obtained from the P 28 type BN framework. Figure 14 C is the superposition of the Raman spectra of the BN@MgO PC material collected using 0.5 mW and 2.0 mW laser powers.

[0036] Figure 15 A is the optical micrograph of both collapsed and uncollapsed hollow BN frameworks. Many of these frameworks wrinkled during drying but remained intact, as Figure 15 shown in the enlarged inset of A, where the wrinkles in the wrinkled shell can be observed. Figure 15 B is the TEM micrograph of the uncollapsed hollow BN framework. From this and Figure 15 the enlarged TEM micrograph of C, circular and spherical unit cell subunits and thin coating walls can be discerned.

[0037] Figure 16 is the photograph of the powder when taken out of the furnace in Example P 29 Multiple phases can be distinguished.

[0038] Figure 17 A is the optical micrograph of the PC material including the coating BC x grown on the contained MgO. The red indicator in the optical micrograph is positioned on the light phase of the particle and indicates the position where the Raman spectrum in Figure 17 A was collected. The Raman spectrum reveals a broad BN peak and a G peak located at approximately 1595 cm -1 −1. Figure 17 B is the optical micrograph of the PC material including the coating carbon grown on the contained MgO. The red indicator in the optical micrograph is positioned on the dark phase of the particle and indicates the position where the Raman spectrum in Figure 17 B was collected.

[0039] Figure 18 It is a cross-sectional view showing the formation of a surface replica and a coating framework.

[0040] Figure 19 It is a cross-sectional view showing the formation of a coating framework using a porous template.

[0041] Figure 20 It is a cross-sectional view showing the difference between coating frameworks in native and non-native morphological states.

[0042] Figure 21 A is a cross-sectional view showing a synthetic labyrinthine framework. Figure 21 B is an SEM micrograph of the labyrinthine framework.

[0043] Figure 22 A is a TEM micrograph of PC particles (at the top) including a layered carbonaceous coating phase and an MgO content phase, and a coating framework after content extraction (at the bottom). Figure 22 B is an HRTEM micrograph showing a disordered nematic arrangement of graphene layers including a section of the coating wall of a synthetic anthracite network.

[0044] Figure 23 It is a cross-sectional view showing different types of superstructural shapes that can be formed. The cross-hatching represents the unit cell substructure at a smaller scale.

[0045] Figure 24 It is a cross-sectional view showing the formation of a labyrinthine framework under restricted and unrestricted diffusion conditions.

[0046] Figure 25 It is a cross-sectional view depicting four coating frameworks with similar overall volumes but different degrees of compaction.

[0047] Figure 26 It is an illustration of the shuttle technique, where the dissolution of the content, the generation of the stock solution, and the precipitation from the stock solution outside the coating framework are shown to occur simultaneously.

[0048] Figure 27 A is an illustration incorporating a sequence of shuttle, coating separation and concentration of the stock solution by increasing the CO2 pressure, and solvent-free precipitation by decreasing the CO2 pressure. Figure 27 B is an illustration of the use of a pressurized reactor for obtaining content extraction and the formation of a concentrated Mg(HCO3)2 stock solution.

[0049] Figure 28 It includes an SEM micrograph of template precursor particles (N1), which include nesquehonite particles with an elongated superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0050] Figure 29SEM micrograph of template precursor particles (H1), said template precursor particles comprising nesquehonite particles having an equiaxed, hierarchical equiaxed superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0051] Figure 30 SEM micrograph of template precursor particles (H2), said template precursor particles comprising nesquehonite particles having an elongated hierarchical superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0052] Figure 31 SEM micrograph of template precursor particles (H3), said template precursor particles comprising nesquehonite particles having a thin plate-like superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0053] Figure 32 SEM micrograph of template precursor particles (L1), said template precursor particles comprising hydromagnesite particles having an equiaxed superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0054] Figure 33 SEM micrograph of template precursor particles (M1), said template precursor particles comprising magnesite particles having an equiaxed superstructure.

[0055] Figure 34 SEM micrograph of template precursor particles (M2), said template precursor particles comprising magnesite particles having an equiaxed superstructure.

[0056] Figure 35 SEM micrograph of template precursor particles (A1), said precursor particles comprising amorphous magnesium carbonate particles having a hollow hierarchical equiaxed superstructure obtained from an aqueous Mg(HCO3)2 stock solution. Some of the particles comprise thin fragments of a hollow spherical shell.

[0057] Figure 36 SEM micrographs (frames A to D) of template precursor particles having a hollow hierarchical equiaxed superstructure, and TEM micrograph (frame E) of a carbon-coated framework having a hollow hierarchical equiaxed superstructure. In frame A, A2-type precursor particles are shown. In frame B, A3-type precursor particles are shown. In frame E, a coated framework synthesized on a template obtained from A2-type particles is shown.

[0058] Figure 37 SEM micrograph of template precursor particles (C1), said template precursor particles comprising magnesium citrate particles having a hollow hierarchical equiaxed superstructure obtained from an aqueous magnesium citrate stock solution.

[0059] Figure 38Is an optical micrograph of template precursor particles (E1), said template precursor particles comprising epsomite (magnesium sulfate heptahydrate) having an elongated superstructure obtained from an aqueous magnesium sulfate stock solution.

[0060] Figure 39 Includes an SEM micrograph of template precursor particles (H4), said template precursor particles comprising hydromagnesite particles obtained from an aqueous Mg(HCO3)2 stock solution in which lithium carbonate is dissolved at a concentration of 2.71·10 -3 mol kg -1 Li.

[0061] Figure 40 Includes an SEM micrograph of template precursor particles (H5), said template precursor particles comprising hydromagnesite particles having a hierarchical equiaxed superstructure obtained from an aqueous Mg(HCO3)2 stock solution in which lithium carbonate is dissolved at a concentration of 2.74·10 -2 mol kg -1 Li.

[0062] Figure 41 A to Figure 41 C include SEM micrographs of template precursor particles, said template precursor particles comprising magnesite particles having an equiaxed superstructure obtained from an aqueous Mg(HCO3)2 stock solution. Figure 41 A includes M3 type precursor particles. Figure 41 B includes M4 type precursor particles. Figure 41 C includes M5 type precursor particles.

[0063] Figure 42 Includes an optical micrograph of template precursor particles (N2), said template precursor particles comprising nesquehonite particles having an elongated superstructure. This precursor material was obtained from an aqueous Mg(HCO3)2 stock solution which was first used to precipitate lansfordite. The lansfordite was then recrystallized into nesquehonite.

[0064] Figure 43 Includes an optical micrograph of template precursor particles (N3), said template precursor particles comprising nesquehonite particles having an elongated superstructure. This precursor material was obtained from an aqueous Mg(HCO3)2 stock solution which was first used to precipitate lansfordite. The lansfordite was then recrystallized into nesquehonite in the presence of sodium dodecyl sulfate as a surfactant.

[0065] Figure 44Optical micrographs of template precursor particles, said template precursor particles comprising hydromagnesite precipitated tritahydrite particles. Panel A is a micrograph of tritahydrite particles precipitated in the absence of a surfactant. Panel B is a micrograph of tritahydrite particles precipitated in the presence of a surfactant.

[0066] Figure 45 SEM micrographs of template precursor particles (Li1), said template precursor particles comprising lithium carbonate particles having a hollow hierarchical equiaxed superstructure obtained from an aqueous Li2CO3 stock solution. The colored arrows indicate observable diverse features such as pinholes (red), cracks (blue), and wrinkled (yellow) spheres.

[0067] Figure 46 SEM micrographs of porous MgO template particles (N1T1) made from N1 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0068] Figure 47 SEM micrographs of porous MgO template particles (H1T1) made from H1 template precursor particles. The template particles have inherited the hierarchical equiaxed superstructure of the precursor.

[0069] Figure 48 SEM micrographs of porous MgO template particles (H2T1) made from H2 template precursor particles. The template particles have inherited the hierarchical equiaxed superstructure of the precursor.

[0070] Figure 49 SEM micrographs of porous MgO template particles (H1T2) made from H1 template precursor particles. Due to sintering, most of the hierarchical equiaxed superstructure of the precursor has been lost.

[0071] Figure 50 SEM micrographs of porous MgO template particles (M1T1) made from M1 template precursor particles. The template particles have inherited the equiaxed superstructure of the precursor.

[0072] Figure 51 SEM micrographs of porous MgO template particles (M1T2) made from M1 template precursor particles. The template particles have inherited the equiaxed superstructure of the precursor.

[0073] Figure 52 SEM micrographs of porous MgO template particles (M1T3) made from M1 template precursor particles. The template particles have inherited the equiaxed superstructure of the precursor.

[0074] Figure 53SEM micrograph of porous MgO template particles (M1T4) made from M1 template precursor particles. The template particles have inherited the equiaxed superstructure of the precursor.

[0075] Figure 54 Optical micrograph of porous MgSO4 template particles (E1T1) made from E1 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0076] Figure 55 SEM micrograph of porous MgO template particles. In panel A, the porous MgO template particles are made from undoped hydromagnesite particles. The associated subunits are on average 50 nm to 60 nm. In panel B, the porous MgO template particles (H4T1) are made from Li-doped hydromagnesite particles. The template particles include associated subunits that are on average 80 nm to 100 nm, with some subunits up to 200 nm. The template particles have inherited the lamellar morphology of the precursor. In panel C, the porous MgO template particles (H5T1) are made from Li-doped hydromagnesite particles. The associated subunits are on average 100 nm to 300 nm. The template particles have inherited the lamellar morphology of the precursor.

[0077] Figure 56 SEM micrograph of porous MgO template particles (H6T1) made from H6 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0078] Figure 57 A set of SEM micrographs comparing carbon-coated frameworks. In panel A, a P1-type framework is shown, which is made from M3T1P1PC particles. In panel B, a P 19 -type framework is shown, which is made from M4T1P 19 PC particles. In panel C, a P 20 -type framework is shown, which is made from M5T1P 20 PC particles.

[0079] Figure 58 SEM micrograph of porous MgO template particles (M1T4) made from M1 template precursor particles. The template particles have inherited the equiaxed superstructure of the precursor.

[0080] Figure 59 SEM micrograph of PC particles (N2T1P 21 ). The template particles (N2T1) are made by treating N2 template material with heat and water vapor.

[0081] Figure 60Shows the TGA mass loss rate (% / °C) of the N2 template precursor material. In Panel A, the mass loss rates are shown at a sample heating rate of 5 °C / min and a sample heating rate of 20 °C / min under 100 sccm flowing Ar. In Panel B, the mass loss rates are shown at a sample heating rate of 5 °C / min and a sample heating rate of 20 °C / min under 100 sccm flowing CO2.

[0082] Figure 61 SEM micrograph of porous MgO template particles (N2T4) made from N2 template precursor particles. The N2 template precursor material was heated at a rate of 5 °C / min under flowing Ar.

[0083] Figure 62 SEM micrograph of porous MgO template particles (N2T5) made from N2 template precursor particles. The N2 template precursor material was heated at a stepped rate of 20 °C / min under flowing Ar. In Panel A, the red arrow indicates the swelling region of the elongated superstructure characteristic of these template particles. The swelling region is associated with the large internal pores generated during heat treatment. In Panel B, the large internal pores are shown.

[0084] Figure 63 SEM micrograph of porous MgO template particles (N2T6) made from N2 template precursor particles. The N2 template precursor material was heated to a temperature of 350 °C at a heating rate of 20 °C / min under flowing CO2 and then further heated at a heating rate of 5 °C / min.

[0085] Figure 64 SEM micrograph of porous MgO template particles (N2T7) made from N2 template precursor particles. The red arrow indicates a rupture associated with the formation and swelling of large internal pores in the template particles.

[0086] Figure 65 SEM micrograph of a carbon-coated framework made on porous MgO template particles (L2T1). Due to uncontrolled localized recrystallization during the template stage, the framework includes features that are both elongated and thin. The elongated and thin features are indicated by red arrows.

[0087] Figure 66 SEM micrograph of a PC structure and a carbon-coated framework made on porous MgO template particles (L3T1).

[0088] Figure 67 SEM micrograph of PC particles obtained from L3T1 template particles. Panels A and B show the typical superstructure associated with the PC structure. Panel C shows the magnified surface.

[0089] Figure 68 SEM micrograph of porous MgO template particles (A1T1) made from A1 template particles. The yellow box and the magnified inset show the porous substructure of the shell of the hollow spherical particles.

[0090] Figure 69 SEM micrograph of porous MgO template particles (A3T1) made from A3 template particles. The shell contains large pores, which are inherited features also present in the superstructure of the A3 template precursor. Several large pores are circled with a yellow dashed line. Additionally, the shell contains medium pores generated by the decomposition of the A3 template precursor.

[0091] Figure 70 is the carbon-coated framework (P 17 ) produced by content extraction of the Ca1T1P 17 PC material. The framework almost retains its original morphology and reflects the template surface of the template material Ca1T1.

[0092] Figure 71 is the carbon-coated framework (P 18 ) produced by content extraction of the Li1T1P 18 PC material. The framework retains its original morphology and reflects the template surface of the removed template particles.

[0093] Figure 72 Optical micrograph of a mixture produced by content extraction via the shuttle technique. The micrograph in Panel A reveals two distinct phases: nesquehonite particles and the carbon-coated framework. The framework is sometimes deformed, as indicated by the yellow arrows. The micrograph in Panel B reveals one of the carbon-coated frameworks. The area within the yellow square is magnified in the micrograph of Panel C.

[0094] Figure 73 SEM micrograph of spray-dried MgSO4 template precursors (in Panel A) and SEM micrograph of the carbon-coated frameworks obtained from these precursor particles (in Panels B and C). The unit cell substructure of the framework indicates the formation of a porous template from the MgSO4 precursor during the template stage.

[0095] Figure 74 Photo of the liquid-liquid separation result, where hexane is blended into an aqueous mixture of the carbon-coated framework and nesquehonite. The carbon-coated framework migrates to the black hexane phase at the top of the scintillation vial, while nesquehonite remains in the bottom aqueous phase, which appears mostly white (although some carbon particles are mixed in and adhere to the sides of the scintillation vial).

[0096] Figure 75is a photograph showing the initial mixing of the carbon-coated framework by the flask under partial vacuum and its subsequent flotation.

[0097] Figure 76 SEM micrographs of carbon-coated frameworks generated by surface replication on the first nesquehonite template particles followed by content extraction. The substructure includes mesoporous cell subunits that have a consistent equiaxed morphology and size throughout the superstructure. Panel A shows particles imaged at a magnification of 250,000x. Panel B shows particles at 100,000x magnification. Panel C shows particles at 25,000x magnification.

[0098] Figure 77 SEM micrographs of carbon-coated frameworks generated from the first nesquehonite, porous MgO template particles. The frameworks include fibrous and tubular elongated superstructures and cell substructures that include associated subunits, mesoporous subunits, and macroporous subunits.

[0099] Figure 78 SEM micrographs of carbon-coated frameworks generated from the first nesquehonite, porous MgO template particles. The frameworks include both thin and hierarchical equiaxed superstructures and mesoporous cell substructures.

[0100] Figure 79 is an SEM micrograph of a carbon-coated framework generated from first nesquehonite template particles. Mechanical agitation during content extraction has produced individualized thin particles that stack on top of each other.

[0101] Figure 80 is an SEM micrograph of a carbon-coated framework generated from first nesquehonite template particles. Long heat treatment during the template stage and mechanical agitation during content extraction have produced smaller subunit clusters with no obvious higher-order organization.

[0102] Figure 81 is an SEM micrograph of a carbon-coated framework generated from first nesquehonite, sintered MgO template particles. The framework includes quasi-polyhedral cell subunits with a diameter greater than 100 nm.

[0103] Figure 82 includes optical micrographs of carbon-coated frameworks rebounding from a non-native shrunk state produced by evaporation drying to their native architecture.

[0104] Figure 83 SEM micrographs of carbon-coated frameworks generated from elongated template particles (N2T4). These carbon frameworks include flexible porous carbon fibers, as shown in Panel A. The cell substructure is blurred due to deformation of the thin coating walls, as shown in Panel B.

[0105] Figure 84SEM micrographs of carbon-coated frameworks generated from elongated template particles (N2T8). These carbon frameworks show damage and fuzziness.

[0106] Figure 85 Including those generated through N2T1P 21 Content extraction of PC particles yields carbon-coated frameworks (P 21 ).) SME micrographs. Through van der Waals interactions between the coating walls, the frameworks wrinkle and cohere to each other. The N2T1 template particles are made by treating the N2 template material with heat and water vapor.

[0107] Figure 86 SEM micrographs of carbon-coated frameworks. Panel A shows the frameworks generated on porous MgO template particles (N2T4). Panel B shows the frameworks generated on porous MgO template particles (N2T1). The N2T1 template particles are generated after treatment with heat and water vapor, thereby increasing the size of the subunits relative to the N2T4 subunits. This difference in the templates can be observed after content extraction based on the smoother appearance of the frameworks in Panel A and the wrinkled appearance of the frameworks in Panel B.

[0108] Figure 87 SEM micrographs of template precursor particles and carbon-coated frameworks obtained from them. In Panel A, precipitated calcium carbonate (CaCO3) template precursor particles are shown. In Panel B, the carbon frameworks obtained from the templates made from these precursors are shown.

[0109] Figure 88 A through Figure 88 B include photos of the furnace scenarios discussed in the '49195 application and Reference A.

[0110] Figure 89 Is a classification chart showing how graphene networks are classified in the present disclosure. Synthetic anthracite networks including x-carbon and z-carbon are highlighted. Each of these categories is further classified as sp x Networks, intermediate networks, or helicoid-like networks, the latter two of which are formed through the maturation of sp x Networks.

[0111] Figure 90 Is a model of a Schwarz structure network, which is an example of a non-layered graphene network with a helical geometry. The Schwarz surface is shown beside the model.

[0112] Figure 91 Shows a curved two-dimensional surface and identifies the tangent xy plane and the orthogonal z-axis. The spaces above and below the curved surface constitute the z-space.

[0113] Figure 92It is a molecular model of a curved-ring disordered graphene structure. The structure is rotated as indicated by the arrow 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 an enlarged inset of its wavy geometry is shown.

[0114] Figure 93 A to Figure 93 C are diagrams of two scenarios that may occur during a tectonic encounter between two ring-ordered graphene structures. In Figure 93 A, a tectonic encounter is shown. In Figure 93 B, a subduction event that produces an edge dislocation is shown. The subducted lattice is marked with 'x'. In Figure 93 C, a sp 2 grafting event that produces edge coalescence to form a new graphene structure is shown, where some slight ring disorder and curvature are produced.

[0115] Figure 94 A to Figure 94 E are diagrams of 5 model systems used to clarify definitions and concepts related to graphene structures and systems.

[0116] Figure 95 A to Figure 95 D are diagrams used to clarify definitions and concepts related to graphene structures and Y dislocations. Figure 95 D highlights the diamond-like seam in the Y dislocation.

[0117] Figure 96 A to Figure 98 C are photos of various equipment used in the program presented in this public display.

[0118] Figure 97 is an SEM micrograph of the coated frame of sample A1. The translucent regions of the coated wall are circled in yellow.

[0119] Figure 98 A to Figure 98 C are TEM micrographs of sample A1 at different magnification levels. At the highest magnification level, the nematic alignment of the coated wall is shown. The yellow line traces the layers of the nematic alignment. The enlarged inset shows the Y dislocation.

[0120] Figure 99 is a TEM micrograph of another coated frame that further demonstrates the concept of nematic alignment.

[0121] Figure 100 A to Figure 100 D are diagrams showing different structural dislocations and their associated appearances in TEM micrographs.

[0122] Figure 101is part of the single-point Raman spectrum of Sample A1, with the region of interest indicated by the yellow circle, such as the unfitted G band (G u ), the unfitted Tr band (Tr u ), the unfitted D band (D u ), and the unfitted shoulder between 1100 - 1200 cm -1 . The inset shows the entire Raman spectrum of Sample A1. The spectrum was acquired using a 532 nm laser with a power setting of 2 mW.

[0123] Figure 102 Shows two fitted peaks (f-1, f-2), the fitted line shape, the actual line shape, and the residual representing the difference between the fitted line shape and the actual line shape of the Raman line shape of Sample A1. Also shows the peak type, peak position, peak height, peak fwhm, and peak area of the fitted peaks in tabular form.

[0124] Figure 103 Shows three fitted peaks (f-1, f-2, f-3), the fitted line shape, the actual line shape, and the residual representing the difference between the fitted line shape and the actual line shape of the Raman line shape of Sample A1. Also shows the peak type, peak position, peak height, peak fwhm, and peak area of the fitted peaks in tabular form.

[0125] Figure 104 Shows four fitted peaks (f-1, f-2, f-3, f-4), the fitted line shape, the actual line shape, and the residual representing the difference between the fitted line shape and the actual line shape of the Raman line shape of Sample A1. Also shows the peak type, peak position, peak height, peak fwhm, and peak area of the fitted peaks in tabular form.

[0126] Figure 105 Shows two fitted peaks (f-1, f-2, f-3, f-4), the fitted line shape, the actual line shape, and the residual representing the difference between the fitted line shape and the actual line shape of the Raman line shape of Sample A1 after annealing. Also shows the peak type, peak position, peak height, peak fwhm, and peak area of the fitted peaks in tabular form.

[0127] Figure 106 is the XRD line shape of Sample A1, where three fitted peaks are labeled I, II, and III.

[0128] Figure 107 is the thermal oxidation line shape of Samples A1, A2, and A3 obtained from thermogravimetric analysis (TGA), which was run in air at a heating rate of 20 °C / min. The graph shows the derivative of the mass loss of the samples with respect to temperature.

[0129] Figure 108 is the SEM micrograph of Sample A2, which shows a coated frame that appears to be fragmented and damaged during processing.

[0130] Figure 109 A to Figure 109 C are TEM micrographs of sample A2 at various magnifications. In Figure 109 A, a damaged coating framework can be observed. In Figure 109 B, a section of the coating wall is shown. In Figure 109 C, the graphite layering of the coating wall is shown. The dark stripe lines are outlined in yellow.

[0131] Figure 110 Shows a single-point Raman spectrum of sample A2 obtained using a 532 nm laser with a power setting of 2 mW.

[0132] Figure 111 Is an SEM micrograph of compressed sample A1, which shows a coating framework maintaining a three-dimensional macroporous morphology with linear features in the wall due to buckling. The magnified inset shows the buckled wall.

[0133] Figure 112 Is an SEM micrograph of compressed sample A2, which shows a paper-like assembly of a broken flattened framework.

[0134] Figure 113 A to Figure 113 C are SEM micrographs of the coating framework in sample A3. Figure 113 A shows the polyhedral morphology and large atomically flat facets of the coating framework. Figure 113 B shows a transparent window and a more opaque border. Two windows of the wall are circled and shaded in yellow. Figure 113 C shows the concave curvature of the transparent window extending across the border.

[0135] Figure 114 Is an SEM micrograph of the polyhedral MgO template used to generate sample A3.

[0136] Figure 115 A to Figure 115 C are TEM micrographs of sample A3 at various magnifications. In Figure 115 A, the cubic shape of the macroporous subunits of the coating framework is shown. The edges of the cube are highlighted with yellow dashed lines. The yellow solid line highlights the more electron-transparent window. Figure 115 B shows a section of the coating wall. The magnified inset shows an example of a Y dislocation found within the stripes. Figure 115 C shows a wall with uniform thickness, even in the transparent "window" regions found within the flat areas. This indicates that electron transparency is correlated with the lack of local sp 3 state.

[0137] Figure 116Shows a portion of the single-point Raman spectrum of sample A3. The features of interest are indicated by yellow circles. The features include the unfitted G band (G u ), the unfitted Tr feature (Tr u ), the unfitted D band (D u ), and the unfitted shoulder between 1100 - 1200 cm -1 . The conventional G peak position at 1585 cm -1 is marked with a dashed line, revealing the blue shift of the G u peak of sample A3. The inset shows the entire Raman spectrum of sample A3. The spectrum was acquired using a 532 nm laser with a power setting of 2 mW.

[0138] Figure 117 is a diagram of a hypothetical zigzag - zigzag geological structure interface formed between two ring - disordered primitive domains (G1 and G2). The participating edge segments are labeled E1 and E2. The E1 - E2 interface includes three different interface regions - offset region I, offset region II, and the horizontal region. For ease of visual inspection, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspectives are shown. In the H2 perspective, the highlighted yellow part is in the background.

[0139] Figure 118 Shows the sp 2 grafting across the horizontal region of the E1 - E2 interface. The resulting sp 2 ring forms a ring connection between G1 and G2, thereby generating a new graphene structure G3. For ease of visual inspection, labeled and unlabeled vertical (V) and horizontal (H1 and H2) perspectives are shown. In the H2 perspective, the highlighted yellow part is in the background.

[0140] Figure 119 Shows the sp 3 grafting across the offset region of the E1 - E2 interface. The new sp 2 atoms are represented as black circles. The new sp 3 atoms are represented as black - and - white circles. The resulting sp x ring includes 4 rings (R1, R3, R5, R6) in a chair conformation and 2 chiral rings (R 2-C , R 4-C ) associated with the transition of the geological structure region. The chiral chains within the 2 chiral rings are indicated by blue arrows, and 5 sp 3 - sp 3 bonds are indicated by red lines. The point - reflection orientation of the rings in the chair conformation and the 2 sp 3 - sp 3 bond lines are shown. The elevated tertiary radicals generated by sp 3 grafting across the offset region are labeled. The chiral ring R 2-CThe structure, where its chiral ring is highlighted in blue and its sp 3 -sp 3 bonds are highlighted in red. For visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow part is in the background.

[0141] Figure 120 is the continuous z-direction growth that occurs at five elevated tertiary free radicals from Figure 119 . The new sp 3 atoms are represented as black and white circles. Four rings (R1, R3, R5, R6) in chair conformation and two chiral rings (R 2-C , R 4-C ) are marked. For visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted part is in the background. The resulting second-level sp 3 -sp 3 bonds are represented by red lines. For visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow part is in the background.

[0142] Figure 121 is a diagram after continuous radical addition on the base layer. The new sp 2 atoms are represented as black circles. The new sp 3 atoms are represented as black and white circles. Three new sp x rings (R7, R8, R9) in chair conformation and two chiral rings (R 2-C , R 4-C ) are marked. The addition of sp x rings in chair conformation produces two diamond-like seams, as isolatedly shown in the inset of the H1 perspective view. These two diamond-like seams form the intersection of two Y dislocations, as shown by the shaded Y shape in the inset of the H1 perspective view. For visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspective views are shown. In perspective view H2, the highlighted yellow part is in the background.

[0143] Figure 122 is a diagram after continuous radical addition on the base layer. The new sp 2 atoms are represented by solid black circles, and the new sp 3 atoms are represented by black and white circles. The third-level sp 3 -sp 3 bonds are highlighted in red. Three new sp x rings (R 10 , R13 , R 14 ), and 1 new chiral ring (R 11-C ). The chiral ring R 11-C is located above the chiral ring R 4-C ), thus generating a chiral column. The chiral column is shown isolated. The chiral chains 1 to 6 and 7 to 12 are indicated by blue arrows. For ease of visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspectives are shown. In perspective H2, the highlighted yellow part is in the background.

[0144] Figure 123 is a diagram after continuous radical addition above the base layer. The rings above the base have coalesced, and the second layer has nucleated. There are now 4 chiral rings (R 2-C , R 4-C , R 11-C , R 12-C ), thus forming 2 chiral columns. For ease of visual inspection, marked and unmarked vertical (V) and horizontal (H1 and H2) perspectives are shown. In perspective H2, the highlighted yellow part is in the background.

[0145] Figure 124 is a diagram after continuous radical addition above the base layer. The third layer has nucleated. One of the cubic diamond-like seams is blackened in the enlarged inset. Another cubic diamond-like seam is highlighted in yellow in the second enlarged inset, and the chiral columns representing the lateral ends of the seam are highlighted in blue (chiral chains) and red (z-direction sp 3 -sp 3 chains). For ease of visual inspection, vertical (V) and horizontal (H1 and H2) perspectives are shown.

[0146] Figure 125 A is Figure 124 an enlarged view of the horizontal perspective (H2). The chiral column is highlighted. The chiral chains in the chiral ring are highlighted in blue, while the z-direction chains of the sp 3 -sp 3 bonds connecting the z-adjacent chiral rings are highlighted in red. In Figure 125 B, the chiral column structure is represented in a simplified diagrammatic form. In Figure 125 C, the sp x helix within each chiral column is isolated.

[0147] Figure 126 A is an SEM micrograph of the C@MgO PC structure specific to samples B1 to B3. MgO can be observed as bright charged regions. In Figure 126 the SEM micrograph of B, the content MgO template has been removed, thus leaving the coated framework specific to samples B1 to B3. In Figure 126In the SEM micrograph of C, a cell sheet stratified coating framework unique to sample B4 is shown.

[0148] Figure 127 A through Figure 127 D show the Raman spectra of samples B1 - B4. Figure 127 B indicates the spectral trend observed with decreasing temperature.

[0149] Figure 128 Shows a zigzag - zigzag geological structure interface produced by grafting through interstitial atom lines to generate a sp x ring in a boat conformation.

[0150] Figure 129 Shows a zigzag - armchair geological structure interface grafted by two z - adjacent lines of 5 - and 7 - membered sp x rings. These 5 - and 7 - membered rings are highlighted in yellow.

[0151] Figure 130 Shows a zigzag - armchair geological structure interface produced by grafting through interstitial atom lines to generate a sp x ring in a boat conformation. These boat conformations are highlighted in yellow.

[0152] Figure 131 Is a diagram representing the growth of multiple primitive domains above a common substrate surface, their grafting, and the nucleation and growth of higher layers. The "X" structures represent diamond - like seams. Some diamond - like seams propagate vertically while others do not. New diamond - like seams are shown to form due to higher - layer geological activity.

[0153] Figure 132 Is the XRD profile of sample B4.

[0154] Figure 133 Are images of samples C1 and C2, which show the degree of brownness of these hydrogenated carbons.

[0155] Figure 134 Is the FTIR of sample C2. Indicates the hydrogenation of this brown coal sample.

[0156] Figure 135 Are the Raman spectra of samples C1 and C2. In each case, a sub - peak at ~600 cm -1 has been observed and attributed to non - hydrogenated nanodiamond. This is an indication of the non - hydrogenated phase of samples C1 and C2.

[0157] Figure 136 Are photographs of samples E1 and E1A of equivalent mass, which show the more granular consistency of sample E1 and the finer and larger - volume properties of sample E1A.

[0158] Figure 137 A throughFigure 137 C is the SEM micrograph of sample E1 (unannealed), and Figure 137 D through Figure 137 F are the SEM micrographs of sample E1A (annealed). Figure 137 The comparison of A with Figure 137 D indicates greater densification and granulation occurring in sample E1 compared to sample E1A. Figure 137 The comparison of B with Figure 137 E shows greater flexibility and tissue - like bending of the coating framework in sample E1, and greater stiffness of the coating framework of sample E1A. Figure 137 The comparison of C with Figure 137 F shows the less distinct sub - structure of the coating framework in sample E1 compared to the more distinct sub - structure of the stiffened sample E1A framework.

[0159] Figure 138 A through Figure 138 C are the SEM micrographs of sample E2, and Figure 138 D through Figure 138 F are the SEM micrographs of sample E2A. Figure 138 The comparison of A with Figure 138 D indicates greater densification and granulation occurring in sample E2 compared to sample E2A. Figure 138 The comparison of B with Figure 138 E shows greater flexibility and tissue - like bending of the coating framework in sample E2, and greater stiffness of the coating framework of sample E2A. Figure 138 The comparison of C with Figure 138 F shows the less distinct sub - structure of the coating framework in sample E2 compared to the more distinct sub - structure of the stiffened sample E2A framework. Figure 138 E through Figure 138 F also indicates the fusion of the stacked plates in sample E2A.

[0160] Figure 139 is the SEM image of the MgO template for generating the unit - cell sheet framework used in study E.

[0161] Figure 140 Shows the Raman spectral effects associated with the maturation of the sp x precursor.

[0162] Figure 141 Shows the maturation - induced disintegration of the monomeric structure including cubic diamond - like seams.

[0163] Figure 142 Shows the role of chiral rings and chiral columns in maintaining perpendicular cross - linking during maturation.

[0164] Figure 143 is a diagram showing the sp x helix to sp 2Illustration of the transformation of the helix.

[0165] Figure 144 Shows sp 2 The helix around sp 2 Illustration of the formation of the helix.

[0166] Figure 145 Shows Figure 124 Of sp x Maturation of the precursor to the helical monomer.

[0167] Figure 146 Provides enhanced visual discrimination Figure 145 Another perspective showing the ring connectivity of the helical monomer shown.

[0168] Figure 147 Is the XRD profile of sample B4A.

[0169] Figure 148 Shows an alternative situation of the E1 - E2 interface where the edges of G1 and G2 do not cross. It has been shown that in this situation, the chiral rings R 2-C And R 4-C Have opposite chirality, as indicated by the blue arrows.

[0170] Figure 149 Shows sp x Precursor growing gradually above the E1 - E2 C Geological interface, which is reflected in Figure 117 The modeled E1 - E2 interface, but assuming that sp 2 Grafting is not possible and instead of a horizontal zone, the E1 - E2 interface includes intersections.

[0171] Figure 150 Shows the formation of a double helix due to the disintegration of the sp Figure 149 Precursor constructed above the E1 - E2 C Geological interface in x

[0172] Figure 151 Shows the complete unzipping of the basal layer due to the unzipping of the sp C -sp 3 -sp 3 Bond line across the E1 - E2 3-C Two chiral chains in are indicated by blue arrows, and the sp 3 -sp 3 Bond is highlighted in red. The chiral chains are shown to be point - reflected. Sp 2 Atoms are indicated by black circles, while sp 3 Atoms are indicated by black - and - white circles.

[0173] Figure 152 Shown in Figure 150 is the formation of the double helix modeled in Figure 149 and the disintegration induced by the maturation of the sp C precursor constructed above the E1 - E2 x geological tectonic interface. The chiral column constructed above R 3-C is shown to contain the sp x double helix, which transforms into the sp 2 double helix upon maturation.

[0174] Figure 153 A through Figure 153 C show how the absence or presence of the horizontal region and the associated sp 2 grafting affect the ring connectivity of the resulting helical system after maturation.

[0175] Figure 154 A through Figure 154 D show individual and combined helices, including combined helices with common and opposite chirality.

[0176] Figure 155 Shows how a monolayer precursor forms non - interlocking truncated double helices if it disintegrates during maturation.

[0177] Figure 156 Shows how a bilayer precursor forms sufficiently elongated double helices to interlock the helices if it disintegrates during maturation.

[0178] Figure 157 A is a graphical - theoretical representation of monomer - to - monomer maturation. Figure 157 B is a graphical - theoretical representation of monomer - to - assembly maturation.

[0179] Figure 158 Shows how two higher - level pathways extending upward from the base layer can reconnect to form a closed loop.

[0180] Figure 159 A is a TEM micrograph of the macroporous - coated framework from annealed sp x precursor. Figure 159 B is a TEM micrograph of the coated wall. The striped lines exhibit a unique "sliced" pattern, as indicated by the yellow line, which corresponds to the z - displacement of the helical graphene lattice around the dislocation line every 180°. In Figure 159 C, the helix spans more than 10 layers of the helical network, as indicated by the yellow dashed guiding line. In Figure 159 D, the combined - helix loop from the unit - cell wall is magnified. By analyzing the Figure 159 HRTEM image in D, we can see that at the center of these two adjacent helices, the sp2 The helical pitch is less than 1 nm.

[0181] Figure 160 A is a TEM micrograph of a helical x-network including a coated framework with an equiaxed cubic morphology. In Figure 160 B, the controlled mesoporous architecture of the coated framework is shown, with a highly uniform coated wall thickness. In Figure 160 B, the coated wall is shown at a higher magnification. It is on average 2 to 3 layers and appears more kinked than thicker walls due to its increased flexibility.

[0182] Figure 161 is a diagram of three coated frameworks demonstrating the concept of mesoscale crosslinking. The cross-hatching of Structures I, II, and III indicates that their molecular-scale crosslinking is the same. However, their mesoscale crosslinking is different, with I having the highest mesoscale crosslinking and III having the lowest mesoscale crosslinking.

[0183] Figure 162 A is a diagram of a hydroxylated edge formed by the vertical ends of two joined helices. Figure 162 B is a diagram of an orifice representing the entrance to the interlayer labyrinth of the network. These orifices provide ubiquitous entry points for the infiltration or exudation of fluids, as Figure 162 indicated in B.

[0184] Figure 163 A to Figure 163 C is an SEM micrograph of the fracture surface of an epoxy nanocomposite. The nanocomposite includes a 0.5 wt% loading of sp x network. Each embedded coated framework includes a unit cell lamellar morphology (as Figure 163 indicated by the yellow circles in C) as well as the sp x network.

[0185] Figure 164 A to Figure 164 C is an SEM micrograph of the fracture surface of an epoxy nanocomposite. The surface is covered with debris generated by the explosive fracture of the cured epoxy nanocomposite near the coated framework. In Figure 164 B, we can see the result of one such explosive fracture. In Figure 164 C, we can observe that the debris is epoxy fragments physically embedded in the surface.

[0186] Figure 165 are two sp x networks pressed together to form a non-native bilayer that can crosslink during maturation.

[0187] Figure 166 are two sp x networks G in static vdW contactA The illustration of the radical addition reaction with G B is shown in Panel I. The geometric structure of the underlying helix aligns the sp B radicals of G 2 towards G A as shown in Panel II of Figure 166 where the radicals are circled. The radical cascade bonds the multiple rows of sp B radicals of G 2 to the z-adjacent atoms in G A to form an sp 2 ring. This reaction extends the helix across the non-native bilayer as shown in Panel III of Figure 166 and pushes the radical-terminated edge dislocations towards the surface.

[0188] Figure 167 A is a photograph of the sample F1 particles. Figure 167 B is a photograph of the sample F2 flakes.

[0189] Figure 168 to Figure 168[[END D is the N2 adsorption-desorption isotherm of the samples F1 - F4.

[0190] ​ is the pore size distribution chart of the samples F1 - F4.

[0191] ​ A to ​ D are the Raman spectra of the samples F1 - F4.

[0192] ​ shows the Raman spectral changes associated with the maturation of the sample F2 flakes into the sample F3.

[0193] ​ A is a photograph of the buckypaper. ​ B is a photograph of a piece of buckypaper.

[0194] ​ A is the SEM micrograph of the cross-section of the buckypaper. ​ B is the SEM micrograph showing the collapsed coated framework that makes up the buckypaper. ​ C is the SEM micrograph of the K2CO3 template.

[0195] ​ A to ​ D are the photographs depicting the solvent impregnation test of the unannealed buckypaper.

[0196] ​ A to ​ D are the photographs depicting the solvent impregnation test of the annealed buckypaper.

[0197] ​ A to Figure 176 B are the Raman spectra of samples F5 and F6. Figure 176 C is a chart showing the peak positions of samples F5 and F6.

[0198] Figure 177 is fibrous buckypaper made from elongated sp x microstructures.

[0199] Figure 178 A is a SEM micrograph of the fibrous buckypaper. Figure 178 B is a SEM micrograph of the flexible elongated sp x Microbody microstructures.

[0200] Figure 179 A to Figure 179 B are SEM micrographs of the hollow globular frameworks.

[0201] Figure 180 A to Figure 180 B are SEM micrographs of the equiaxed frameworks.

[0202] Figure 181 is a photograph of sample G1 that has undergone resistive heating at 1 atmosphere.

[0203] Figure 182 is a sequence of photographs showing sample G1 exhibiting the Meissner effect.

[0204] Figure 183 A to Figure 183 D are photographs of various disordered carbon samples that have undergone resistive heating at 1 atmosphere.

[0205] Figure 184 A to Figure 184 B are photographs of disordered carbon samples exhibiting the Meissner effect.

[0206] Figure 185 A to Figure 185 B are photographs of disordered carbon samples exhibiting flux pinning in the presence of a neodymium magnet.

[0207] Figure 186 A is a TEM micrograph showing a typical coated framework in sample G1. Figure 186 B is the XRD profile of sample G1. Figure 186 C is the Raman spectrum of sample G1.

[0208] Figure 187 is a model showing the growth of the sp x layer around the underlying template surface within the sp x network to completion. This can be considered a transverse cross-section of the sp x network.

[0209] Figure 188 A is a photograph of the flaky MgO template used in Study H. Figure 188 B is a photograph of the porous PC structure formed on the MgO flakes.

[0210] Figure 189 is a photograph of the contact between the four-point probe and the PC material in Study H.

[0211] Figure 190 is a graph of the sample sheet resistance versus chamber pressure in Study H.

[0212] Figure 191 is the Raman spectrum of the sample used in Study H. The Raman spectrum did not change after the tests performed in Study H.

[0213] Figure 192 is a schematic diagram showing a method of forming an ambient superconducting article such as a filament by evacuating internal gas, applying an impermeable barrier phase, and then restoring the article to ambient external pressure.

[0214] Figure 193 is a photograph of the probe tip showing the melted area of the plastic housing where probe tip heating occurred. The melted area is circled.

[0215] Figure 194 : A diagram representing the process of surface replication that starts with defect-catalyzed nucleation on the template surface, followed by conformal growth above the template surface.

[0216] Figure 195 : SEM image of the K2SO4 oxyanion template precursor powder.

[0217] Figure 196 : SEM image of the PC structure produced by growing carbon coating on the oxyanion template.

[0218] Figure 197 : SEM image of the wrinkled carbon-coated framework including graphene carbon.

[0219] Figure 198 : Optical micrograph of the MgSO4·7H2O template precursor crystal.

[0220] Figure 199 : SEM image of the PC structure produced by growing carbon coating on the oxyanion template.

[0221] Figure 200 : SEM image of the carbonaceous coating framework synthesized on the porous oxyanion template.

[0222] Figure 201: Average Raman spectra of the carbonaceous coated frameworks generated in Experiments 1 - 5.

[0223] Figure 202 : Unsmoothed and smoothed average Raman spectra of the carbonaceous coated framework generated in Experiment 3.

[0224] Figure 203 : SEM images of the PC structures synthesized in Experiment 3.

[0225] Figure 204 : SEM images of the buckypaper and lamellar wrinkled coated fragments produced by growth on a Li2CO3 template.

[0226] Figure 205 : SEM images of the lamellar wrinkled coated fragments produced by growth on a Li2CO3 template. The individual graphene lattices within the coated walls are outlined.

[0227] Figure 206 is an overview of the exemplary samples P 24 through P 29 discussed in Sections I through IV.

[0228] Figure 207 is an overview of exemplary types of template precursor materials, template materials, PC materials, and coating materials.

[0229] Figure 208 Outlines the expected Raman peak positions and TGA mass losses for several MgCO3·xH2O template precursor materials.

[0230] Figure 209 Outlines the N2 gas adsorption analysis for the template materials M3T1, M4T1, M5T1, M3T2, M4T2, and M5T2.

[0231] Figure 210 Outlines the N2 gas adsorption analysis for the template materials N2T1 and N2T2.

[0232] Figure 211 Shows the template precursor materials, carrier gas, furnace program, heating rate for each heat treatment segment, temperature settings, and isothermal duration for the template materials N2T3, N2T4, N2T5, and N2T6.

[0233] Figure 212 is an overview of all the template materials used in the following exemplary replication stage procedures. Figure 212 Includes the basic parameters for fabricating the template materials, including the template precursor materials, furnace program for the template stage treatment, and temperature, time, heating rate, carrier gas, and gas flow rate related to the template stage treatment.

[0234] Figure 213It is an overview of the surface replication parameters used in the exemplary replication stage program.

[0235] Figure 214 Overview the Raman indicators and yields of the exemplary carbonaceous coated frameworks.

[0236] Figure 215 Overview the conditions associated with the classification of "minimal grafting", "partial grafting", and "highly grafted" carbonaceous sp x networks.

[0237] Figure 216 Present the XRD peak angles, d-spacing, area, area percentage, and FWHM values of sample A1.

[0238] Figure 217 Present the XRD peak angles, d-spacing, area, area percentage, and FWHM values of sample A2.

[0239] Figure 218 Present the Raman spectral information of samples B1 - B4.

[0240] Figure 219 Present the XRD peak angles, d-spacing, area, area percentage, and FWHM values of sample B4.

[0241] Figure 220 Present the Raman spectral information of samples C1 and C2.

[0242] Figure 221 Present the Raman spectral information and approximate carbon yields of samples D1 and D2.

[0243] Figure 222 Present the Raman spectral information of samples E1, E1A, E2, and E2A.

[0244] Figure 223 Present the XRD peak angles, d-spacing, area, area percentage, and FWHM values of sample B4A.

[0245] Figure 224 Show the BET surface area and BJH pore volume data of samples F1 - F4.

[0246] Figure 225 Show the Raman spectral information of samples F5 and F6.

[0247] Figure 226 Present the XRD peak angles, d-spacing, area, area percentage, and FWHM values of sample G1.

[0248] Figure 227 Present the basic information on the synthesis of the exemplary template precursor in reference C.

[0249] Figure 228It is an overview of the surface replication parameters used in an exemplary replication stage program.

[0250] Figure 229 Presents Raman spectroscopic information of the coating materials obtained in Experiments 1 - 5. Detailed implementation

[0251] The detailed description of the present disclosure is organized according to the following parts:

[0252] I. Terms and concepts

[0253] II. Description of general methods and variations

[0254] III. Furnace protocols, analytical techniques, and material nomenclature

[0255] IV. Coating framework examples

[0256] V. Reference A: Detailed description from the '49195 application

[0257] VI. Reference B: Detailed description from the '37435 application

[0258] VII. Reference C: Detailed description from the '154 application

[0259] Notes on References A - C

[0260] The purpose of including References A - C in the present disclosure is to enable quick reference to the detailed descriptions of these related patent applications and to concentrate the exposition as much as possible in the expositions of Parts I - IV.

[0261] Part V or "Reference A" is the detailed description of the specification from the '49195 application, which teaches the scalable synthesis of carbonaceous coating materials (a subset of the larger class of coating materials). The detailed description included in Reference A has been modified in certain ways to harmonize its presence in the present disclosure and to avoid the confusion that might otherwise arise from its inclusion. For example, in cases where figures are cited in Reference A, the original numbers of the figures in the '49195 application have been changed as needed to avoid redundancy. The names of the specific furnace protocols originally presented in the '49195 application have been renamed in Reference A to avoid redundancy with the furnace protocols labeled in other parts of the present disclosure. The measurement results and data reported in Reference A were measured according to the analytical techniques specified in Reference A and not necessarily according to the analytical techniques specified in other parts of the present disclosure. Finally, the parts originally numbered with Roman numerals in Reference A are labeled with single asterisks (e.g., the content originally labeled as Part I in the '49195 application is labeled as Part I* in Reference A).

[0262] Part VI or "Reference B" is the detailed description from the specification of the '37435 application, which teaches the synthesis of graphene networks (a subset of the larger class of encapsulating materials). The detailed description included in Reference B has been modified in certain ways to reconcile its presence in this disclosure and to avoid the confusion that might otherwise result from including it. For example, in cases where figures are referenced in Reference B, the original numbers of the figures in the '37435 application have been changed as needed to avoid redundancy. The names of specific furnace protocols originally presented in the '37435 application have been renamed in Reference B to avoid redundancy with the furnace protocols designated in other parts of this disclosure. The measurement results and data reported in Reference B were measured according to the analytical techniques specified in Reference B and not necessarily according to the analytical techniques specified in other parts of this disclosure. Finally, the parts originally numbered with Roman numerals in Reference B are marked with double asterisks (e.g., what was originally designated as Part I in the '37435 application is designated as Part I** in Reference B).

[0263] Part VII or "Reference C" is the detailed description from the specification of the '154 application, which teaches surface replication on certain soluble templates (a subset of the larger class of templates that can be used according to a general method). The detailed description included in Reference C has been modified in certain ways to reconcile its presence in this disclosure and to avoid the confusion that might otherwise result from including it. For example, in cases where figures are referenced in Reference C, the original numbers of the figures in the '154 application have been changed as needed to avoid redundancy. The names of specific furnace protocols originally presented in the '154 application have been renamed in Reference C to avoid redundancy with the furnace protocols designated in other parts of this disclosure. The measurement results and data reported in Reference C were measured according to the analytical techniques specified in Reference C and not necessarily according to the analytical techniques specified in other parts of this disclosure. Finally, the parts originally numbered with Roman numerals in Reference C are marked with triple asterisks (e.g., what was originally designated as Part I in the '154 application is designated as Part I*** in Reference C).

[0264] We further note that the material naming scheme used in the '49195 application is adopted again in Parts I through IV of this disclosure, and the numbering in this disclosure continues where the numbering in the '49195 application breaks. This is done to facilitate easy reference to the previously described materials and procedures and to avoid confusion. The continuity of the numbering does not imply that this disclosure is a continuation or supplement to any prior disclosure.

[0265] The compatibility and combinability of many of the exemplary techniques, procedures, and materials set forth in Parts I through VII will be apparent to a knowledgeable practitioner in the art. For example, Raman spectroscopic features associated with the exemplary x-carbon shown in Part VI may be readily obtained in a coated framework including the hollow superstructure shown in Part V. Generally speaking, Parts I through VII disclose a general and industrially scalable method for producing architected nanostructured materials, and these parts describe a variety of coating materials.

[0266] I. Terms and Concepts

[0267] In any case where there is a contradiction between the definition or description of a term or concept in References A through C and the definition or description of the same term or concept in Parts I through IV, the definition or description of the set of terms or concepts set forth in Parts I through IV shall be understood to be authoritative in this disclosure. In any case where a term or concept is defined or described in Parts A through C and there is no contradiction with the corresponding definition or description in Parts I through IV, the definition or description set forth in Parts A through C shall be understood to be authoritative in this disclosure.

[0268] As defined herein, a "stratified" coated framework includes a multiphase framework in which two or more different coating layers can be identified within the coating wall. When describing a stratigraphic pattern, this disclosure describes the pattern with a string of letters, where each different layer is represented by a letter, the position of a layer relative to other layers is represented by the position of its letter in the string of letters relative to the other letters, and compositionally similar layers are denoted by the same letter. Thus, the string of letters AB represents a coating wall including two different and compositionally dissimilar layers, while the string of letters BAB represents a coating wall including three different layers, with one inner layer sandwiched between two outer layers that are compositionally similar.

[0269] As defined herein, a "coating layer" (or "layer") includes a different phase within a coating wall having a stratigraphic organization. Coating layers generally have an overall arrangement and topology similar to other coating layers and to the coating wall itself. For example, a coating wall may include a graphene layer positioned above or below a silica layer. Even all-carbon coating walls may include different carbon layers, as described in the '580 application.

[0270] As defined herein, "pre-extraction replication" includes surface replication techniques performed prior to content extraction. Pre-extraction replication can be used to exclusively adsorb an adsorbate to one side of an existing coating material, thereby producing an A → AB → ABC construction of the coating wall (where A is synthesized on a template surface, then B is synthesized on A, then C is synthesized on B, and then content extraction is performed).

[0271] As defined herein, "post-extraction replication" includes surface replication techniques performed after content extraction. Post-extraction replication can be used to adsorb an adsorbate onto both sides of an existing coating material, thereby creating an A→BAB→CBABC construction of the coating wall (where A is synthesized on the template surface, then content extraction is performed, then a B layer is synthesized on both sides of A, and then a C layer is synthesized on both sides of the BAB formation).

[0272] Pre-extraction and post-extraction replication strategies can be combined. For example, an ABC stratification can be obtained by sequential pre-extraction replication. Subsequently, post-extraction replication can be utilized to obtain a DABCD stratification.

[0273] As defined herein, "stratigraphic occlusion" includes using one or more coating layers to occlude another coating layer in a conformal configuration. One way to achieve stratigraphic occlusion is to use post-extraction replication techniques to obtain a BAB-type stratification, where the coating layer (A) is occluded by two conformal coating layers (B).

[0274] As defined herein, "stratigraphic encapsulation" includes using one or more coating layers to encapsulate a coating framework. One way to achieve stratigraphic encapsulation is to apply a coating layer around the perimeter of an existing coating framework.

[0275] As defined herein, "two-dimensional" materials include materials having a bonding configuration that produces an atomic monolayer structure over small distances.

[0276] Figure 1 A shows an AB stratification arrangement. In this illustration, both A and B are substantially present throughout the framework and share a common topology imparted by the template surface. Figure 1 B shows a BAB stratification arrangement, where A is stratigraphically occluded by two conformal B layers that share a common topology with A. Figure 1 C shows another AB stratification arrangement. In this illustration, B is not present throughout the framework and does not share a common topology with A. Instead, B is only present around the perimeter of the framework. It encapsulates the entire framework rather than being present throughout the coating wall. This stratigraphic encapsulation can be facilitated by applying a B layer that is not conformal to the A layer everywhere and may cover or block the extra-cellular pores of the framework in some places.

[0277] Figure 2Two potential approaches for synthesizing a layered coated framework are shown. A hypothetical PC structure synthesized by pre-copying before extraction is shown. From this point on, two approaches can be used to synthesize a layered coated framework. In the upper approach, content extraction is first performed on the PC, and then a new coating layer is adsorbed onto the existing coating framework using post-extraction replication techniques, resulting in a layered coated framework. In the lower approach, a second pre-extraction replication technique is first performed on the PC, resulting in a layered PC structure, and then content extraction is used to remove the content template material, resulting in a layered coated framework.

[0278] II. Description of General Methods and Variants

[0279] The "general method" is the most basic form of the method and is applicable to the synthesis of coated products of any chemical composition. It includes a method for synthesizing a coated product in which most of the template material and process liquid are preserved and reusable. Therefore, the general method can be performed cyclically. All variants of the methods disclosed in this disclosure include some variant of the general method.

[0280] The general method includes a series of steps presented herein for ease of description in 4 stages, namely, the precursor stage, the template stage, the replication stage, and the separation stage. Each stage is defined according to one or more steps as described below:

[0281] Precursor stage: The precursor material is obtained from a stock solution by solventless precipitation. A portion of the process liquid is preserved.

[0282] Template stage: The precursor material formed in the precursor stage is modified through one or more processes to form the template material.

[0283] Replication stage: The adsorbate material is adsorbed onto the template surface of the template material to form the coating material, and the coating material and the content template material together form the PC material.

[0284] Separation stage: Content extraction and coating separation are performed. The stock solution is obtained through content extraction. Coating separation separates the coated product from the preserved process material.

[0285] In practice, each step within these stages can itself include multiple subsidiary steps. Additionally, each step in these steps can occur simultaneously with steps from another stage, such that in practice different stages can overlap in chronological order. This is particularly anticipatable in variants that employ a one-pot technique. As a hypothetical example of this, the stock solution and the adsorbate material can be continuously sprayed into a furnace together. In this hypothetical furnace, continuously and simultaneously, precursor particles can be precipitated from the stock solution, template particles can be formed by heating the precursor particles, and the coating material can be adsorbed onto the template particles. This would correspond to the steps respectively attributed herein to the precursor stage, the template stage, and the replication stage.

[0286] Similarly, it is contemplated that, in practice, many variations of the general method can incorporate the steps described in the four phases in different orders. Moreover, in some variations, steps that are defined to belong to one of the four phases herein can alternatively occur in different phases. Such variations are contemplated herein and do not depart from the method of the present invention, which is presented herein only as a discrete sequence of four phases for the purpose of describing the overall cycle.

[0287] Ancillary processing steps (e.g., rinsing, drying, blending, condensing, spraying, stirring, etc.) can also be incorporated into each phase of the method. As a hypothetical example of this, the replication phase can involve coating a template material with a coating material via a liquid-phase adsorption procedure and then filtering, rinsing, and drying the resulting PC material. Incorporating these processing steps in many variations will be obvious to those skilled in the art, and thus, these steps are not enumerated herein.

[0288] The inputs and outputs of the general method are shown in Figure 3 The general method includes a template cycle by which the template material can be preserved and reused, and a liquid cycle by which the process liquid can be preserved and reused.

[0289] Variations of the general method

[0290] The following discussion enumerates various ways in which the general method can be implemented differently. The omission of variations in this discussion should not be construed as restrictive, as an exhaustive list of ways to implement the general method is impracticable.

[0291] The general method is intended to provide a way to cyclically produce coated products while preserving process materials. In each cycle of the general method, a portion of the process materials used is preserved and reused. In some variations, substantially all of the process materials used can be preserved and reused. In other variations, a portion of the process materials may be lost. A hypothetical example of this is the evaporation loss of process liquid from an open tank or a wet filter.

[0292] In some variations of the general method, the process steps can correspond to a batch process. In other variations, the process steps can correspond to a continuous process.

[0293] In some variations of the general method, solventless precipitation can include at least one of the following techniques: heating or cooling a stock solution to change the solubility of the solute in the stock solution; volatilizing dissolved gas within the stock solution; subjecting the stock solution to reduced pressure; atomizing the stock solution; spray drying the stock solution or spray pyrolysis.

[0294] In some variants of the general method, the precursor structure may include at least one of the following: an elongated, thin, equiaxed or hierarchically equiaxed superstructure; an elongated superstructure with an aspect ratio greater than 200:1; an elongated superstructure with an aspect ratio between 50:1 and 200:1; a spheroid or spherical superstructure; a hollow superstructure; a fragmented superstructure including fragments of some other parent superstructure; a curved fragmented superstructure including fragments of a hollow superstructure.

[0295] In some variants of the general method, the precursor structure may precipitate around one or more other sacrificial structures, which may be present as inclusions in the precursor structure after the precursor structure has precipitated. In some variants, these inclusions in the precursor structure may then be removed, creating voids.

[0296] In some variants of the general method, the measurement along the long axis of the precursor structure may be less than 1 μm. In some variants, the measurement along the long axis of the precursor may be between 1 μm and 100 μm. In some variants, the measurement along the long axis of the precursor may be between 100 μm and 1,000 μm.

[0297] In some variants of the general method, the precursor material may include at least one of the following: a hydrate; a metal hydroxide; a metal bicarbonate or carbonate; a Group I or II metal bicarbonate or carbonate; a mixture of salts. In some variants, the precursor may include MgCO3·xH2O in at least one of the following forms: hexahydrate, nesquehonite, lansfordite, hydromagnesite, artinite, magnesite, and nanocrystalline or amorphous structures.

[0298] In some variants of the general method, the stock solution may include at least one of the following: metal cations and oxyanions; an aqueous solution of a metal bicarbonate; a Group I or II metal bicarbonate; an organic salt; Mg(HCO3)2. In some variants, the stock solution may include at least one of a dissolved gas, an acid, and a base. In some variants, the stock solution may be metastable.

[0299] In some variants of the general method, the process liquid preserved in the precursor stage may include distillate. In some variants, the distillate may be formed by condensing the process liquid vapor formed during spray drying or spray pyrolysis. In some variants, the process liquid preserved in the precursor stage may carry solvated ions, and the process liquid and the ions together constitute the mother liquor.

[0300] In some variations of the general method, the treatment performed on the precursor material during the templating stage may include at least one of the following: heating the precursor; decomposing the precursor; partially or locally decomposing the precursor; decomposing the precursor surface; thermally decomposing the precursor; and oxidizing the organic phase present within the precursor structure. In some variations, the treatment may include at least one of flash drying, spray drying, spray pyrolysis, vacuum drying, rapid heating, slow heating, and sublimation. In some variations, the vapors released during the treatment may be preserved. In some variations, the released vapors may include at least one of CO2 and H2O. In some variations, the treatment may include at least one of the following: roughening the grain structure of the precursor or the decomposition product of the precursor; exposure to reactive vapors; exposure to water vapor; sintering; and sintering assisted by a dopant.

[0301] In some variations of the general method, the template material may include at least one of the following: metal hydroxides, metal sulfates, metal carbonates, metal nitrates, metal oxides, group I or II metal oxides, transition metals, and MgO. In some variations, the template structure may include at least one of the following: macropores, mesopores, hierarchical porosity, subunits greater than 100 nm, subunits between 20 nm and 100 nm, and subunits between 1 nm and 20 nm.

[0302] In some variations of the general method, the template structure may include at least one of the following: elongated, thin, equiaxed or hierarchically equiaxed superstructures; elongated superstructures with an aspect ratio greater than 200:1; elongated superstructures with an aspect ratio between 50:1 and 200:1; spheroids or spherical superstructures; hollow superstructures; fragmented superstructures including fragments of some other parent superstructure; and curved fragmented superstructures including fragments of a hollow superstructure.

[0303] In some variations of the general method, adsorbing the coating material onto the template surface may include at least one of the following: liquid phase application of the adsorbate, atomization of the adsorbate, physical vapor deposition, chemical vapor deposition, application of a liquid adsorbate, and application of a solid adsorbate. In some variations, the vapor deposition of the adsorbate may include pyrolytic decomposition of the vapor at a temperature between 350 °C and 950 °C.

[0304] In some variations, the adsorbate may include at least one of the following: organic compounds, hydrocarbons, organosilicon compounds, organometallic compounds, metal organic compounds, organoboron compounds, organonitrogen compounds, pre-ceramic compounds, polymers, graphene networks, synthetic anthracite networks, sp xNetworks, spiral networks, carbonaceous materials, x-carbon, z-carbon, boron nitride, carbon boron nitride, electrical conductors, electrical insulators, and electrical semiconductors. In some variants, the pre-ceramic compound may include silicon-containing molecules, which may include at least one of the following: polysiloxanes, polyhedral oligomeric silsesquioxanes, polycarbosiloxanes, polycarbosilanes, polysilcarbodiimides, polyhedral oligomeric silcarbodiimides, polyhedral oligomeric silyl nitrides, polysilyl nitrides, and metal-containing variants of these molecules, etc.

[0305] In some variants, the adsorbate may be altered by at least one of the following processes after adsorption to the template surface: crystallization, sintering, grain growth, coalescence, decomposition, pyrolysis, polymerization, chemical functionalization, molecular grafting, chemical etching, activation, passivation, orbital rehybridization, maturation, and formation of spiral networks.

[0306] In some variants, the PC structure formed by adsorption of the adsorbate may include at least one of the following: a single coating phase, two or more different coating phases, and two or more coating phases arranged in different coating layers. In some variants, different layers may be applied by multiple sequential surface replication procedures that occur before or after content extraction. In some variants, the coating layer may be sandwiched between two z-adjacent layers.

[0307] In some variants of the general method, content extraction may utilize an extractant solution containing a weak acid as the extractant. In some variants, the extractant solution may be formed by dissolving a process gas in process water. In some variants, the extractant solution may be an aqueous H2CO3 solution formed by dissolving liquid or gaseous CO2 in process water. In some variants, content extraction may include a shuttle technique. In some variants, content extraction may be performed under elevated pressure or temperature conditions.

[0308] In some variants of the general method, coating separation may include at least one of the following: decantation, hydrocycloning, sedimentation, deposition, flotation, froth flotation, centrifugation, filtration, and liquid-liquid extraction. In some variants, coating separation may separate the coating product from substantially all of the process liquid. In some variants, the coating product may retain a residual portion of the process liquid. In some variants, the coating product may be naturally floating due to the retention of internal gas. In some variants, the internal gas of the coating product may be expanded by reducing the pressure of the surrounding process liquid, increasing the buoyancy of the coating product, and causing flotation. In some variants, a portion of the internal gas of the coating product may exude by reducing the pressure of the surrounding process liquid and then repressurizing the surrounding process liquid such that the hydrostatic pressure causes the process liquid to penetrate the coating product.

[0309] In some variations of the general method, the stock solution generated by content extraction can be concentrated by dissolving one or more additional solutes in the stock solution. In some variations, the additional solute(s) can include at least one of the solid precipitated from the stock solution and the process gas. In some variations, the dissolution of one or more additional solutes in the stock solution can be achieved by changing the temperature or pressure of the stock solution. In some variations, the concentrated aqueous Mg(HCO3)2 stock solution can be formed by precipitating and diluting the stock solution to form MgCO3.

[0310] In some variations of the general method, the coated product can include a coated framework. In some variations, the morphology of the coated framework can include at least one of the following: native morphology, non-native morphology, wrinkled morphology, hollow morphology, hierarchical morphology, macropores, mesopores, micropores, globular superstructural geometries, prismatic superstructural geometries, shells, shell fragments, amorphous cell spaces, and labyrinth pore structures.

[0311] In some variations, the coated framework can include at least one of the following: hydrophobic materials, hydrophilic materials, amphiphilic materials, and dual-sided materials including hydrophobic and hydrophilic surfaces. In some variations, the coated framework can include at least one of flexible, rigid, and elastic. In some variations, the coated framework can contain internal gas and can float when immersed in a liquid.

[0312] In some variations, the measured value of the long axis of the coated framework can be at least one of the following: less than 1 μm, between 1 μm and 100 μm, and between 100 μm and 1,000 μm. In some variations, the framework can include a BET surface area of at least one of 1,500 to 3,000 m 2 / g and between 10 and 1,500 m 2 / g. In some variations, the framework can include an elongated, thin, or equiaxed superstructure. In some variations, the elongated framework can include an aspect ratio between 50:1 and 200:1.

[0313] In some variations of the general method, the coated framework can include a carbonaceous phase, which includes at least one of the following: carbonaceous materials, pyrolytic carbon, graphene networks of carbon, anthracite networks of carbon, sp x networks of carbon, and helical networks of carbon, x-carbon, and z-carbon. In some variations, the coated framework can include functional groups, which include at least one of the following: carbon atoms, oxygen atoms, halogen atoms, metal atoms, boron atoms, sulfur atoms, phosphorus atoms, and nitrogen atoms.

[0314] In some variations of the general method, under 532 nm excitation, the carbonaceous phase of the coated framework can include at least one of the following: Raman spectrum I between 4.0 and 1.5 D / I G Ratio; Raman spectrum I between 1.5 and 1.0 D / I G Ratio; Raman spectrum I between 1.0 and 0.1 D / I G Ratio; Raman spectrum I between 0.0 and 0.1 Tr / I G Ratio; Raman spectrum I between 0.1 and 0.5 Tr / I G Ratio; Raman spectrum I between 0.5 and 1.0 Tr / I G Ratio; Raman spectrum I between 0 and 0.15 2D / I G Ratio; Raman spectrum I between 0.15 and 0.3 2D / I G Ratio; and Raman spectrum I between 0.30 and 2.0 2D / I G Ratio.

[0315] In some variants of the general method, under 532 nm excitation, the carbonaceous phase coating the framework may include at least one of the following: an unfitted Raman spectrum D peak located between 1345 and 1375 cm -1 ; an unfitted Raman spectrum D peak located between 1332 and 1345 cm -1 ; an unfitted Raman spectrum D peak located between 1300 and 1332 cm -1 ; an unfitted Raman spectrum G peak located between 1520 cm -1 and 1585 cm -1 ; an unfitted Raman spectrum G peak located between 1585 cm -1 and 1600 cm -1 ; and an unfitted Raman spectrum G peak located between 1600 cm -1 and 1615 cm -1 .

[0316] In some variants of the general method, the coated framework may contain a non-carbonaceous phase including ceramics. In some variants, the ceramic phase may include at least one of the following: one or more post-transition metals, one or more metalloids, one or more reactive non-metals, and decomposition products of one or more pre-ceramics. In some variants, the ceramic phase may include at least one of the following: silicon oxycarbide (Si-O-C), silicon carbide (Si-C), silicon nitride (Si-N), silicon boride (Si-B), silicon carbonitride (Si-C-N), and silicon boron carbonitride (Si-B-C-N), as well as metal-modified and various stoichiometric compositions of these compounds.

[0317] In some variants, the ceramic phase coating the framework may include a nanostructured BN phase, the phase including at least one of the following: sp 2 hybrid state, sp 3 hybrid state, sp 2 and sp 3 mixtures of hybrid states, hierarchical architectures, and structural dislocations providing internal cross-linking between layers. In some variants, the BN phase coating the framework may include a synthetic anthracite network, sp x network, and a helicoid-like network.

[0318] In some variants, the substantially sp 2 hybridized BN phase may include one or more atomic monolayers. In some variants, two or more atomic BN monolayers may exhibit a nematic alignment. In some variants, the BN phase may include a single broad unfit Raman spectral band between 500 and 2500 cm -1 upon excitation at 532 nm. In some variants, the peak position of this band may be between at least one of the following ranges: 1300 cm -1 to 1400 cm -1 、1400 cm -1 to 1500 cm -1 and 1500 cm -1 to 1600 cm -1 .

[0319] In some variants, the ceramic phase coating the framework may include a nanostructured BC x N phase, the phase including at least one of the following: sp 2 hybrid state, sp 3 hybrid state, sp 2 and sp 3 mixtures of hybrid states, hierarchical architectures, and structural dislocations providing internal cross-linking between layers. In some variants, the BC x N phase coating the framework may include a synthetic anthracite network, sp x network, and a helicoid-like network. In some cases, the BC x N phase coating the framework may include an engineerable electronic bandgap based on its carbon fraction composition.

[0320] In some variants, the substantially sp 2 hybridized BC x N phase may include one or more atomic monolayers. In some variants, two or more atomic BC x N monolayers may exhibit a nematic alignment. In some variants, the BC x N phase may include at least one of the following upon excitation at 532 nm: located at 1500 cm-1 between 1650 cm -1 and the G peak between 500 cm -1 and 2500 cm -1 and the broad unfit Raman spectral band between, the G peak associated with sp 2 carbon, and the underlying broadband associated with BN, and the substantially absent D peak associated with sp 2 carbon rings.

[0321] In some variants, the nanostructured ceramic phase may include at least one of the following single-element atomic monolayers: borophene, silicene, germanene, stanene, phosphorene, arsenene, antimonene, bismuthene, and tellurene. In some variants, the nanostructured ceramic phase may include substantially two-dimensional transition metal dichalcogenides.

[0322] In some variants, the nanostructured ceramic phase may include metal oxides, or oxides of metalloids or reactive non-metals. In some variants, the metal oxides may include layered transition metal oxides. In some variants, the metal oxides may include mixed metal oxides. In some variants, the metal oxides may include at least one of catalysts and photocatalysts.

[0323] In some variants, the coating wall may include a nanostructured metal phase. In some variants, the nanostructured metal phase may include at least one of the following: Group I metals, Group II metals, transition metals, transition metal alloys, Ni, Ni-Mo, reduction decomposition products of metallocenes, electroless coatings, and catalysts.

[0324] In some variants, the coating wall may include two or more nanostructured phases. In some variants, the two or more phases may include different coating layers. In some variants, electrically insulating, conductive, or semi-conductive coating layers may alternate. In some variants, a coating layer may be sandwiched between two other coating layers to shield it. In some variants, a carbonaceous coating layer may be shielded from thermal oxidation by one or more other coating layers.

[0325] In some variants of the general method, the coated product may be subjected to further processing after coating separation. In some variants, the further processing after coating separation may include at least one of the following: flash drying, spray drying, spray pyrolysis, decomposition, chemical reaction, annealing, sintering, and chemical functionalization.

[0326] In some variants of the general method, the liquid circulation may also incorporate the re-capture and preservation of process liquids released or evaporated during the template stage, although this is not shown as an output in Figure 3It is not reflected because in most (but not all) variants of the contemplated general method, the amount of process liquid saved during the templating stage will be significantly less than the amount of process liquid saved during the precursor stage.

[0327] In some variants of the general method, gas recycling may be incorporated into the method. The inputs and outputs of the general method with gas recycling are shown in Figure 4 In gas recycling, process gas is released during the precursor stage and / or the templating stage. This released gas is saved. Then, during the separation stage, the saved process gas can be dissolved into the saved process liquid to form an extractant solution.

[0328] The preferred method described below includes a variant of the general method in which MgCO3·xH2O template precursor material is obtained from an aqueous Mg(HCO3)2 stock solution, and a portion of the CO2 process gas is saved by gas recycling. The inputs and outputs of the preferred method are shown in Figure 5 The preferred method includes:

[0329] Precursor stage: Obtain MgCO3·xH2O precursor material from an aqueous Mg(HCO3)2 stock solution, where said obtaining includes solvent-free precipitation of MgCO3·xH2O and emission of CO2 process gas. Save a portion of the released CO2 process gas. Separate the MgCO3·xH2O precursor material and process water. Save the process water.

[0330] Templating stage: Thermally decompose the MgCO3·xH2O precursor material formed in the precursor stage in one or more procedures to form a porous MgO template material. The released CO2 process gas may be saved.

[0331] Copying stage: Adsorb the coating material onto the template surface of the porous MgO template to form a PC material.

[0332] Separation stage: Dissolve the saved CO2 process gas into the saved process water to form an aqueous H2CO3 extractant solution. Content extraction includes the reaction between the content MgO and the aqueous H2CO3 extractant solution, from which the Mg(HCO3)2 stock solution is obtained. Coating separation may include techniques for removing process water from the coated product to minimize residual process water. Foam flotation, liquid-liquid separation, or other techniques for separating the coated framework from the process water may be used.

[0333] Certain variants of the preferred method may employ pressure regulation in order to form a concentrated stock solution and improve the precipitation process. A concentrated stock solution may be associated with many benefits, including excellent precipitation kinetics, reduced process water usage, smaller vessels, and improved energy efficiency. Two exemplary ways to achieve this are shown in Figure 27 A toFigure 27 shown in B and described below.

[0334] In Figure 27 the first screen of A, a shuttle technique has been used to achieve content extraction. The shuttle technique produces a mixture comprising an aqueous Mg(HCO3)2 stock solution, one or more coated frameworks, and a MgCO3·xH2O precipitate. This precipitate is represented in Figure 27 the first screen of A as a mixture of nesquehonite rods and acicular nesquehonite aggregates. Next, the coated product is separated from other process liquids and solids. After that, the MgCO3·xH2O precipitate is dissolved by increasing the CO2 pressure, which increases the concentrations of dissolved CO2, H2CO3, and HCO3 - to form a concentrated stock solution, as shown in Figure 27 the second screen of A. Finally, as shown in the third screen, the MgCO3·xH2O precursor can be rapidly nucleated and precipitated from the concentrated stock solution by reducing the CO2 pressure (and optionally the total pressure).

[0335] Another way to obtain a concentrated stock solution is to perform content extraction in a pressurized reactor. A schematic diagram showing this way is shown in Figure 27 B. Similar to the procedure shown in Figure 27 A, the procedure shown in Figure 27 B employs an increased CO2 pressure to increase the concentrations of dissolved CO2, H2CO3, and HCO3 - In Figure 27 B, a PC material, CO2, and H2O (possibly an aqueous Mg(HCO3)2 mother liquor) are fed into a pressurized reactor. Content extraction and the formation of a concentrated stock solution occur inside the pressurized reactor. A mixture of the coated product and the concentrated stock solution is discharged from the pressurized reactor, and then coated separation can occur in the pressurized reactor. The separation can advantageously be achieved using a liquid-liquid separation that eliminates the need for rinsing. The MgCO3·xH2O precursor can be rapidly nucleated and precipitated from the concentrated stock solution by reducing the CO2 pressure (and optionally the total pressure).

[0336] III. Furnace Schemes, Analytical Techniques, and Material Nomenclature

[0337] During the process of describing the procedures for generating exemplary materials described in the subsequent sections, certain furnace schemes have been detailed. These schemes can be used for the exemplary template stage procedures detailed in Part V and the exemplary replication stage procedures detailed in Part VI.

[0338] Scenario A: In Scenario A, a Thermcraft tube furnace modified into a rotary furnace and a quartz tube can be used. The furnace has a clamshell design including a cylindrical heating chamber with a 160 mm diameter and a 610 mm heating length. The wattage of the furnace is 6800 W, and the maximum operating temperature is 1100 °C. The quartz tube can be a 60 mm OD quartz tube containing an extended intermediate section ("belly") of a 130 mm OD tube positioned within the heating zone of the furnace. The tube can rotate. A quartz baffle inside the belly can promote agitation of the powder sample during rotation. The furnace can be kept horizontal (i.e., not tilted). A template powder sample can be placed inside the belly in the heating zone, and ceramic blocks are inserted outside the belly on each side of the heating zone of the furnace. Glass wool can be used to fix the positions of the ceramic blocks.

[0339] For an exemplary procedure carried out using Scenario A, a material sample can be placed inside the belly such that it is agitated within the reactor. Loose-fitting ceramic blocks located outside the belly section on each side of the heating zone of the furnace allow gas flow and block the powder. Packed glass wool can be used to fix the positions of the ceramic blocks while acting as a gas-permeable layer. The ends of the tube can be fitted with two stainless steel flanges to allow gas flow through the system.

[0340] Scenario B: An MTI rotary tube furnace and a quartz tube can be used. The furnace has a clamshell design including a cylindrical heating chamber sized with a 120 mm diameter and a 440 mm heating length. The wattage of the furnace is 2500 W, and the maximum operating temperature is 1150 °C. The OD of the quartz tube can be 60 mm. The tube can be substantially horizontal. For an exemplary procedure carried out using Scenario B, a material sample can be placed inside a ceramic boat. It can then be placed inside the quartz tube within the heating zone, and then heating can be started. Loose-fitting ceramic blocks located outside the heating zone of the furnace allow gas flow. Packed glass wool can be used to fix the positions of the ceramic blocks while acting as a gas-permeable layer. The ends of the tube can be fitted with two stainless steel flanges. If ammonia borane (H3NBH3) is used, solid H3NBH3 can be placed in a ceramic boat just outside the upstream side of the furnace heating zone such that it can reach a temperature between 130 °C and 170 °C when the furnace reaches the set temperature.

[0341] Scenario C: A Lindberg Blue-M tube furnace and a quartz tube can be used. The OD of the quartz tube can be 150 mm. The furnace has a clamshell design with a cylindrical heating chamber sized 190 mm in diameter and 890 mm in heating length. The wattage of the furnace is 11,200 W, and the maximum operating temperature is 1200 °C. The tube can be substantially horizontal. For an exemplary procedure carried out using Scenario C, the sample can be placed inside a ceramic boat. It can then be placed inside the quartz tube in the heating zone, and then heating can be started. Loose-fitting ceramic blocks outside the heating zone of the furnace allow gas flow. The ends of the tube can be fitted with two aluminum flanges to allow gas to flow through the system.

[0342] Scenario D: A Vulcan 3-550 muffle furnace can be used. The furnace has a rectangular heating chamber sized 190 mm x 240 mm x 228 mm. The wattage of the furnace is 1440 W, and the maximum operating temperature is 1100 °C. For an exemplary procedure carried out using Scenario D, a material sample can be placed inside a ceramic boat. It can then be placed inside the muffle furnace, and then heating can be started.

[0343] Scenario E: A TA Instruments Q600 TGA / DSC can be used. For an exemplary procedure carried out using Scenario E, a 90 μL alumina pan can be used to hold the material sample. Unless otherwise specified, the gas flow can be a specified gas at 100 sccm. The heating rate can be mentioned in the exemplary procedure using Scenario E.

[0344] Multiple analytical techniques are used to characterize the procedures and materials presented herein. These are detailed below.

[0345] Electrolytic conductivity (“conductivity”) is used to measure the concentration of a solution. Conductivity is a measure of the conductance response of a solution. The electrical response of a solution can be related to the concentration of ions dissolved in the solution, and as the ions in the solution precipitate, the conductivity value decreases. Similar to this measurement is total dissolved solids (“TDS”), which relates the conductivity measurement result to a reference ion concentration (usually potassium chloride), and the ion concentration depends on the dissolved salt compound.

[0346] Raman spectroscopy is performed using a ThermoFisher DXR Raman microscope equipped with a 532 nm excitation laser. For each sample analyzed, a 16-point spectrum is generated using measurements made on a 4x4 point rectangular grid with a point-to-point spacing of 5 μm. The 16-point spectra are then averaged to produce an average spectrum. The Raman peak intensity ratios and Raman peak positions reported for each sample are derived from the average spectrum of the sample. No line-fitting software is used, so the reported peak intensity ratios and peak positions are related to the unfitted peaks related to the overall Raman line shape.

[0347] Gas adsorption measurements were carried out using a Micromeritics Tristar IIPlus. Nitrogen adsorption was measured across a range of pressure (p) values at a temperature of 77 K, where the pressure increment range was up to The BET specific surface area was calculated using Micromeritics MicroActive software, and the specific surface area was derived from the BET monolayer capacity assuming a cross-sectional area of σ m (N2,77K) = 0.162 nm 2 Samples were pretreated by degassing with continuous flowing dry nitrogen at 100 °C prior to analysis.

[0348] Pore size distribution (PSD) and pore cumulative volume are another technique that can be performed on gas adsorption data to gain insight into the sintering behavior of the particles. The data was collected by a Micromeritics Tris tar IIPlus, which measured nitrogen adsorption and desorption at 77 K between pressures and with an increment range of up to Samples were pretreated by degassing with continuous flowing dry nitrogen at 100 °C prior to analysis.

[0349] The adsorption - desorption PSD and pore cumulative volume were calculated using Micromeritics MicroActive software by applying the Barrett, Joyner, and Halenda (BJH) method. This method provides a comparative evaluation of the mesopore size distribution of the gas adsorption data. For all BJH data, the Faas correction and the Harkins and Jura thickness curves can be applied. The pore cumulative volume V PORE (cm 3 / g) can be measured for both the adsorption and desorption parts of the isotherm.

[0350] Multiple exemplary materials are described in this disclosure. To help identify and track these exemplary materials, a material naming system has been adopted and is described below. All names of exemplary materials are in bold; herein, N2 describes an exemplary material, and N2 refers to nitrogen.

[0351] Exemplary types of template precursor materials are designated as S x, where S designates the first or first two letters of the template precursor (i.e., N represents nesquehonite, L represents hydromagnesite, Li represents lithium carbonate, C represents magnesium citrate, A represents amorphous MgCO3·xH2O, H represents hydrotalcite, M represents magnesite, E represents epsom salt, Ca represents calcium carbonate), and where x designates different types of precursor compounds (e.g., H1 and H2 represent two different types of hydrotalcite precursors).

[0352] Exemplary types of template materials are named in the format S x T y . S x The name component designates the precursor type used to produce template type S x T y , and T y The name component designates the specific treatment used to produce template type S x T y . For example, N1T1 and N1T2 indicate two different template types formed by two different treatments of precursor type N1. It should be noted that while the complete S x T y name represents a specific template type, the T y name component itself is specific only to a given S x precursor type. For example, the treatments used to make template types N1T1 and N2T1 are different, even though these template types share the same T1 name component.

[0353] Exemplary types of PC materials are named in the format S x T y P z , where S x T y The name component designates the template type, and P z The name component designates the specific type of coating material. For example, M3T1P1 and M3T1P2 indicate two different PC materials formed from the same M3T1 template material. The P x T y P z within the S z T z T x name component is unique, i.e., each P y name component designates a unique type of coating material, regardless of the S

[0354] Exemplary types of coating frameworks (i.e., porous coating products produced by content extraction) are named in the format P z , where P z The name component does not depend on S x T yThe beginning of the template type. It is itself used to specify the framework type P z The name component and S from which the framework type is obtained x T y P z P of PC material z The name components match.

[0355] Exemplary types of template precursor materials, template materials, PC materials, and coating materials in this disclosure are enumerated in Figure 206 enumerated. Figure 206 Is arranged to show the progress of the synthesized materials starting from the template precursor material.

[0356] IV. Coating framework examples

[0357] This section details the small-scale production of exemplary coating materials using exemplary procedures. The full implementation of the general method is not described in conjunction with each exemplary procedure, although such an implementation would be possible for each exemplary procedure. Additionally, it should be understood that many of the techniques or materials used in these exemplary procedures are only intended to demonstrate the effects or characteristics of techniques or materials that can be used in larger-scale industrial implementations.

[0358] The ’49195 application teaches the synthesis of various exemplary types of template precursor materials, template materials, PC materials, and coating frameworks. Collectively, these materials demonstrate the breadth of carbonaceous coating products that can be synthesized, as well as the breadth of template precursor materials and template materials that can be used. In this section, we will show how general methods can also be used to produce hierarchical coating frameworks and non-strictly carbonaceous coating frameworks. The procedures and materials presented in this section are intended to be exemplary because a wide variety of procedures and materials can be readily envisioned and used without departing from the invention. The types of coating materials synthesized in the following examples are outlined in Figure 206 outlined.

[0359] Example P 24 、P 25 : In two exemplary procedures, hierarchical coating materials (P 24 ) and silica-like coating materials (P 25 ) can be synthesized, depending on the choice of atmosphere during the final heat treatment performed after surface replication.

[0360] For demonstration purposes, P 23 type carbonaceous coating materials can first be synthesized by performing surface replication on a porous protomagnesite MgO template structure in a manner consistent with the general method (and the preferred method). This precursor stage and template stage procedure is described in the ’49195 application and reference A, and the surface replication parameters can be found in Figure 213 found. P 23The Type-C carbonaceous coated framework includes a synthetic anthracite network including a helical network; this helical network classification is based on their synthesis, including subjecting the sp x precursor network to the temperature at which maturation occurs (>1000 °C). As described in the '37435 application, the helical network is formed by the maturation of the sp x precursor network.

[0361] Next, the Type-P 23 carbon can be chemically functionalized. For this purpose, an aqueous paste containing approximately 13 wt% of Type-P 23 carbon content can be prepared. A 144 g amount of the paste containing approximately 18.7 g of carbon can be added to 500 g of deionized water in a beaker and stirred using an overhead Cowles blade mixer to suspend the carbon. Then this mixture can be transferred from the beaker to the reservoir of a high-shear rotor-stator homogenization processor (IKA Magic Lab, or "ML"). The mixture in the reservoir can be mixed using the overhead Cowles blade mixer to keep the particles well suspended in the reservoir. The residue in the beaker can be rinsed with 50 g of deionized water, and the residue and the rinse liquid can be added to the ML reservoir. The mixture can be maintained at a temperature of 5 °C using the external thermal control system on the ML, and the rotor-stator speed can be set to 15,000 RPM. Using these settings, the mixture can be circulated for 30 min, thereby maintaining the mixture at a temperature of 5 °C. The mixture can have a pH value of approximately 10. At this time, 2.5 g of aqueous HCl can be added within 15 s. Then, 15.5 g of aqueous NaOCl (14.5% concentration) can be added within 15 s. The mixture can have a pH value of approximately 2.35. The mixture can be made to flow for another 15 min at a temperature of 5 °C. At this time, 2 g of aqueous H2O2 (35% concentration) can be added. Next, the mixture can be removed from the ML. The residue in the ML can be rinsed with deionized water, and the residue and the rinse liquid can be added to the mixture. Then the mixture can be filtered, rinsed with deionized water, and then rinsed with ethanol, thereby producing an ethanol paste of the carbon-coated material.

[0362] Next, 92 g of an ethanol paste containing approximately 15.9 g of carbon content can be diluted with 400 g of ethanol in a beaker and stirred using a top-mounted Cowles blade mixer to suspend the carbon. This mixture can then be transferred from the beaker to an ML reservoir. The mixture in the reservoir can be mixed using a top-mounted Cowles blade mixer to keep the particles well suspended in the reservoir. The rotor-stator speed can be set to 15,000 RPM and the mixture can be kept at approximately room temperature. 15.8 g of 3-[2-(2-aminoethyl)amino]propyltrimethoxysilane (AEAPTMS) can be added to the reservoir within 1 minute. After this, 95 g of deionized water and 1.6 g of NaOH can be added to bring the pH to approximately 10.6. The mixture can be circulated for 30 min and then removed from the ML and transferred to a beaker. The residue in the ML can be rinsed with 100 g of deionized water and then with 50 g of ethanol, and the residue and the rinse solution can be added to the mixture. The beaker can be magnetically stirred and heated for the next 150 min at a temperature range of approximately 78 °C to 93 °C. During this time, the inside of the beaker can be rinsed twice, each time with 50 g of deionized water to raise the boiling point of the mixture. At this point, heating can be stopped. The mixture can then be filtered and rinsed with ethanol to produce an ethanol paste. The paste can be dried at 60 °C to form a powder, and the framework contains AEAPTMS-functionalized carbon. Figure 6 is a diagram showing the attachment of AEAPTMS molecules to the carbon surface.

[0363] Next, the AEAPTMS-functionalized carbon powder can be subjected to post-replication heat treatment. In Example P 24 and Example P 25 , the treatment can be carried out in a TGA instrument as described in furnace protocol E detailed in Part III. In Example P 24 , the treatment can be carried out under flowing Ar, while in Example P 25 , the treatment can be carried out under flowing air. In each treatment, the powder sample can be heated from room temperature to a final temperature of 900 °C at a heating rate of 20 °C / min. After reaching 900 °C, the sample can be cooled back to room temperature. The oxidative atmosphere of the heat treatment used in Example P 25 completely oxidizes the carbon coating layer and the organic phase of the polysiloxane, resulting in a silica-like coating material that is Figure 7 the brownish-white powder shown in B. On the other hand, the inert atmosphere of the heat treatment used in Example P 24 retains the carbon coating layer and produces a SiO x C y layer that is arranged in a BAB stratigraphic arrangement, where the A layer is carbon and the B layer contains SiO x C y . The resulting stratified coating material isFigure 7 The black powder shown in A.

[0364] Silica-like P 25 The SEM micrograph of the type framework is shown in Figure 8 A. Although deformation of the native superstructure geometry has occurred during the removal of the underlying carbon layer, the superstructure of the silica-like framework is still similar to that of the template precursor particles ( Figure 8 B). The angles and edges of the native prisms are still distinguishable, as indicated by the yellow dashed lines in Figure 8 A.

[0365] N2 desorption analysis indicates that the silica-like P 25 type framework has a non-native unit cell substructure. In Figure 9 , the BJH pore size distributions of the P 23 type carbon-coated, AEAPTMS-functionalized P 23 type carbon-coated, and silica-like P 25 type coating materials are shown. All three materials have a unit cell substructure with N2-accessible mesopores. Comparison of the three pore size distributions shows that the unit cell substructures of the P 23 type framework and the AEAPTMS-functionalized framework are similar, but the unit cell substructure of the silica-like P 25 type framework includes smaller mesopores. This densification explains the slightly contracted deformed superstructure geometry observed in the silica-like framework in Figure 8 A.

[0366] N2 adsorption analysis also reveals that the silica-like framework has an average surface area of 1273 m 2 / g. This is significantly higher than the average surface area of 461 m 23 / g for the P 2 type carbon framework and the average surface area of 463 m 2 / g for the AEAPTMS-functionalized framework. This reflects the elimination of the carbonaceous coating layer in Example P 25 in which oxidative heat treatment is employed. The remaining silica-like coating layer after heat treatment is thinner than the eliminated carbon layer.

[0367] Similar procedures can be used to produce hierarchical or silica-like coated frameworks with other engineered features. Other exemplary templates and procedures described in References A and B can be readily combined with Example P 24 and Example P 25used in conjunction with the methods described therein. Similarly, a stratigraphic encapsulation of the coating material can be obtained using a similar procedure. One way to achieve this is to form a pre-ceramic layer, such as an inorganic polymer, on an existing coating layer, pyrolyze the pre-ceramic layer to form a ceramic layer, and then sinter or melt the ceramic layer such that a continuous ceramic phase forms around the underlying coating material. The stratigraphic encapsulation can be used, for example, to shield a carbonaceous coating framework from oxidation in a high-temperature oxidizing environment.

[0368] As an example, an elongated coating material is shown in Figure 10 which shows SEM micrographs and spectra generated by energy-dispersive X-ray spectroscopy. These elongated coating frameworks were prepared using a procedure that is conceptually similar to that of Example P 25 but in this case, elongated coating wall carbon was used and functionalized with a bidentate organosilane. The functionalized coating carbon was then exposed to an oxidative heat treatment. In Figure 10 some sintering of the silica-like encapsulation phase is evident within and between the initially discrete frameworks. Figure 10 The spectra shown indicate atomic percentages of approximately 20%, 52%, and 27% of C, O, and Si, respectively, which indicates a silica-like phase and carbon associated with the aromatic carbon framework used. Although the sample fluoresces strongly when excited at 532 nm, the aromatic character of the carbon phase was confirmed by Raman spectroscopy, which, in addition to revealing the G peak associated with sp 2 carbons, further revealed a D peak associated with the radial breathing mode phonons in the sp 2 carbon rings. From the survival of the coated carbon material during heat treatment in an oxidizing atmosphere, we can conclude that the coated carbon material was retained due to its encapsulation by a gas-impermeable silica-like phase.

[0369] Based on this demonstrated impermeability to O2 gas, we can conclude that if pyrolysis and sintering are performed in a vacuum, the framework will be encapsulated in an internally evacuated state and then sealed relative to the surrounding air. In certain coating architectures where the mass of the encapsulated gas becomes significant relative to the mass of the framework, especially in hierarchical superstructures with large central cavities, the apparent density of the framework can be reduced by evacuating the gas from the internal pores of the framework and then encapsulating the entire framework in such a vacuum or partial vacuum state. Therefore, obtaining an encapsulation of the coating material in a vacuum can be useful.

[0370] Using approaches similar to those described in Example P 24 and Example P 25 coated frameworks and layers with a variety of morphologies and polymer-derived ceramic compositions can be readily obtained. Figure 11For example, SEM micrographs show silica-like coated frameworks with hollow superstructures. These frameworks are obtained from hollow MgCO3·xH2O template precursor particles, such as those described in reference A. Some of the frameworks have been damaged by pressing them into the tape used for imaging. Ceramic-acquiring polymers like this can be obtained from silicon-based pre-ceramic polymers such as polysiloxanes, polyhedral oligomeric silsesquioxanes, polycarbosilanes, polycarbosilanes, polysilcarbodiimides, polyhedral oligomeric silcarbodiimides, polyhedral oligomeric silazanes, polysilazanes, and metal-containing variants of these molecules. Using this approach, various engineering ceramic chemistries can be obtained, including metal-modified ceramics.

[0371] Example P 26 , P 27 : In another exemplary procedure, boron nitride (BN)-coated materials and layered coated materials including BN and carbon layers can be synthesized.

[0372] For illustrative purposes, P7-type carbonaceous coated materials can be synthesized first by surface replication on a porous pre-magnesite MgO template structure in a manner consistent with the general (and preferred) method. The precursor stage and template stage procedures are described in the '49195 application and reference A, and the surface replication parameters can be found in Figure 213 . The P7-type carbonaceous coated framework contains a z-sp x category of synthetic anthracite network, as indicated by the interpolated Raman D peak position of the sample at 1334 cm -1 upon excitation at 532 nm. As described in the '37435 application, the redshifted D peak position in this range reflects the presence of Y dislocations and C(sp 3 )-C(sp 3 ) bonds between the edges of graphene domains.

[0373] Next, the BN-coated layer can be adsorbed onto each side of the P7-type carbon-coated framework, resulting in a BAB stratigraphic arrangement. For this purpose, according to Scheme B, a 40 mg quantity of the P7-type carbon framework can be placed in a ceramic boat, which can be placed in a tube furnace as detailed in Part III. A ceramic boat containing 2 g of ammonia borane complex (H3NBH3) can be placed in a quartz tube just outside the furnace heating zone such that when the furnace reaches a temperature of 700 °C, H3NBH3 reaches a temperature between 130 °C and 170 °C. The furnace can then be heated to a temperature of 700 °C at a heating rate of 20 °C / min under Ar flowing at 2000 sccm. Upon reaching 700 °C, the furnace can be maintained at 700 °C for 60 minutes and then cooled to room temperature under a continuous Ar flow.

[0374] Next, according to Scheme D, the powder can be placed in a muffle furnace as detailed in Part III. The furnace can be heated in air to a temperature setting of 800 °C, then held at this temperature for 1 hour, and then allowed to cool to room temperature.

[0375] The resulting powder can contain two phases. The first phase includes a layered coated framework, the layered coated framework includes a BAB stratigraphic arrangement, where B represents the outer layer of BN and A represents the inner layer of carbon, and this phase includes a coating material identified herein as P 26 . The P 26 -type phase is optically black, as shown in the optical micrographs in Figure 12 A to Figure 12 B. The P 26 -type coated framework includes a thin lamellar superstructure morphology, which has no change from the P7-type framework on which BN is adsorbed. The outer layer of the BAB arrangement stratigraphically shields the inner carbon layer from thermal oxidation under conditions where the unshielded carbon would be completely thermally oxidized. This indicates that the BN adsorbate completely covers a substantial portion of the coated walls of these carbon frameworks and shields them from thermal oxidation at 800 °C.

[0376] This stratigraphic arrangement is further confirmed by Raman spectroscopy. Figure 12 A to Figure 12 Each spectrum in Figure 12 A is an average spectrum generated from multi-point spectral analysis under 532 nm excitation. Each analysis was performed with a 2 mW laser power setting. In 26 A, the Raman spectrum of the thermally oxidation-resistant P 2 -type layered framework is shown. The retained D peak of sp -1 carbon is at 1362 cm -1 under 532 nm excitation, which is blue-shifted from the D peak position of 1334 cm 26 . At least a portion of this blue shift is attributed to the exposure of the P 26 -type carbon layer to a higher temperature compared to the P7-type carbon. The position of the G peak of the P -1 -type carbon is also blue-shifted from the G peak position of approximately 1594 cm -1 of the P7-type carbon. Additionally, the G peak appears to broaden, possibly at least in part due to merging with the D’ peak at 1620 cm 2 where the center of the peak is located, or possibly at least in part due to the spread of the compressive strain state after the stratigraphic shielding of the sp Figure 12 carbon by the BN layer. The range of the magnified peak in the inset of -1 A is from 1600 cm -1 to 1630 cm

[0377] Overall, comparing the line shape of this P 26 spectrum with the line shape of the individual P7-type carbon (Figure 12 C) Comparison reveals P 26 a broad basal peak in the spectrum that raises the D peak above the G peak. By comparing the spectrum of the P 26 type hierarchical framework with the second optically white phase of the material observable in the optical micrographs in Figure 12 A to Figure 12 B, the attribution of this basal peak is elucidated. The type of coating material in this second phase is identified herein as P 27 , which consists of a disordered BN framework left after complete removal of the carbon layer by thermal oxidation. In addition to the particles changing color from black to white, the Raman spectrum of this phase further confirms the elimination of carbon from the P 27 type framework, as shown in Figure 12 B. The broad peak centered at approximately 1410 cm -1 indicates disordered BN and is similar to the line shape of the Raman spectrum of amorphous BN in the literature. Thus, Figure 12 the spectrum of the P 26 type framework in A represents Figure 12 the P7 spectrum shown in Figure 12 C and the complex of the P 27 spectrum shown in

[0378] different P 26 and P 27 powder phases are formed due to the static bed CVD procedure used to grow BN in Examples P 26 and P 27 . In the absence of agitation to promote gas-solid mixing, during surface replication, the carbon framework near the surface of the static bed is substantially covered with BN adsorbates on both sides of the coating wall. This results in the occlusion of the carbon strata sandwiched between two BN strata and the formation of a hierarchical coating material near the surface of the static bed. However, due to gas diffusion limitations, during surface replication, the carbonaceous coating frameworks farther from the surface of the static bed are not completely covered with BN adsorbates. Then, these unoccluded carbonaceous frameworks are completely thermally oxidized during the 800 °C treatment.

[0379] Due to the ability to grow BN on a carbon substrate and vice versa, a multi-stage replication procedure can be utilized to produce various stratigraphic arrangements of BN and carbon. For example, if the BN growth procedure is performed in the pre-extraction replication procedure (i.e., before content extraction), the resulting stratigraphic arrangement will be AB instead of BAB. Another pre-extraction replication step of growing carbon on the BN layer can be performed to produce an ABA stratigraphic arrangement. Any number of steps, chemical compositions, and stratigraphic arrangements are possible, and it can be useful to produce alternating conductive, semiconductive, and insulating layers.

[0380] Coated frameworks having various chemical compositions and phases may be of interest for weight-sensitive ceramic applications, ceramic applications that desire unusual mechanical properties such as flexibility or pseudoelasticity, and ceramic applications that desire high thermal stability or thermal shock resistance. It may be desirable to retain a carbon layer within the coating walls, not only because of its own function in the application, but also because it can stabilize the coating architecture of other ceramic layers during high-temperature production and service. The exposed carbon layer can be readily chemically functionalized, while certain ceramics may be more difficult to functionalize, so the carbon layer can also be used for functionalization purposes. This is similar to the concept presented in the '580 application, where a disordered and easily oxidized coating layer or "skin" is formed over a less disordered graphite coating layer that is not easily oxidized.

[0381] Other desirable coating compositions include transition metal dichalcogenides ("TMDCs") and layered coating materials that include multiple TMDCs or carbon and TMDCs. Similarly, layered compositions involving carbon and metal oxides such as TiO 2) will be desirable for a variety of applications such as photoanodes. General methods can be used to generate these compositions in the form of controllable compact coating frameworks having engineered superstructure and substructure architectures. Thus, the method is not limited to carbon-coated frameworks, or even single-phase frameworks, and can also be used to synthesize coating materials including diverse chemical compositions and combinations of chemical compositions. It can be applied to numerous heterostructures and composite materials known in the art and / or described herein. It can also be applicable to structures that are unknown or undiscovered.

[0382] Example P 28 : In another exemplary procedure, a BN coating material including a synthetic anthracite network can be directly synthesized on a template material by chemical vapor deposition. This synthesis demonstrates that a BN anthracite network can be synthesized from graphene BN by surface defect-catalyzed BN lattice nucleation and radical-driven BN lattice growth in a manner similar to the formation of a synthetic anthracite network from graphene carbon. Thus, a BN coating framework can be synthesized by a template-directed surface replication procedure in a manner similar to the template-directed synthesis of carbonaceous coating frameworks. As such, general methods (and preferred methods) can be used to synthesize these coating materials and other coating materials formed according to similar nucleation and growth mechanics.

[0383] In addition, similar to the radical-driven carbon growth process, the formation of the BN sp x network by the radical-driven BN growth process should be optimized by adjusting the amount of hydrogen in the gas medium during growth. This will prevent hydrogen from being released too quickly from the growing BN domains and enable the geological interface to rearrange to maximize the edge-to-edge sp 2 and sp 3Grafted configurations. These BN sps can then be utilized x The maturation of the precursor network by annealing to transform them into substantially sp 2 Hybridized BN helical networks, which also proceeds according to mechanics similar to the maturation of the carbonaceous sp x Precursor network and the formation of carbonaceous helical networks.

[0384] For illustrative purposes, an N2T1 type porous MgO template structure can first be synthesized by thermal decomposition of an N2 type nesquehonite template precursor structure in a manner consistent with the general (and preferred) method. This synthesis is described in the '49195 application and reference A.

[0385] Next, in an exemplary replication stage procedure, the N2T1 type template material can be utilized to direct the chemical vapor deposition of disordered BN. For this purpose, according to Scheme B, a 176 mg quantity of the N2T1 type template structure can be placed in a ceramic boat, which can be placed in a tube furnace as detailed in Part III. A ceramic boat containing 1.0 g of ammonia borane complex (H3NBH3) can be placed in a quartz tube just outside the furnace heating zone such that when the furnace reaches a temperature of 900 °C, H3NBH3 reaches a temperature between 130 °C and 170 °C. The furnace can initially be purged with Ar flowing at 2000 sccm for 30 minutes at room temperature. Thereafter, the furnace can be heated to a temperature of 900 °C at a heating rate of 20 °C / min under Ar flowing at 2000 sccm. When 900 °C is reached, the furnace can be maintained at 900 °C for 60 minutes and then cooled to room temperature under a continuous Ar flow.

[0386] Next, content extraction can be performed as in the separation stage of the general or preferred method. This can be carried out in an aqueous H2CO3 extractant solution. After the content MgO is dissolved, the BN-coated framework can be filtered, rinsed, and dried. In the full implementation of the general method, an H2CO3 aqueous solution can be generated using the retained process water from the precipitation in the precursor stage, and an aqueous solution of Mg(HCO3)2 can be utilized as a solution reservoir for precipitating MgCO3·xH2O template precursor materials such as N2 type nesquehonite. In this way, both the template material and the process liquid are preserved for recycling. The CO2 process gas can also be beneficially preserved and used for regenerating the extractant solution. The type of BN-coated framework produced by this process is identified herein as P 28 .

[0387] Figure 13 A is an image of a light brown powder including the P 28 Type coating material. Figure 13B is an optical micrograph of an elongated BN framework extracted from a N2T1-type template material. The BN framework is elongated and has inherited the elongated superstructure of N2-type (magnesite) template precursor particles. This is shown in Figure 13 the optical micrograph of B. The unit cell substructure of the BN framework is shown in Figure 13 C (a TEM micrograph showing 50 - 400 nm unit cell subunits). Thus, we can clearly infer the superstructure of the removed template of the rounded subunits, without obvious wrinkling or collapse of the BN-coated walls. Therefore, it can be concluded that the framework retains substantially the native substructure morphology. The adsorption of the BN-coated phase to the template surface appears to be highly conformal, resulting in a uniform 4 - 5 nm thick coated wall of a nematic-aligned atomic monolayer. This layering is shown in Figure 13 D (a HR-TEM micrograph of the BN-coated wall). The layering reflects the prevalence of sp 2 hybrid bonding that produces an atomic monolayer. Y dislocations are circled and traced in Figure 13 D.

[0388] Figure 13 E shows the layering of the BN-coated wall at a higher magnification. In this cross-section of the BN-coated wall, screw dislocations providing three-dimensional crosslinking of the nematic-aligned BN layers are evident. The yellow traced lines of the intra- and inter-layer connectivity of this non-graphitic anthracite network are shown in Figure 13 E. This screw dislocation reflects the screw dislocations in the TEM micrograph of the graphitic helical network synthesized in the ’37435 application. Like the graphitic anthracite network, the BN anthracite network is crosslinked by structural dislocations, and these structural dislocations can be discerned in the Figure 13 helical network pattern in E.

[0389] P 28 The native or near-native morphological state of the P Figure 13 type BN-coated framework (as shown in Figure 13 C) is another indication of the three-dimensional crosslinking at the molecular scale throughout the coated wall. In the absence of inter-layer crosslinking provided by structural dislocations in the anthracite network, the van der Waals cohesive force between the two-dimensional layers would be too weak to prevent the shear yielding and shear-related mechanical rupture of these microfibers that are structurally intact (as shown in Figure 13 B). Their substructure is also intact and undeformed after evaporation drying. In the absence of crosslinking between the layers of the anthracite network, the stress associated with evaporation drying - i.e., the stress caused by the surface tension of the contained water - would cause the unit cell subunits of the coated framework (shown in the magnified region of

[0390] Figure 14 A is P 28 type and P 27Superposition of Raman spectra of the P-type BN framework. Each spectrum is the average spectrum generated from multi-point spectral analysis under 532 nm excitation. To avoid sample heating and fluorescence in the P 28 -type framework, a laser power setting of 0.5 mW and 60 two-second exposures were used. P 28 The Raman spectrum of the -type BN framework includes a single broad peak stretching from approximately 1100 to 2300 cm -1 and centered at approximately 1655 cm -1 . Compared with the broad peak associated with the P 27 -type BN framework, the broad peak associated with the P 28 -type BN framework is narrower and blue-shifted by approximately 245 cm -1 . To confirm that the difference is not solely attributable to different laser power and exposure settings, the P 27 -type framework was re-analyzed using a laser power setting of 0.5 mW and 60 two-second exposures. Although the Raman signal was much lower at the lower power setting, making it difficult to discern the exact peak position, the center of the peak appears to be near 1410 cm -1 .

[0391] Figure 14 B is the superposition of the Raman spectra of the P 28 -type framework and the BN@MgO PC material for obtaining the P 28 -type framework. Each spectrum is the average spectrum generated from multi-point spectral analysis under 532 nm excitation. To avoid sample heating and fluorescence, a laser power setting of 0.5 mW and 60 two-second exposures were used. Compared with the spectrum of the P 28 -type framework, the spectrum of the BN@MgO PC material is red-shifted to 1470 cm -1 . The peak widths are similar. Thus, there appears to be an interaction between the BN-coated wall and the underlying template surface. When acquired at 2 mW, the Raman spectrum of the BN@MgO PC material reveals features at approximately 610 cm -1 , 1103 cm -1 and 1377 cm -1 that are weakly present in the 0.5 mW spectrum, as shown by the superposition of these two BN@MgO spectra in Figure 14 C. The feature at 1377 cm -1 is a characteristic of sp 2 -hybridized BN and may indicate that the laser at the 2 mW power setting is heating the sample to the point of annealing it.

[0392] Similar to the coated walls constructed by the deposition of carbonaceous graphene, the coated walls constructed by the deposition of other two-dimensional molecular structures such as sp 2 -hybridized BN can be thinned or thickened through shorter or longer CVD procedures, respectively. Thinning them produces more flexible frameworks, asFigure 15 Shown in A (optical micrographs of collapsed and uncollapsed hollow BN-coated frameworks). These were made using the A2-type template precursor described in the ’49195 application and reference A and vapor-assisted calcination to generate the template structure. Many of these frameworks wrinkled during drying but remained intact, as Figure 15 shown in the magnified inset of A, where the folds in the wrinkled shell can be observed.

[0393] Figure 15 B is a TEM micrograph of an uncollapsed hollow BN framework. From this and from Figure 15 the magnified TEM micrograph of C, circular and spherical unit cell subunits can be discerned. The more curved unit cell geometry may contribute to the flexibility of these BN frameworks, while the more angular unit cell geometry may have corners and regions that are more resistant to wrinkling and bending. As with the Figure 13 elongated BN frameworks shown in A through Figure 13 E, Figure 15 the hollow frameworks in A through Figure 15 C exhibit a degree of mechanical robustness and elasticity, which requires crosslinking in the anthracite network.

[0394] Example P 29 : In another exemplary procedure, boron carbonitride (BC x N) coating materials including a synthetic anthracite network can be directly synthesized on a template material by chemical vapor deposition. This synthesis demonstrates that BC x N lattice nucleation and radical-driven BC x N lattice growth can be used to synthesize BC x N anthracite networks from graphene BC x N in a manner similar to the formation of synthetic anthracite networks from graphene carbon and graphene BN. Thus, BC x N coating frameworks can be synthesized by a template-directed surface replication procedure in a manner similar to the template-directed synthesis of carbonaceous coating frameworks. As such, the general method (and preferred methods) can be used to synthesize these coating materials and other coating materials formed according to similar nucleation and growth mechanics.

[0395] In addition, similar to the radical-driven carbon growth process, the formation of BC x N sp x networks by the radical-driven BC x N growth process should be optimized by adjusting the amount of hydrogen in the gas medium during growth. This will prevent hydrogen from being released too quickly from the growing BC x N domains and allow the tectonic interfaces to rearrange to maximize the edge-to-edge sp x of the BC 2 and sp3 The grafted configuration. Then, these BN sp x The maturation of the precursor network by annealing is used to transform them into substantially sp 2 Hybridized BN helical networks, which also proceeds according to mechanics similar to the maturation of the carbonaceous sp x Precursor network and the formation of carbonaceous helical networks.

[0396] For demonstration purposes, an N2-type template precursor material can first be synthesized in a manner consistent with the general (and preferred) method. This synthesis is described in the '49195 application and reference A.

[0397] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace according to Scheme B, as detailed in Part III. For this treatment, approximately 7.88 g of the N2-type powder can be placed in the tube furnace. A ceramic boat containing 1.30 g of ammonia borane complex (H3NBH3) can be placed in a quartz tube just outside the furnace heating zone such that when the furnace reaches a temperature of 700 °C, H3NBH3 reaches a temperature between 130 °C and 170 °C. After sealing the tube, an Ar gas flow of 2000 sccm can be initiated. Under the flowing Ar, the furnace can be heated from room temperature to a temperature setting of 700 °C at a heating rate of 20 °C / min. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to recapture and preserve the CO2 process gas released during the decomposition of the template precursor material. The type of porous MgO template material produced by this thermal process is identified herein as N2T7. The elongated superstructure of these porous templates is obtained from N2-type nesquehonite template precursor particles, which are also elongated.

[0398] Approximately 2 minutes after the furnace reaches the temperature setting of 700 °C, white smoke can gradually form and be observed in the tube and exhaust duct. This indicates the initial evaporation of H3NBH3. Approximately 5 minutes after the furnace reaches the temperature setting of 700 °C, a 64 sccm flow of C3H6 can be initiated and this condition can be maintained for 5 minutes such that H3NBH3 and C3H6 flow simultaneously. Then, the C3H6 gas flow can be terminated and the H3NBH3 flow can continue for an additional 5 minutes. Then the furnace can be cooled to room temperature under a continuous Ar flow.

[0399] The powder bed produced by this procedure includes a light phase and a dark phase on the surface. The powder bed in the boat when removed from the furnace is shown in Figure 16 The light phase and the dark phase are marked in Figure 16 These correspond to the light phase and the dark phase found in the optical micrographs of the powder in Figure 17 A to Figure 17 B. The Raman spectrum of the light phase (asFigure 17 The broad peak between 1000 and 2300 cm -1 is revealed, which is consistent with disordered BN. A second peak can be observed at approximately 1595 cm -1 . This feature includes the G peak associated with sp 2 hybridized carbon bonding. This indicates that both carbon and BN are present in the light phase. At the same time, the absence of the D peak associated with the radial breathing mode of sp 2 carbon rings indicates that carbon does not exist in the form of polyatomic carbon rings - i.e., as a graphene phase coexisting with the BN phase, but its presence is distributed throughout the BC x N molecular structure. This phase of the powder in the crucible is identified herein as N2T7P 29 .

[0400] Next, the content extraction of N2T7P 29 phase can be performed, just as in the separation stage of the general method (or the preferred method). This can be carried out in an aqueous H2CO3 extractant solution. After the content MgO is dissolved, the BN-coated framework can be filtered, rinsed, and dried. In the full implementation of the general method, the H2CO3 aqueous solution can be generated using the retained process water from the precipitation in the precursor stage, and the Mg(HCO3)2 aqueous solution can be utilized as the solution reserve for the precipitation of the MgCO3·xH2O template precursor material (such as N2-type nesquehonite). In this way, both the template material and the process liquid are preserved for recycling. The CO2 process gas can also be beneficially preserved and used for regenerating the extractant solution. The type of BC x N-coated framework generated by this process is identified herein as P 29 .

[0401] The Raman spectrum of the light phase associated with the BC x N-coated material can be compared with the dark phase as shown in Figure 17 B, which has a more typical disordered sp 2 carbon spectrum including both the D peak and the G peak. This phase presenting brown (as shown in Figure 16 ) may include BC x N with a higher x value compared to the light phase.

[0402] V. References A: Detailed description from the '49195 application

[0403] The detailed description begins with an initial section of "Terms and Concepts" which provides the language and concepts for describing and understanding the present invention. The subsequent sections are organized according to the following four method stages: "Precursor Stage", "Template Stage", "Replication Stage", and "Separation Stage". Multiple exemplary procedures and materials related to each of the four stages are presented. Many potential variations of each stage can be readily conceived by those skilled in the art and can be combined without departing from the method to form numerous variations.

[0404] The detailed description is organized according to the following sections:

[0405] I*. Terms and Concepts

[0406] II*. Description of General Methods and Variations

[0407] III*. Furnace Schemes, Analytical Techniques, and Material Nomenclature

[0408] IV*. Precursor Stage – Examples

[0409] V*. Template Stage – Examples

[0410] VI*. Replication Stage – Examples

[0411] VII*. Separation Stage – Examples

[0412] VIII*. Coated Frame Examples

[0413] I*. Terms and Concepts

[0414] As defined herein, a "template" is a potential sacrificial structure that imparts a desired morphology to another material formed in or on it. Associated with surface replication techniques are the surface of the template that is positively replicated (i.e., the "template surface") and the bulk phase that is negatively replicated (i.e., the "template bulk"). The template can also serve other roles, such as catalyzing the formation of a coating material. A "templated" structure is a structure that replicates a certain feature of the template.

[0415] A "coating" or "coated" material is a material formed in or on a solid or "hard" template material.

[0416] As defined herein, "surface replication" includes template techniques in which the surface of a template is used to direct the formation of a thin coating wall of an adsorbed material that substantially encapsulates and replicates the template surface on which the wall is formed. Subsequently, when displaced, the template bulk is negatively replicated by the intracellular space within the coating wall. Surface replication produces a coated frame with a templated pore wall architecture.

[0417] As defined herein, a "coated framework" (or "framework") is a nanostructured coating body formed during surface replication. The coated framework includes a nanostructured "coating wall" (or "wall") having a thickness that can range from less than 1 nm to 100 nm but is preferably between 0.6 nm and 5 nm. Since the coating wall substantially encapsulates and replicates the template surface, the coating wall can be described as "conformal". Coated frameworks can be made to have diverse architectures ranging from simple hollow architectures formed on non-porous templates to maze architectures formed on porous templates. They can also have different chemical compositions. A typical framework can be constructed of carbon and can be referred to as a "carbon-coated framework".

[0418] As defined herein, "contents" includes the template as it exists within a substantially encapsulated coating phase. Thus, after a coating phase has been formed around the template, the template can be described as the contents or "content".

[0419] As defined herein, a "coated complex" or "PC" material is a composite structure that includes the contents and the coating body. The PC material can be represented as x@y, where x is the coating element or compound and y is the content element or compound. For example, a PC structure that includes a carbon coating body on a MgO contents can be represented as C@MgO.

[0420] The term "positive" is used herein to describe the space occupied by a solid mass of material. The space occupied by the contents in a coated complex (i.e., the "content space") is an example of a positive space. A non-porous template includes only positive space. Except for the space occupied by its thin walls, a coated framework does not include positive space.

[0421] The term "negative" is used herein to describe the space not occupied by a solid or liquid mass of material. Negative space can be empty, gas-filled, or liquid-filled. The pores inside an unimpregnated porous template include negative space. A porous template includes both positive and negative space. Except for the space occupied by its thin walls, a coated framework includes only negative space.

[0422] The term "unit cell" is used herein to describe the pore wall morphology associated with a coated framework. A "unit cell" or "unit cell subunit" includes the region of pores within a specified unit cell and the coating wall surrounding the pores.

[0423] The term "intra-unit cell" is used herein to describe the negative space within a coated framework that is formed by removing the contents from the coated complex. The intra-unit cell space is substantially encapsulated by the coating wall, just as the contents from which it is derived.

[0424] The term "extra-crystalline" is used herein to describe the negative space in the coating framework, which is inherited from the pore space of the coated complex, which in turn is inherited from the pore space of the porous template. We note that despite the "-extra" prefix, the extra-crystalline space can be substantially within the coating framework.

[0425] The intra-crystalline and extra-crystalline spaces of the coating framework are substantially separated by the coating wall. However, the ability to remove the contents from the template composite implies that the wall is open somewhere or is an incomplete barrier, since perfectly encapsulated contents cannot be removed. Thus, while the coated body is described herein as substantially encapsulating the template surface, the encapsulation may still be incomplete or there may be fissures.

[0426] The term "native" is used herein to describe the morphological state of the coating structure in the coated complex. "Native" features include features that are substantially in their native state, and we may say that a structure "natively" has a certain feature (e.g., a coating wall that is natively 1 nm thick). After removing the contents from the coated complex, the coated body may substantially retain its native characteristics or may change.

[0427] The term "non-native" is used herein to describe the morphological state of the coating structure that has changed significantly from its native morphological state (i.e., its original state in the coated complex). Such a change can occur at the sub-structure or super-structure level. For example, during the evaporation drying of the internal liquid, the coating wall may be pulled inward by the liquid, causing a portion of the intra-crystalline space to collapse. The deformation of the framework to a non-native collapsed morphology can be reversible - i.e., the framework may be able to substantially resume its native morphology.

[0428] The term "labyrinth" or "labyrinthine" is used herein to describe a network of interconnected pores in the template or coating framework. The labyrinth can be intra-crystalline or extra-crystalline. The coating framework formed on the porous template may natively include intra-crystalline and extra-crystalline labyrinths; thus, the framework formed on the porous template can be described as a "labyrinthine framework". The intra-crystalline and extra-crystalline labyrinths of the labyrinthine framework, while not overlapping, can be intertwined. The labyrinthine framework includes a preferred class of coating frameworks.

[0429] As defined herein, a "template precursor" or "precursor" is a material from which a template is obtained through a process that may include decomposition, grain growth, and sintering. The template may retain a pseudo-morphological similarity to the template precursor; thus, engineering the precursor can provide a way to engineer the template. The precursor is formed in a process liquid and is obtained from a stock solution.

[0430] The term "superstructure" is defined herein as the overall size and geometric structure of a porous template or coated framework. The superstructure of a coated framework can be inherited from the morphology of the template precursor. The superstructure of a coated framework is important because the overall size and geometric structure of the framework will affect its properties, including the way it interacts with other particles. Some superstructures can facilitate the drying of a wet paste of a coated framework into a fine powder, while other superstructures can cause the wet paste to dry into macroscopic particles that may require subsequent grinding. Superstructures can include the following shapes:

[0431] · "Isometric", which is defined herein as a shape that is similar in size (size difference less than 5-fold) along its long axis, medium axis, and short axis.

[0432] · "Elongated", which is defined herein as a shape that is significantly larger in size along its long axis than along its medium axis and short axis (5-fold up to 50-fold).

[0433] · "Thin", which is defined herein as a shape that is more than 5 times along its long axis and medium axis than along its short axis.

[0434] · "Hierarchical", which is defined herein as an isometric or elongated shape with thin features.

[0435] The term "substructure" is defined herein as the local morphology of a porous template or coated framework - i.e., the internal architecture. Certain porous templates or coated frameworks have substructures that include repeating associated substructural units or "subunits". Different substructures can be characterized by subunits that differ in shape, size, and spacing from one another.

[0436] The term "void cell" is used herein to describe the internal negative space that is not considered herein to be templated nor part of the coated framework, but which is still substantially surrounded by and located within the framework. The void cell space is not templated space because it does not strictly correspond to the positive space, negative space, or surface of the template, and it only occurs when surface replication cannot occur on a certain part of the template surface (usually an inaccessible internal region).

[0437] Void cell space may be desirable for density reduction in certain applications and can be engineered using a combination of reasonable template engineering and diffusion-limited synthesis techniques. In particular, large template precursors can be used to produce large templates that can combine long diffusion paths with small pores with minimal sintering. Rational design of surface replication parameters can also help. For example, during CVD, low concentrations of carbonaceous vapors can be more readily scavenged by reaction sites and prevented from penetrating throughout the porous substructure of the porous template.

[0438] Another way to achieve density reduction is by using a porous template precursor material. This results in extra-cellular internal porosity that is superior to the amorphous cell space, as it is more engineered and does not require diffusion constraints. The porous template precursor can be made by using a blowant (e.g., hollow microspheres generated during spray drying) or by using a sacrificial material during the preparation of the template precursor (e.g., around sacrificial micelles or polymer synthesis template precursors).

[0439] The concept of "compactness" as used herein refers to the area of the coating walls contained within a given volume of the coated framework - i.e., the volume surface area. A framework with a more compact sub-structure will have a finer and denser arrangement of coating walls within a given volume, while a framework with a less compact sub-structure will have a coarser and more spatially diffuse arrangement of coating walls within a given volume. The porous template and the labyrinthine framework formed thereon can be engineered to have varying degrees of compactness. Compactness includes a measure of the mesoscale cross-linking of the framework - i.e., cross-linking not at the molecular scale but at a higher scale - where the cross-linking is derived from the topology of the template surface.

[0440] The compactness and pore phase of the coated framework can be adjusted by engineering the positive and negative spaces of the template. For example, a porous MgO structure generated by decomposing a magnesium carbonate precursor has a positive space that includes a network of associated MgO microcrystals. Its negative space includes a porous network that extends between and throughout the MgO microcrystals. It is well known that microcrystals can grow at elevated temperatures, thereby coarsening the grain structure. The same process can also lead to the growth and coarsening of the pores. This coarsening of the positive and negative spaces will reduce the surface area of the porous MgO template and, therefore, the compactness of the coated framework formed on the template. As the template coarsens, it will densify, and its densification will reduce the amount of extra-cellular space in the coated framework formed on the template.

[0441] For many reasons, the roughness of the template can be important. For example, expanding the pores of the template and reducing its surface area can allow reactive vapors to diffuse more quickly and deeply throughout the pores of the template during CVD. If sufficient diffusion kinetics can be achieved, the coating walls synthesized in such a process can be more uniform in thickness.

[0442] The compactness and pore phase of the coated framework can also be adjusted by selecting different template precursors. Different precursors will have different proportions of volatile mass. The negative space of the template will depend on the degree of loss of the starting mass of the template precursor during its decomposition. Calcining a template precursor that contains a large proportion of volatile material (e.g., a highly hydrated salt) can produce a porous template with a high specific porosity that is more open to the diffusion flow during CVD. Such a template may also be desirable if a greater amount of extra-cellular space in the coated framework is desired.

[0443] The term "recycled" is used herein to describe process materials that are used in a given step of a production process that have been previously used in that step. Due to the actual losses of process materials that may occur during the production of the coated product (e.g., losses of process liquids due to evaporation or filtration), virgin process materials may be used to replenish these losses, and "recycled" process materials may partially comprise virgin raw materials.

[0444] As defined herein, "process materials" include potentially recyclable non-coated materials used to generate the coating material. Process materials can include process liquids, process gases, extractants, template precursor materials, and template materials.

[0445] As defined herein, "stock solution" contains solvated cations and anions as well as a process liquid, with the solvated ions being carried by the process liquid (which may be referred to herein as the "host"). The stock solution is formed during the separation stage. Precursors are obtained from the stock solution via one or more precipitation, dissolution, or decomposition reactions.

[0446] As defined herein, "process liquid" is the raw material of liquid water ("process water") or a solvent ("process solvent") used in the precursor stage and the separation stage. The process liquid can serve multiple different roles in these stages. In the precursor stage, the formation of the template precursor is carried by the process liquid, and the precursor can incorporate the process liquid into its crystal - for example, a hydrated salt can form in process water and incorporate some process water into its crystal structure. In the separation stage, the extractant is carried by the process liquid, and the solvated ions resulting from the reaction between the template, the process liquid, and the extractant are carried by the process liquid. The process liquid can participate in the generation of the extractant and itself can react with the template during the separation stage.

[0447] As defined herein, "residual liquid" is the portion of the process liquid that may or may not carry solvated ions and that remains non-separated from the solid (e.g., precursor or coated product) when the solid is separated from the main portion of the process liquid. The residual liquid can be contained within the coated product or wetted to its surface. The residual liquid can represent a very small fraction of the total process liquid. If a dry solid is desired, the retention of the residual liquid by the solid may require further separation.

[0448] As defined herein, "extractant" includes an acid carried by the process liquid, and the two phases together constitute the "extractant solution". The extractant can be present in the extractant solution at extremely dilute concentrations. In some cases, the extractant can be generated from the process liquid (and within the process liquid). For example, according to the reaction H2O (l) +CO 2(aq) →H2CO 3(aq) , the carbonic acid (H2CO3) extractant can be generated from (and within) the process water.

[0449] As defined herein, "content extraction" includes the selective removal of a portion of the contents from a content complex. Content extraction includes a reaction between the contents and an extractant solution that produces solvated ions that exude from the surrounding contents, resulting in the simultaneous removal of the contents, the consumption of the extractant from the extractant solution, and the formation of a stock solution. Generally, it is desirable to remove substantially all of the content mass. Sometimes, it may be desirable to partially remove the content mass, or only partial removal of the content mass may be achievable.

[0450] As defined herein, "coating separation" includes separating the coated product from the uncoated saved process materials after content extraction. The saved uncoated phase may include process liquids, stock solutions, and precipitates of the stock solutions. Coating separation may include many different industrial separation techniques (e.g., filtration, centrifugation, foam flotation, solvent-based separation, etc.).

[0451] As defined herein, "solvent-free precipitation" includes the precipitation of a template precursor in a precursor stage, where the precipitation is driven substantially by a solution destabilization mechanism that does not require the introduction of a miscible anti-solvent into the process liquid. As a first example of a solvent-free precipitation technique, a stock solution may be spray dried. As a second example of a solvent-free precipitation technique, a metastable metal bicarbonate stock solution may be depressurized to reduce the CO2 solubility, resulting in the release of CO2 gas and the precipitation of a metal carbonate. We note that the term "solvent-free precipitation" does not mean that there is absolutely no miscible liquid or solvent during precipitation, but rather indicates that the precipitation is not primarily driven by mixing a miscible liquid into the stock solution. One conceivable scenario is that the miscible liquid mixed with the process liquid remains at substantially the same concentration throughout the liquid cycle.

[0452] As defined herein, "shuttle" includes a content extraction technique that may be used during a separation stage, where, simultaneously: (i) an extractant is generated by the reaction of a process gas with a process liquid; (ii) the contents are reacted with the extractant solution; (iii) the extractant is consumed; (iv) solvated ions in the stock solution exude from the contents; and (v) a precipitate is formed from the stock solution outside the contents. For example, shuttle may include simultaneously: (i) forming an H2CO3 extractant by dissolving CO2 into process water; (ii) reacting MgO contents with the H2CO3 extractant solution; (iii) consuming H2CO3; (iv) forming Mg 2+ and (HCO3) - ions; and (v) precipitating magnesium carbonate in the surrounding process water.

[0453] “MgCO3·xH2O” is used herein to describe magnesium carbonate. It can include any hydrated or anhydrous magnesium carbonate, as well as basic magnesium carbonate such as hydromagnesite.

[0454] As defined herein, "template cycle" includes a cyclic loop in which a template is constructed, utilized, and reconstructed.

[0455] As defined herein, "liquid cycle" includes a cyclic loop in which process liquid is used for liquid-phase extraction of contents and liquid-phase formation of precursors.

[0456] As defined herein, "gas cycle" includes a cyclic loop in which a process gas is dissolved into a process liquid to produce an extractant solution, and then subsequently released and recaptured. The release can be associated with the formation of a template precursor or a template.

[0457] The "yield" of a coating material or a process for preparing a coating material is defined herein as the coating mass divided by the sum of the content mass and the coating mass. The yield can be used to understand the amount of template material required to produce a given amount of coating material.

[0458] Figure 18 is a cross-sectional view showing surface replication. The first structure in the sequence represents a simple non-porous template including a template body and a template surface. The second structure in the sequence represents a PC structure including a content and a coating body. This complex is formed by applying a conformal coating wall on the template surface. The third structure in the sequence includes a coating framework in a liquid. This represents the framework after removing the content by liquid-phase extraction. The fourth structure in the sequence represents the framework in its native state after drying. The wall of the coating framework substantially replicates the template surface, and its pores substantially replicate the template body.

[0459] Figure 19 is a cross-sectional view showing the formation of a coating framework using a porous template. The first structure in the sequence represents a template having a number of pores leading to a central pore. The entire pore space is not occupied by a solid or liquid mass and includes negative space. The second structure in the sequence represents a PC structure including a content and a coating body. This complex is formed by applying a conformal coating body on the template surface. The PC structure includes a positive space associated with the content and a negative space associated with the pores of the porous template. The third structure in the sequence represents a coating framework formed by removing the content. The framework includes a negative intracrystalline space corresponding to the content of the PC structure and a negative extracellular space corresponding to the pores of the PC structure. Both the intracrystalline space and the extracellular space are located inside the coating framework.

[0460] Figure 20A cross-sectional view showing the differences between the coated frameworks in their native and non-native morphological states. The first structure in the sequence represents a PC structure comprising a content and a coating body. The morphology of the coating body in the PC structure represents its native form. The second structure in the sequence represents a coated framework formed by removing the content. The morphology of the framework is essentially unchanged from its original form in the PC structure, and thus the framework is in its native state. The third structure in the sequence represents a coated framework that has been deformed and collapsed. In this non-native state, the wall no longer represents a replica of the template surface, nor does the intracrystalline space represent a negative replica of the content. If elastic deformation occurs, the framework may reversibly deform back to its native form.

[0461] Figure 21 A is a cross-sectional view showing the synthesis of a labyrinthine framework. From left to right, the first structure in the sequence represents a template precursor. The second structure represents a porous template. The porous template comprises a labyrinth of interconnected template pores (although their connectivity is not represented in the cross-section). The surface of this porous structure guides the formation of the coating body. The third structure in the sequence represents a PC structure comprising a content and a coating body. The labyrinth of template pores in the template is inherited by the PC structure. The fourth structure in the sequence represents a labyrinthine framework formed by removing the content. The framework inherently includes an intracrystalline labyrinth that reflects the positive space of the template and an extracrystalline labyrinth that reflects its negative space. The intracrystalline and extracrystalline labyrinths, although not overlapping, can interweave throughout the volume of the framework.

[0462] Figure 21 B is an SEM micrograph of a labyrinthine carbon framework synthesized on a porous MgO template. The content has been removed, and the framework retains its native form. From the main image, we can see that the framework includes a rhombohedral superstructure. This superstructure is inherited from a rhombohedral magnesite precursor. From the magnified inset, we can see the crystallographic substructure of the unit cell subunits. Two such subunits are outlined and labeled in the magnified inset. Each unit cell subunit includes intracrystalline pores and an encapsulated portion of the coating wall. We can also see extracrystalline pores in the magnified inset, and two such pores are labeled. The extracrystalline labyrinth traverses the interior of the framework, interweaving with the intracrystalline labyrinth.

[0463] Figure A22 is a TEM micrograph of (top) a PC particle comprising a graphene-coated phase and a MgO content phase and (bottom) a graphene-coated framework after content extraction. Figure 22 B is a HRTEM micrograph showing a disordered nematic arrangement of graphene layers comprising segments of the coating wall.

[0464] Figure 23 A cross-sectional view showing four types of superstructure shapes: elongated, thin, equiaxed, and hierarchical equiaxed. The cross-hatching represents the crystallographic substructure at a smaller scale that exists throughout the superstructure. Figure 23The exemplary "hierarchical equiaxed" superstructure shown is a hollow sphere with a thin shell.

[0465] Figure 24 Shows how density reduction of the coated framework can be achieved through hierarchical pore engineering. This is a cross-sectional representation, so the template subunits, although appearing disconnected, are connected. Figure 24 A shows the generation of a density-reduced non-crystalline cell space within the coated framework through a diffusion-limited surface replication process. In this case, the template precursor can be poreless. Diffusion limitation can prevent the uniform distribution of the adsorbate material throughout the porous substructure. This can be beneficial for generating a coated wall with a certain thickness and integrity gradient, and in some cases, this can even generate a hollow non-crystalline cell space within the coated framework, as Figure 24 shown in A. Figure 24 B shows the generation of a density-reduced extra-crystalline cell space within the coated framework through a porous template precursor material formed around a trapped gas region. This can occur due to the influence of an internal blowing body or due to the formation around a gas bubble. Figure 24 C shows the generation of a density-reduced extra-crystalline cell space within the coated framework through a porous template precursor material formed around a sacrificial material that is subsequently removed.

[0466] Figure 25 Is a cross-sectional view showing three labyrinthine frameworks with different substructures. The substructure represented on the left side of the illustration is the least compact of the three. Its volume is similar to the volumes of the others, but it contains less coated area within this volume. The substructure represented in the center of the illustration is slightly more compact than the left-side substructure because its volume contains a larger coated area. The substructure represented on the right side of the illustration is the most compact - its volume, although similar to the volumes of the other two substructures, contains the largest coated area. This illustration shows that the degree of compaction of the coated framework is imparted by the volume-specific surface area of the porous template - that is, the total internal and external surface area per unit volume of the template, where the template volume includes the positive and negative spaces of the template.

[0467] Figure 26 Is a cross-sectional view showing a shuttle. The first frame in the sequence represents the PC material immersed in the extractant solution. The second frame in the sequence represents the coated framework containing the incompletely extracted contents. In this second frame, the reaction of the contents with the extractant solution is ongoing. The solvated ions formed by this reaction are diffusing out of the coated framework as indicated by the arrows and precipitating in the surrounding process liquid. In other words, the content mass is "shuttling" out of the coated body in the form of solvated ions, and a portion of the solvated ions then reprecipitate outside the framework. We note that the precipitate and the contents may not include the same compounds.

[0468] II*. Description of general methods and variants

[0469] "General method" is the most basic form of a method. It includes a method for synthesizing a coated product in which most of the template material and process liquid are preserved and reusable. Therefore, the general method can be performed cyclically. All variations of the methods disclosed in this disclosure include some variation of the general method.

[0470] The general method includes a series of steps presented herein for ease of description in four stages, namely, the precursor stage, the template stage, the replication stage, and the separation stage. Each stage is defined according to one or more steps as described below:

[0471] Precursor stage: Obtain precursor material from a stock solution by solventless precipitation. A portion of the process liquid is preserved.

[0472] Template stage: Process the precursor material formed in the precursor stage in one or more procedures to form template material.

[0473] Replication stage: Adsorb an adsorbate material onto the template surface of the template to form PC material.

[0474] Separation stage: Perform content extraction and coating separation. Content extraction yields a stock solution. Coating separation separates the coated product from the preserved process material.

[0475] In practice, each step within these stages can itself include multiple subsidiary steps. Additionally, each of these steps can occur simultaneously with steps from another stage such that in practice different stages can overlap in chronological order. This is particularly anticipatable in variations that employ a one-pot technique. As a hypothetical example of this, a stock solution and an adsorbate material can be continuously sprayed into a furnace together. In this hypothetical furnace, continuously and simultaneously, precursor particles can be precipitated from the stock solution, template particles can be formed by heating the precursor particles, and a coating material can be adsorbed onto the template particles. This would correspond to the steps herein attributed respectively to the precursor stage, the template stage, and the replication stage.

[0476] Similarly, it is envisioned that in practice many variations of the general method can incorporate the steps described in the four stages in different orders. Moreover, in some variations, steps that are by definition attributed to one of the four stages herein can alternatively occur in different stages. Such variations are envisioned herein and do not deviate from the inventive method which is presented herein as a discrete sequence of four stages only for the purpose of describing the overall cycle.

[0477] Ancillary processing steps (such as rinsing, drying, blending, condensing, spraying, stirring, etc.) can also be incorporated into each stage of the method. As a hypothetical example of this, the replication stage can involve coating a template material with a coating material via a liquid-phase adsorption procedure, followed by filtering, rinsing, and drying the resulting PC material. Incorporating these processing steps in many variations will be obvious to those skilled in the art, and thus, these steps are not enumerated herein.

[0478] The inputs and outputs of the general method are shown in Figure 3 . The general method includes a template cycle by which the template material can be preserved and reused, and a liquid cycle by which the process liquid can be preserved and reused.

[0479] Variations of the general method

[0480] The following discussion enumerates various ways in which the general method can be implemented differently. The omission of variations in this discussion should not be construed as restrictive, as an exhaustive list of ways to implement the general method is impracticable.

[0481] The general method is intended to provide a way to produce coated products cyclically while preserving process materials. In each cycle of the general method, a portion of the process materials used is preserved and reused. In some variations, substantially all of the process materials used can be preserved and reused. In other variations, a portion of the process materials may be lost. A hypothetical example of this is the evaporation loss of process liquid from an open tank or a wet filter.

[0482] In some variations of the general method, the process steps can correspond to a batch process. In other variations, the process steps can correspond to a continuous process.

[0483] In some variations of the general method, solventless precipitation can include at least one of the following techniques: heating or cooling a stock solution to change the solubility of the solute in the stock solution; volatilizing dissolved gas within the stock solution; reducing the pressure of the stock solution; atomizing the stock solution; spray drying the stock solution or spray pyrolysis.

[0484] In some variations of the general method, the precursor structure can include at least one of the following: an elongated, thin, equiaxed or hierarchically equiaxed superstructure; an elongated superstructure with an aspect ratio greater than 200:1; an elongated superstructure with an aspect ratio between 50:1 and 200:1; a spheroid or spherical superstructure; a hollow superstructure; a fragmented superstructure including fragments of some other parent superstructure; a curved fragmented superstructure including fragments of a hollow superstructure.

[0485] In some variants of the general method, the precursor structure can precipitate around one or more other sacrificial structures, which can be present as inclusions in the precursor structure after the precursor structure precipitates. In some variants, these inclusions in the precursor structure can then be removed, creating voids.

[0486] In some variants of the general method, the measurement of the precursor structure along its long axis can be less than 1 μm. In some variants, the measurement of the precursor along its long axis can be between 1 μm and 100 μm. In some variants, the measurement of the precursor along its long axis can be between 100 μm and 1,000 μm.

[0487] In some variants of the general method, the precursor material can include at least one of the following: hydrates; metal bicarbonates or carbonates; Group I or II metal bicarbonates or carbonates; mixtures of salts. In some variants, the precursor can include MgCO3·xH2O in the form of at least one of the following: hexahydrate, nesquehonite, lansfordite, hydromagnesite, artinite, magnesite, and nanocrystalline or amorphous MgCO3·xH2O.

[0488] In some variants of the general method, the stock solution can include at least one of the following: metal cations and oxyanions; aqueous solutions of metal bicarbonates; Group I or II metal bicarbonates; organic salts; Mg(HCO3)2. In some variants, the stock solution can include at least one of dissolved gases, acids, and bases. In some variants, the stock solution can be metastable.

[0489] In some variants of the general method, the process liquid preserved in the precursor stage can include distillate. In some variants, the distillate can be formed by condensing the process liquid vapor formed during spray drying or spray pyrolysis. In some variants, the process liquid preserved in the precursor stage can carry solvated ions, and the process liquid and the ions together constitute the mother liquor.

[0490] In some variants of the general method, the treatment performed on the precursor material in the template stage can include at least one of the following: decomposing the precursor; partially or locally decomposing the precursor; decomposing the precursor surface; thermal decomposition; and oxidizing the organic phase present within the precursor structure. In some variants, the treatment can include flash drying, spray drying, spray pyrolysis, vacuum drying, rapid heating, slow heating, sublimation. In some variants, the vapor released during the treatment can be preserved. In some variants, the released vapor can include at least one of CO2 and H2O. In some variants, the treatment can include at least one of the following: roughening the grain structure of the precursor or the decomposition product of the precursor; exposure to reactive vapors; exposure to water vapor; sintering; sintering with the assistance of dopants.

[0491] In some variants of the general method, the template material may include at least one of the following: metal carbonates, metal oxides, Group I or II metal oxides, transition metals, and MgO. In some variants, the template structure may include at least one of the following: macropores, mesopores, hierarchical porosity, subunits greater than 100 nm, subunits between 20 nm and 100 nm, and subunits between 1 nm and 20 nm.

[0492] In some variants of the general method, the template structure may include at least one of the following: elongated, thin, equiaxed, or hierarchically equiaxed superstructures; elongated superstructures with an aspect ratio greater than 200:1; elongated superstructures with an aspect ratio between 50:1 and 200:1; globular or spherical superstructures; hollow superstructures; fragmented superstructures comprising fragments of some other parent superstructure; and curved fragmented superstructures comprising fragments of a hollow superstructure.

[0493] In some variants of the general method, adsorbing the coating material to the template surface may include at least one of the following: coating techniques, physical vapor deposition, and chemical vapor deposition. In some variants, the coating technique may include coating a liquid or solid organic coating onto the template surface and then obtaining a carbon coating from the parent coating. In some variants, the deposition may include pyrolytic decomposition of a vapor-phase organic compound at a temperature between 350 °C and 950 °C. In some variants, the coated carbon may be annealed after adsorption to the template surface.

[0494] In some variants of the general method, content extraction may utilize an extractant solution comprising a weak acid as the extractant. In some variants, the extractant solution may be formed by dissolving a process gas in process water. In some variants, the extractant solution may be an aqueous solution of H2CO3 formed by dissolving liquid or gaseous CO2 in process water. In some variants, content extraction may include a shuttle technique. In some variants, content extraction may be performed under elevated pressure or temperature conditions.

[0495] In some variants of the general method, coating separation may include at least one of the following: decantation, hydrocycloning, sedimentation, deposition, flotation, froth flotation, centrifugation, filtration, and liquid-liquid extraction. In some variants, coating separation may separate the coated product from substantially all of the process liquid. In some variants, the coated product may retain a residual portion of the process liquid. In some variants, the coated product may be naturally floating due to the retention of internal gas. In some variants, the internal gas of the coated product may be expanded by reducing the pressure of the surrounding process liquid, increasing the buoyancy of the coated product and causing flotation. In some variants, a portion of the internal gas of the coated product may exude by reducing the pressure of the surrounding process liquid and then repressurizing the surrounding process liquid such that the hydrostatic pressure causes the process liquid to penetrate the coated product.

[0496] In some variations of the general method, the coated framework may include at least one of the following: a carbonaceous material, pyrolytic carbon, an anthracite network of carbon, a sp x network of carbon, and a helical network of carbon.

[0497] In some variations of the general method, under 532 nm excitation, the carbonaceous coated framework may include at least one of the following: a Raman spectral I D / I G ratio between 4.0 and 1.5; a Raman spectral I D / I G ratio between 1.5 and 1.0; a Raman spectral I D / I G ratio between 1.0 and 0.1; a Raman spectral I Tr / I G ratio between 0.0 and 0.1; a Raman spectral I Tr / I G ratio between 0.1 and 0.5; a Raman spectral I Tr / I G ratio between 0 and 0.15; a Raman spectral I 2D / I G ratio between 0.15 and 0.3; a Raman spectral I 2D / I G ratio between 0.30 and 2.0; and a Raman spectral I 2D / I G ratio.

[0498] In some variations of the general method, under 532 nm excitation, the carbonaceous coated framework may include at least one of the following: an unfitted Raman spectral D peak located between 1345 and 1375 cm -1 ; an unfitted Raman spectral D peak located between 1332 and 1345 cm -1 ; an unfitted Raman spectral D peak located between 1300 and 1332 cm -1 ; an unfitted Raman spectral G peak located between 1520 cm -1 and 1585 cm -1 ; an unfitted Raman spectral G peak located between 1585 cm -1 and 1600 cm -1 ; and an unfitted Raman spectral G peak located between 1600 cm -1 and 1615 cm -1 .

[0499] In some variations of the general method, the coated product may include a coated framework. In some variations, the coated framework may include at least one of the following: native form, non-native form, internal gas, hydrophobic surface, hydrophilic surface, mesopores, one or more macropores, hierarchical porosity.

[0500] In some variations of the general method, the coated framework may have a measurement along its long axis of less than 1 μm. In some variations, the coated framework may have a measurement along its long axis between 1 μm and 100 μm. In some variations, the coated framework may have a measurement along its long axis between 100 μm and 1,000 μm. In some variations, the coated framework may include an elongated, thin, equiaxed, or hierarchically equiaxed superstructure. In some variations, an elongated coated framework may have an aspect ratio between 50:1 and 200:1. In some variations, the equiaxed superstructure of the coated framework may be spheroidal or spherical. In some variations, the equiaxed superstructure of the coated framework may be hollow. In some variations, the coated framework may include fragments of a hollow shell. In some variations, the coated framework may include non-crystalline cell space.

[0501] In some variations of the general method, the coated framework may include a BET surface area of 1,500 to 3,000 m 2 / g. In some variations of the general method, the coated framework may include a BET surface area of 10 to 1,500 m 2 / g.

[0502] In some variations of the general method, the coated product may be subjected to further processing after coated separation. In some variations, the further processing after coated separation may include at least one of the following: flash drying, spray drying, spray pyrolysis, decomposition, chemical reaction, annealing, and chemical functionalization.

[0503] In some variations of the general method, the liquid recycle may also incorporate the re-capture and preservation of process liquids released or evaporated (possibly in the vapor phase) during the templating stage, although this is not reflected as an output in Figure 3 It is not reflected because in most (but not all) variations of the envisioned general method, the amount of process liquid preserved during the templating stage will be significantly less than the amount of process liquid preserved during the precursor stage.

[0504] In some variations of the general method, a gas recycle may be incorporated into the method. The inputs and outputs of the general method with gas recycle are shown in Figure 4 In the gas recycle, process gas is released during the precursor stage and / or the templating stage. This released gas is preserved. Then, during the separation stage, the preserved process gas may be dissolved into the preserved process liquid to generate an extractant solution.

[0505] The preferred methods described below include variants of the general method, in which MgCO3·xH2O template precursor material is obtained from an aqueous Mg(HCO3)2 stock solution, and a portion of the CO2 process gas is conserved by a gas recycle process. The inputs and outputs of the preferred method are shown in Figure 5 . The preferred method includes:

[0506] Precursor stage: Obtaining MgCO3·xH2O precursor material from an aqueous Mg(HCO3)2 stock solution, where said obtaining includes solvent-free precipitation of MgCO3·xH2O and emission of CO2 process gas. A portion of the released CO2 process gas is conserved. The MgCO3·xH2O precursor material and process water are separated. The process water is conserved.

[0507] Template stage: Thermally decomposing the MgCO3·xH2O precursor material formed in the precursor stage in one or more procedures to form a porous MgO template material. The released CO2 process gas may be conserved.

[0508] Copying stage: Adsorbing an organic or carbonaceous coating material onto the template surface of the porous MgO template to form a PC material.

[0509] Separation stage: Dissolving the conserved CO2 process gas into the conserved process water to form an aqueous H2CO3 extractant solution. Content extraction includes the reaction between the content MgO and the aqueous H2CO3 extractant solution, thereby generating an aqueous Mg(HCO3)2 stock solution. Coating separation may include techniques for removing process water from the coated product to minimize residual process water. Foam flotation, liquid-liquid separation, or other techniques based on hydrophobicity may be used to separate the carbon coating.

[0510] Certain variants of the preferred method may employ pressure regulation in order to form a concentrated stock solution and improve the precipitation process. A concentrated stock solution may be associated with many benefits, including excellent precipitation kinetics, reduced process water usage, smaller vessels, and improved energy efficiency. Two exemplary ways of achieving this are shown in Figure 27 A to Figure 27 B and described below.

[0511] In Figure 27 the first screen of A, a shuttle technique has been used to effect content extraction. The shuttle technique produces a mixture containing an aqueous Mg(HCO3)2 stock solution, one or more coated frameworks, and MgCO3·xH2O precipitate. This precipitate is in Figure 27In the first view of A, it is represented as a mixture of nesquehonite rods and acicular nesquehonite aggregates. Next, the coated product is separated from other process liquids and solids. After that, the MgCO3·xH2O precipitate is dissolved by increasing the CO2 pressure, which increases the concentrations of dissolved CO2, H2CO3, and HCO3 - , thereby forming a concentrated stock solution, as Figure 27 shown in the second view of A. Finally, as shown in the third view, the MgCO3·xH2O precursor can be rapidly nucleated and precipitated from the concentrated stock solution by reducing the CO2 pressure (and optionally the total pressure).

[0512] Another way to obtain a concentrated stock solution is to perform content extraction in a pressure reactor. A schematic diagram showing this way is shown in Figure 27 B. Similar to the procedure shown in Figure 27 A, the procedure shown in Figure 27 B uses an increased CO2 pressure to increase the concentrations of dissolved CO2, H2CO3, and HCO3 - . In Figure 27 B, a PC material, CO2, and H2O (possibly an aqueous Mg(HCO3)2 mother liquor) are fed into a pressure reactor. Content extraction and the formation of a concentrated stock solution occur inside the pressure reactor. The mixture of the coated product and the concentrated stock solution is discharged from the pressure reactor, and then coated separation can occur in the pressure reactor. The separation can advantageously be achieved using liquid-liquid separation that eliminates the need for rinsing. The MgCO3·xH2O precursor can be rapidly nucleated and precipitated from the concentrated stock solution by reducing the CO2 pressure (and optionally the total pressure).

[0513] III*. Furnace Schemes, Analytical Techniques, and Material Nomenclature

[0514] During the process of describing the procedures for generating exemplary materials described in the subsequent sections, certain furnace schemes have been detailed. These schemes can be used for the exemplary template stage procedures detailed in Part V and the exemplary replication stage procedures detailed in Part VI.

[0515] Scheme A: In Scheme A, a Thermcraft tube furnace modified into a rotary furnace with a quartz tube ( Figure 88A). The furnace has a clamshell design including a cylindrical heating chamber with a diameter of 160 mm and a heating length of 610 mm. The wattage of the furnace is 6800 W, and the maximum operating temperature is 1100 °C. The quartz tube can be a 60 mm OD quartz tube containing an extended intermediate section ("belly") of a 130 mm OD tube positioned within the heating zone of the furnace. The tube is rotatable. The quartz baffle inside the belly can facilitate agitation of the powder sample during rotation. The furnace can be kept horizontal (i.e., not tilted). The template powder sample can be placed inside the belly in the heating zone, and ceramic blocks are inserted outside the belly on each side of the heating zone of the furnace. Glass wool can be used to fix the positions of the ceramic blocks.

[0516] For an exemplary procedure performed using Scheme A, a material sample can be placed inside the belly such that it is agitated within the reactor. The loose-fitting ceramic blocks located outside the belly section on each side of the heating zone of the furnace allow gas flow and block the powder. Packed glass wool can be used to fix the positions of the ceramic blocks while acting as a gas-permeable layer. The ends of the tube can be fitted with two stainless steel flanges to allow gas flow through the system.

[0517] Scheme B: An MTI rotary tube furnace with a quartz tube can be used ( Figure 88 B). The furnace has a clamshell design including a cylindrical heating chamber sized with a diameter of 120 mm and a heating length of 440 mm. The wattage of the furnace is 2500 W, and the maximum operating temperature is 1150 °C. The OD of the quartz tube can be 60 mm. The tube can be substantially horizontal. For an exemplary procedure performed using Scheme B, a material sample can be placed inside a ceramic boat. Then it can be placed inside the quartz tube within the heating zone, and then heating is started. The loose-fitting ceramic blocks located outside the heating zone of the furnace allow gas flow. Packed glass wool can be used to fix the positions of the ceramic blocks while acting as a gas-permeable layer. The ends of the tube can be fitted with two stainless steel flanges.

[0518] Scheme C: A Lindberg Blue-M tube furnace with a quartz tube can be used. The OD of the quartz tube can be 150 mm. The furnace has a clamshell design with a cylindrical heating chamber sized with a diameter of 190 mm and a heating length of 890 mm. The wattage of the furnace is 11,200 W, and the maximum operating temperature is 1200 °C. The tube can be substantially horizontal. For an exemplary procedure performed using Scheme C, a sample can be placed inside a ceramic boat. Then it can be placed inside the quartz tube within the heating zone, and then heating is started. The loose-fitting ceramic blocks located outside the heating zone of the furnace allow gas flow. The ends of the tube can be fitted with two aluminum flanges to allow gas flow through the system.

[0519] Protocol D: A Vulcan 3-550 muffle furnace can be used. The furnace has a rectangular heating chamber with dimensions of 190 mm x 240 mm x 228 mm. The wattage of the furnace is 1440 W, and the maximum operating temperature is 1100 °C. For an exemplary procedure carried out using Protocol D, a material sample can be placed inside a ceramic boat. It can then be placed inside the muffle furnace, and heating can be initiated thereafter.

[0520] Protocol E: A TA Instruments Q600 TGA / DSC can be used. For an exemplary procedure carried out using Protocol E, a 90 μL alumina pan can be used to hold the material sample. Unless otherwise stated, the gas flow can be a specified gas at 100 sccm. The heating rate can be mentioned in the exemplary procedure using Protocol E.

[0521] Multiple analytical techniques are used to characterize the procedures and materials presented herein. These are detailed below.

[0522] Electrolytic conductivity (“conductivity”) is used to measure the concentration of a solution. Conductivity is a measure of the conductance response of a solution. The electrical response of a solution can be related to the concentration of ions dissolved in the solution, and as the ions in the solution precipitate, the conductivity value decreases. Similar to this measurement is total dissolved solids (“TDS”), which correlates the conductivity measurement results with a reference ion concentration (usually potassium chloride), and the ion concentration depends on the dissolved salt compound.

[0523] Thermogravimetric analysis (TGA) is used to analyze the thermal stability and composition of materials. All TGA characterizations are performed on a TA Instruments Q600 TGA / DSC. During TGA analysis, a 90 μL alumina pan is used to hold the sample. Unless otherwise stated, all analytical TGA procedures are carried out at 20 °C / min. Unless otherwise stated, air or Ar (Ar) is used as the carrier gas during the analytical TGA procedure.

[0524] Raman spectroscopy is performed using a ThermoFisher DXR Raman microscope equipped with a 532 nm excitation laser. For each sample analyzed, a 16-point spectrum is generated using measurements taken on a 4x4 point rectangular grid with a point-to-point spacing of 5 μm. The 16-point spectra are then averaged to produce an average spectrum. The Raman peak intensity ratios and Raman peak positions reported for each sample are derived from the average spectrum of the sample. No line fitting software is used, so the reported peak intensity ratios and peak positions are related to the unfitted peaks associated with the overall Raman line shape.

[0525] Gas adsorption measurements are carried out using a Micromeritics Tristar IIPlus. Nitrogen adsorption is measured across a range of pressure (p) values at a temperature of 77 K, where The pressure increment range is up to The BET specific surface area is calculated using Micromeritics MicroActive software, and the specific surface area is assumed to have a cross-sectional area of σ m (N2, 77K) = 0.162 nm 2 and is derived from the BET monolayer capacity. The samples are pretreated by degassing at 100 °C with continuously flowing dry nitrogen before analysis.

[0526] Pore size distribution (PSD) and cumulative pore volume are another technique that can be performed on gas adsorption data to gain insight into the sintering behavior of the particles. The data is collected by Micromeritics Tris tar IIPlus, which measures nitrogen adsorption and desorption at 77 K between pressures and in increments ranging from up to The samples are pretreated by degassing at 100 °C with continuously flowing dry nitrogen before analysis.

[0527] The adsorption-desorption PSD and cumulative pore volume are calculated using Micromeritics MicroActive software by applying the Barrett, Joyner, and Halenda (BJH) method. This method provides a comparative evaluation of the mesopore size distribution of the gas adsorption data. For all BJH data, the Faas correction and Harkins and Jura thickness curves can be applied. The cumulative pore volume V PORE (cm 3 / g) can be measured for both the adsorption and desorption portions of the isotherm.

[0528] Multiple exemplary materials are described in this disclosure. To help identify and track these exemplary materials, a material naming system has been adopted and is described below. All names of exemplary materials are in bold; herein, N2 describes an exemplary material, and N2 refers to nitrogen gas.

[0529] Exemplary types of template precursor materials are designated as S x , where S designates the first or first two letters of the template precursor material (i.e., N represents nesquehonite, L represents lansfordite, Li represents lithium carbonate, C represents magnesium citrate, A represents amorphous or non-crystalline MgCO3·xH2O, H represents hydromagnesite, M represents magnesite, E represents epsomite, Ca represents calcium carbonate), and where x designates different types of precursor compounds (e.g., H1 and H2 represent two different types of hydromagnesite precursors).

[0530] Exemplary types of template materials are in the format S x Ty Nomenclature. S x The name component designates for producing the template type S x T y as the precursor type, and T y The name component designates for producing the template type S x T y for the specific treatment. For example, N1T1 and N1T2 indicate two different template types formed by two different treatments of the precursor type N1. It should be noted that although the complete S x T y name represents a specific template type, but the T y name component itself is only specific to a given S x precursor type. For example, the treatments for making the template types N1T1 and N2T1 are different, although these template types share the same T1 name component.

[0531] Exemplary types of PC materials are in the format S x T y P z named, where S x T y The name component designates the template type, and P z The name component designates a specific carbon-coated body type. For example, M3T1P1 and M3T1P2 indicate two different PC materials formed from the same M3T1 template material. S x T y P z The P within the name z name component is unique - that is, each P z name component designates a unique coated body type, regardless of the S x T y template type used for preparing the coated body.

[0532] Exemplary types of coated frameworks (i.e., porous coated products produced by content extraction) are in the format P z named, where P z The name component does not start with S x T y The P name component used for naming the framework type z matches the S x T y P z P name component of the PC material type z matched.

[0533] Exemplary types of template precursor materials, template materials, coated composite materials, and coated materials in this disclosure are enumerated in Figure 207 . Figure 207Is arranged to show the progress of the synthesized material starting from the template precursor material. Although each exemplary material is not tracked through all four stages, it should be understood that any exemplary material can be tracked if desired. Figure 207 Also follows the above material naming system.

[0534] IV*. Precursor stage – Examples

[0535] This section details the small-scale production of exemplary template precursor materials using exemplary procedures. Thus, these procedures include partial implementation of the general method. Therefore, it should be understood that these procedures must be combined with other procedures in the full implementation of the general method. Additionally, it should be understood that these procedures only demonstrate similar larger-scale procedures that will be used for industrial-scale manufacturing.

[0536] Various techniques can be used for the precipitation of the precursor material. For example, the stock solution can be heated to evaporate the process liquid, causing the stock solution to become supersaturated and precipitate the precursor material. This can be combined with techniques for controlling the shape and size of the precipitated template precursor particles. For example, the stock solution can be spray-dried to produce discrete spheres or hollow spheres. Other techniques that will be obvious to those skilled in the art can be utilized.

[0537] Example N1: In the exemplary precursor stage procedure, elongated nesquehonite (MgCO3·3H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0538] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated during the separation stage of the full implementation of the general method. For this example, water, CO2 gas, and MgO can be used to generate a representative aqueous Mg(HCO3)2 stock solution.

[0539] First, a 0.24 mol kg -1 Mg mixture containing deionized water and the commercial magnesium oxide (MgO) product Akrochem Elastomag 170 can be prepared. This mixture can be carbonated in a circulation tank using a sparger tube through which CO2 is bubbled to generate carbonic acid. After the MgO has completely dissolved to form the stock solution, the CO2 bubbling can be interrupted. The stock solution can be at approximately 14.5 °C.

[0540] Next, it can be at approximately 12 scfm through the sparger tube 空气The flow rate initiates air bubbling within the stock solution in the recycle tank. This bubbling can result in the precipitation of nesquehonite particles and the associated emission of CO2 process gas. Bubbling and recycling can continue until the conductivity of the solution stabilizes. At this point, the aqueous mixture of nesquehonite particles can be filtered to separate the particles from the aqueous Mg(HCO3)2 filtrate. This filtrate contains the mother liquor and substantially all of the process water. In the full implementation of the general method, the separated process water can be conserved for reuse, as Figure 3 shown. Additionally, in the full implementation of the general method, conventional techniques can also be used to conserve the emitted CO2 process gas for reuse.

[0541] The type of nesquehonite template precursor particles generated by this procedure can be identified herein as N1 and can be seen in the Figure 28 SEM micrographs. The template precursor is confirmed to be nesquehonite by its elongated morphology and 70.4% TGA mass loss, which is very consistent with the expected 70.9% nesquehonite mass loss as Figure 208 shown.

[0542] Except for the presence of some small debris, the crystals have a smooth thin surface. The elongated morphology of these crystals may be valuable. In applications that require interlocking particles, such as filtration membranes, the elongated morphology may be useful. In applications that require the assembly of percolation networks, such as for electron transport, compared to equiaxed particle morphologies, elongated particles can achieve percolation with fewer particles. In applications that require mechanical reinforcement, elongated particles can provide excellent tensile properties.

[0543] Example H1: In another exemplary precursor stage procedure, graded equiaxed hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0544] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, an aqueous Mg(HCO3)2 stock solution with an approximate molality of 0.14 mol kg -1 Mg(aq) can be prepared first as the representative stock solution.

[0545] Next, the stock solution can be placed in a 1L Buchi rotary evaporator vessel and then the rotary evaporator vessel can be rotated at 280 RPM in a 100 °C water bath. Crystallization can be allowed to continue until most of the Mg ions have precipitated as hydromagnesite precursor particles. Along with this precipitation, CO2 process gas can be emitted. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during precipitation.

[0546] The resulting hydromagnesite mixture can then be filtered to separate the solids from the aqueous Mg(HCO3)2 filtrate. This filtrate contains the mother liquor and substantially all of the process water. In the full implementation of the general method, the separated mother liquor can be saved for reuse.

[0547] The type of hydromagnesite template precursor particles produced by this procedure are identified herein as H1 and can be seen in Figure 29 representative SEM micrographs. The TGA mass loss of these particles is 56.6%, which is in good agreement with the expected hydromagnesite mass loss of 56.9% ( Figure 208 ). Thin (thickness < 100 nm) hydromagnesite plates are arranged in a hierarchical equiaxed superstructure. Due to the combination of the thin morphological feature and the equiaxed morphological feature, this template precursor morphology is of interest. In applications where a high surface area is required, the hierarchical equiaxed morphology can prevent the surfaces of the thin crystals from being blocked, while simple planar particles can tend to stack on top of each other and block each other's surfaces.

[0548] Example H2: In another exemplary precursor stage procedure, elongated hierarchical hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0549] To demonstrate this acquisition on a small scale, nesquehonite can first be precipitated from a representative aqueous Mg(HCO3)2 stock solution. This stock solution represents the stock solution that can be generated during the separation stage of the full implementation of the general method. For this example, the representative stock solution and the aqueous mixture for precipitating nesquehonite can be obtained using the procedure described in Example N1. Along with this nesquehonite precipitation, the CO2 process gas can be vented. In the full implementation of the general method, conventional techniques can be used to save the released CO2 process gas.

[0550] Next, the nesquehonite mixture can be heated to 100 °C and maintained at that temperature until recrystallization into hydromagnesite is complete. In this exemplary procedure, the process water can completely evaporate, thereby separating it from the solid residue of the elongated hydromagnesite particles. In the full implementation of the general method, conventional techniques can be used to save the released process water.

[0551] The type of hydromagnesite template precursor particles produced by this procedure are identified herein as H2 and can be seen in Figure 30 representative SEM micrographs. This template precursor material can combine the advantages of the above-mentioned elongated and thin morphologies.

[0552] Example H3: In another exemplary precursor stage procedure, tabular hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0553] To demonstrate this obtaining on a small scale, hierarchical hydromagnesite can first be obtained from a representative aqueous Mg(HCO3)2 stock solution. This stock solution represents the stock solution that can be generated during the separation stage of the full implementation of the general method. For this example, the representative stock solution and precipitated hydromagnesite can be obtained using the procedure described in Example H2. Along with the precipitation, CO2 process gas can be vented. In the full implementation of the general method, conventional techniques can be used to conserve the released CO2 process gas. Additionally, in the full implementation of the general method, the separated process water can be conserved.

[0554] Next, the hierarchical hydromagnesite particles can be mechanically disrupted. This can be achieved in a variety of ways using known milling techniques. For demonstration purposes, the particles can be slurried in process water. The mixture can then be stirred using high-shear techniques to break down the fine hierarchical hydromagnesite particles into their constituent individual plates. The tabular hydromagnesite particles can then be filtered out of the process water. In the full implementation of the general method, the separated process water can be conserved for reuse.

[0555] The type of hydromagnesite template precursor particles generated by this procedure are identified herein as H3 and can be seen in Figure 31 the representative SEM micrographs. The TGA mass loss of these particles is 56.6%, which is in very good agreement with the expected hydromagnesite mass loss of 56.9% as seen in Figure 208 .

[0556] Example L1: In another exemplary precursor stage procedure, cubic nesquehonite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0557] To demonstrate this obtaining on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated during the separation stage of the full implementation of the general method. For this example, a representative aqueous Mg(HCO3)2 stock solution with a concentration of approximately 0.25 mol kg -1 Mg(aq) can be prepared and cooled to 2 °C.

[0558] The cooled stock solution can then be subjected to N2 bubbling at a flow rate of 4 scfh 空气 . The resulting precipitation can cause the CO2 process gas to be vented. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during the precipitation.

[0559] After 67 minutes, N2 bubbling can be interrupted. After the interruption of N2 bubbling, the formed crystals can be allowed to be stirred for another 50 minutes, and then the mixture can be filtered to separate the solid from the mother liquor. The solid can be rinsed with deionized water at 5 °C. In the full implementation of the general method, the separated mother liquor can be saved for reuse.

[0560] The nesquehonite template precursor particles of the type generated by this procedure are identified herein as L1 and can be seen in Figure 32 representative SEM micrographs. The template precursor particles have a prismatic equiaxed morphology characteristic of nesquehonite, and the TGA mass loss of these particles is 76.4%, which is in good agreement with the expected nesquehonite mass loss of 76.9% as seen in Figure 208 For applications where the coated product must be combined with a liquid and viscosity effects must be minimized, a prismatic equiaxed morphology may be desirable. Additionally, due to the relatively high hydration state of nesquehonite, for a given mass of Mg, the volume of the generated template precursor is more than that obtainable using MgCO3·xH2O with a lower degree of hydration, and upon decomposition of the precursor material, more template pore volume can be obtained. This can be used to produce a coated framework with more extra-crystalline space.

[0561] Raman spectroscopy can be used to characterize the chemical composition of the template precursor material. Application of this Raman spectroscopy produces a match of peak positions consistent with nesquehonite at 1083 cm Figure 208 as seen in -1 .

[0562] Example L2: In another exemplary precursor stage procedure, equiaxed nesquehonite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0563] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, the representative stock solution can be obtained as follows. First, an aqueous mixture of precipitated nesquehonite can be obtained using the procedure described in Example N1. The concentration of this mixture can be adjusted to 0.62 mol kg -1 Mg. Then the mixture can be added to a high-pressure baffle reactor equipped with a self-aspirating stirrer. The system can be stirred at 700 RPM and cooled to 5 °C while injecting CO2 process gas into the headspace of the reactor until a pressure of 850 psi is reached or until all solids have dissolved, thereby producing a representative pressurized stock solution.

[0564] When the stock solution is depressurized to atmospheric pressure, the stirring rate can be reduced to 500 RPM, and the solution can be maintained at 12 °C while air is passed through the headspace. The resulting precipitation of nesquehonite particles can cause the CO2 process gas to be discharged. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation.

[0565] After 228 minutes, the mixture of nesquehonite particles can be discharged from the reactor and then filtered to separate the nesquehonite solid from the mother liquor. In the full implementation of the general method, the separated mother liquor can be preserved for reuse. For analytical purposes, the nesquehonite solid can be rinsed with deionized water, resuspended in ethanol, filtered again, and dried in a vacuum oven at up to 29 inHg at room temperature.

[0566] The type of nesquehonite template precursor particles generated by this procedure are identified herein as L2. Raman spectroscopic analysis confirms that the product of this reaction matches the product of nesquehonite (as seen in Figure 208 .

[0567] Compared to other isometric MgCO3·xH2O-type precursors (e.g., magnesite), nesquehonite is significantly more industrially scalable and less costly. For applications where the coated product must bind to a liquid and viscosity effects must be minimized, a prismatic isometric morphology may be desirable. Additionally, due to the relatively high hydration state of nesquehonite, for a given mass of Mg, the volume of template precursor generated is more than that obtainable using a less hydrated MgCO3·xH2O, and more template pore volume is obtainable when the precursor material decomposes. This can be used to produce a coated framework with more extra-crystalline space.

[0568] Example L3: In another exemplary precursor stage procedure, isometric partially dehydrated template nesquehonite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0569] To demonstrate this acquisition on a small scale, an aqueous nesquehonite mixture can first be obtained from a representative aqueous Mg(HCO3)2 stock solution. This stock solution represents the stock solution that can be generated during the separation stage of the full implementation of the general method. For this example, a representative stock solution and an aqueous nesquehonite mixture can be obtained using the procedure described in Example L2. As described in Example L2, the precipitation of nesquehonite particles can cause the CO2 process gas to be discharged. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation.

[0570] The concentration of the nesquehonite mixture can be adjusted to a solids concentration of 7 wt%. The mixture can then be spray dried, which results in partial dehydration of the nesquehonite material. To demonstrate this on a small scale, a Sinoped LPG-5 spray dryer can be used for spray drying. The nesquehonite particles in the 7 wt% mixture can be continuously suspended by stirring in a container. The mixture can be pumped from this container into the BETE XAER250 air atomizing nozzle of the spray dryer at a rate ranging between 116 mL / min and 162 mL / min. Compressed air can also be delivered to the nozzle at a flow rate ranging between 1.2 scfm at 20 psig 空气 and 3.6 scfm at 59 psig 空气 . The inlet temperature of the spray dryer can be set to 300 °C, resulting in an outlet temperature ranging between 111 °C and 123 °C.

[0571] The dried, partially dehydrated nesquehonite particles can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve the process water vapor generated by spray drying.

[0572] The type of partially dehydrated nesquehonite template precursor particles generated by this procedure are identified herein as L3. Process liquids and gases can be recovered by typical industrial methods for reuse in the separation stage.

[0573] The 67.1% TGA mass loss of the L3 template precursor material generated according to the above procedure confirms that partial dehydration has occurred (the theoretical mass loss of nesquehonite is 76.9%, as Figure 208 shown). This partial dehydration is due to the elevated temperature experienced during the spray drying process.

[0574] Example M1: In another exemplary precursor stage procedure, an isometric magnesite (MgCO3) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0575] To demonstrate this on a small scale, a representative stock solution can be first prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a stock solution with a concentration of 0.25 mol kg -1A representative aqueous Mg(HCO3)2 stock solution of Mg(aq). This stock solution can then be slurried with additional MgO to provide more Mg ions. In the full implementation of the general method, MgCO3·xH2O precipitated from the stock solution can be utilized to provide more Mg ions. However, for the purposes of this demonstration, the additional MgO can include a commercial MgO product (Elastomag 170) that has been calcined at 1050 °C for 1 hour. By additionally loading Mg ions, the total Mg present in the stock solution mixture can be 1.5 mol kg -1 Mg.

[0576] Next, this stock solution - mixture can be placed in a pressure vessel equipped with magnetic stirring, a high - pressure gas inlet, and a purge needle valve. CO2 can be flowed for 2 minutes to purge the air in the vessel, after which it can be completely sealed and pressurized with CO2 to 725 psi at 14.4 °C. The vessel can be heated on a heating magnetic stirrer. Under magnetic stirring and heating, after 291 minutes, the vessel can reach 193.7 °C and 975 psi. Inside the vessel, magnesite precipitates during this heat treatment, and the CO2 process gas can be vented into the headspace of the vessel. The vessel can then be depressurized and allowed to cool over a 30 - minute period, continuously releasing steam and CO2. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during precipitation and subsequent depressurization.

[0577] Then the mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solids from the mother liquor. In the full implementation of the general method, the separated mother liquor can be conserved for reuse in the separation stage. The magnesite can be dried at 100 °C.

[0578] The type of magnesite template precursor particles generated by this procedure are identified herein as M1. The particles exhibit an equiaxed rhombohedral morphology and are shown in the Figure 33 SEM micrograph. Thermogravimetric analysis of the sample can demonstrate the magnesite composition due to no thermal decomposition occurring prior to the decarboxylation stage at 400 °C. The TGA mass loss of these particles is 52.2%, which matches the expected magnesite mass loss of 52.2% as seen in Figure 208 . Raman spectroscopic analysis also confirms that the particles are magnesite, as seen in Figure 208 . This experiment demonstrates the use of a Mg(HCO3)2 stock solution that is enriched with additional Mg 2+ and HCO3 - ions via MgO and CO2 gas, respectively, to produce equiaxed magnesite template precursor particles.

[0579] Example M2: In another exemplary precursor stage procedure, an isometric magnesite (MgCO3) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0580] To demonstrate this obtaining on a small scale, the procedure described in Example N1 can be used to generate nesquehonite from an aqueous Mg(HCO3)2 stock solution. This precipitation can cause the evolution of CO2 process gas. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during precipitation. Similarly, in the full implementation of the general method, the separated mother liquor can be conserved.

[0581] In this exemplary procedure, nesquehonite can then be combined with water to prepare a mixture with a concentration of 1.5 mol kg -1 Mg. The mixture can be placed in a pressure vessel with magnetic stirring, a high-pressure gas inlet, and a purge needle valve. The headspace of the pressure vessel can contain ambient pressure air with no additional gas input. The pressure vessel can then be sealed.

[0582] The mixture can be magnetically stirred in the vessel for 10 minutes. Then, the vessel can be heated to 175 °C over 68 minutes. During this heat treatment, the reaction temperature can fluctuate, reaching a maximum temperature of 180 °C and a maximum pressure of 1190 psi, under which any CO2 released from nesquehonite in the reaction can become supercritical. The pressure vessel can then be cooled for 199 minutes.

[0583] The resulting magnesite particle mixture can be discharged from the reactor and then filtered to separate the magnesite solid from the mother liquor. In the full implementation of the general method, the separated mother liquor can be conserved for reuse in the separation stage. The magnesite can be dried at 100 °C.

[0584] The type of magnesite template precursor particles generated by this procedure are identified herein as M2. The particles exhibit an isometric rhombohedral morphology and are shown in the Figure 34 SEM micrograph. Raman spectroscopic analysis confirms that the product of this reaction matches the product phase of magnesite, as Figure 208 shown.

[0585] Example A1: In another exemplary precursor stage procedure, a hollow amorphous MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0586] To demonstrate this obtaining on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a stock solution with a concentration of 0.43 mol kg -1A representative aqueous Mg(HCO3)2 stock solution of Mg(aq). This can be achieved by mixing a commercial MgCO3·xH2O product ("Light Magnesium Carbonate" supplied by Akrochem Corporation) at a solid concentration equivalent to 0.43 mol kg -1 of Mg in water. This mixture can be carbonated using pressurized CO2 gas in a circulating pressure vessel. The system can be pressurized to a total pressure of 555 psi by injecting CO2 gas into the vessel. This can be maintained at 34 °C for 2 hours and 13 minutes, or until all the solid has dissolved. At this point, the vessel can be depressurized and stored at 4 °C under atmospheric pressure.

[0587] The cooled stock solution can then be spray dried. To demonstrate this, the stock solution can be pumped at a rate of 35 mL / min through the BETE XAER150 air atomizing nozzle of a Sinoped LPG-5 spray dryer. Compressed air can be delivered to the nozzle at a flow rate of 2.8 scfm 空气 at 45 psig. The inlet temperature of the spray dryer can be set to 165 °C, resulting in an outlet temperature of 110 °C.

[0588] The particles produced by spray drying the stock solution can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve both the process water vapor and the CO2 process gas discharged by spray drying.

[0589] The type of MgCO3·xH2O template precursor material produced by this process is identified herein as A1. SEM image analysis of A1 particles as shown in the SEM micrograph in Figure 35 indicates that the amorphous MgCO3·xH2O particles produced by spray drying include substantially hollow multi-stage equiaxed particles with a smooth outer surface. There are also shell fragments. The shell fragments indicate the presence of large pores within the shell.

[0590] Raman spectroscopic analysis indicates that the product of this reaction does indeed have a Raman peak at 1106 cm -1 that can be associated with crystalline carbonate. However, it does not match any of the typical MgCO3·xH2O peaks ( Figure 208 ). Additionally, TGA analysis of the template precursor fails to match the common crystalline form of MgCO3·xH2O with a mass loss of 66.3% as seen in Figure 208 . Therefore, it is considered amorphous.

[0591] Example A2: In another exemplary precursor stage procedure, a hollow hierarchical equiaxed amorphous MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0592] To demonstrate this acquisition on a small scale, a representative stock solution can be first prepared. This stock solution represents the stock solution that can be generated in the separation phase of the full implementation of the general method. For this example, a representative aqueous Mg(HCO3)2 stock solution with a concentration of 1.39 mol kg -1 Mg(aq) can be prepared. This can be done by mixing a commercial Mg(OH)2 product ("Versamag" supplied by Akrochem Corporation) at a solid concentration equivalent to 1.49 mol kg -1 Mg in water. This mixture can be carbonated using pressurized CO2 gas in a circulating pressure vessel. The system can be pressurized to a total pressure of 700 - 800 psig by injecting CO2 gas into the vessel. This can be maintained at 10 °C for 2 hours, or until all (i.e., >90%) of the solid has dissolved. At this point, the contents can be depressurized and stored at 4 - 10 °C at atmospheric pressure.

[0593] The stock solution can then be spray dried. To demonstrate this, the stock solution can be pumped at a rate of 2.7 mL / min through a 0.7 mm Buchi B-290 two-fluid air atomizing nozzle in a Buchi B-191 spray drying system. Compressed air can be delivered to the nozzle at a flow rate of 0.6 scfm 空气 at 88 psig. The inlet temperature of the spray dryer can be set to 130 °C, resulting in an outlet temperature between 85 - 89 °C. The aspirator can be set to 18 scfm 空气 .

[0594] The particles produced by spray drying the stock solution can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve both the process water vapor and the CO2 process gas discharged by spray drying.

[0595] The type of MgCO3·xH2O template precursor material produced by this process is identified herein as A2. As shown by the SEM micrographs in Figure 36 A to Figure 36 B, the SEM image analysis of A2 particles shows that the amorphous MgCO3·xH2O particles produced by spray drying include generally hollow, multi-stage isometric particles with a smooth outer surface. There are also shell fragments. The shell fragments indicate that in addition to the central cavity, the shell has a closed-pore macroporous structure. Compared to the shell of A1 particles, the shell of A2 particles is thicker due to its increased shell porosity. The spheres are also smaller, with 95% or more in the population having a diameter less than 10 μm.

[0596] Raman spectroscopic analysis revealed that the MgCO3·xH2O spheres did not have distinct Raman peaks associated with crystalline carbonates. Additionally, TGA analysis of the template precursor did not match the common crystalline form of MgCO3·xH2O with a 68.4% mass loss as seen in Figure 208 . Thus, it was considered amorphous.

[0597] Example A3: In another exemplary precursor stage procedure, a hollow hierarchical equiaxed amorphous MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0598] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a representative aqueous Mg(HCO3)2 stock solution with a concentration of 1.08 mol kg -1 Mg(aq) can be prepared. This can be done by mixing a commercial Mg(OH)2 product ("Versamag" supplied by Akrochem Corporation) in water at a solid concentration equivalent to 1.12 mol kg -1 Mg. The mixture can be carbonated using pressurized CO2 gas in a circulating pressure vessel. The system can be pressurized to a total pressure of 700 - 800 psig by injecting CO2 gas into the vessel. This can be maintained at 10 °C for 2 hours, or until substantially all (i.e., >90%) of the solid has dissolved. At this point, the contents can be depressurized and stored at 4 - 10 °C at atmospheric pressure.

[0599] The stock solution can then be spray dried. To demonstrate this, the stock solution can be pumped at a rate of 2.7 mL / min through a 0.7 mm Buchi B - 290 two - fluid air - atomizing nozzle in a Buchi B - 191 spray drying system. Compressed air can be delivered to the nozzle at a flow rate of 0.6 scfm 空气 at 88 psig. The inlet temperature of the spray dryer can be set to 90 °C, resulting in an outlet temperature between 56 - 58 °C. The aspirator can be set to 18 scfm 空气 .

[0600] The particles produced by spray drying the stock solution can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve both the process water vapor and the CO2 process gas exhausted by spray drying.

[0601] The type of MgCO3·xH2O template precursor material produced by this process is identified herein as A3. As Figure 36 C toFigure 36 SEM image analysis of A3 particles as shown in the SEM micrographs in D indicates that the amorphous MgCO3·xH2O particles produced by spray drying include substantially hollow multi-stage equiaxed particles with a smooth outer surface. There are also shell fragments. The shell fragments indicate that in addition to the central cavity, the shell also has a closed-pore macroporous structure. Compared with the shells of A1 and A2 particles, the shell of A3 is thicker due to its increased shell porosity. The average aspect ratio representing the ratio of particle radius to shell thickness is also lower. The particle circled by the solid yellow line has an aspect ratio of approximately 5:1, while the particle circled by the dashed yellow line has an aspect ratio of approximately 2:1.

[0602] Macropores are throughout the shell, which can be seen in the carbon-coated framework grown thereon. Figure 36 E is a TEM image of the carbon-coated framework grown on a template obtained from A3 particles. The mottled appearance corresponding to its porosity of the shell extends throughout the outer shell. The macropores of the shell are sandwiched between two surface layers - an outer surface layer and an inner surface layer (which represent the inner and outer surfaces of the shell respectively). These surface layers appear darker in TEM. The macroporous shell is part of the coated superstructure; the unit cell substructure is finer, as Figure 36 shown in the inset of E (i.e., the TEM micrograph showing the mesoporous unit cell substructure).

[0603] Raman spectroscopic analysis indicates that the MgCO3·xH2O spheres do not have distinct Raman peaks associated with crystalline carbonates. Additionally, TGA analysis of the template precursor fails to match the common crystalline form of MgCO3·xH2O with a mass loss of 72.9% as seen in Figure 208 Therefore, it is considered amorphous.

[0604] Example C1: In another exemplary precursor stage procedure, a hollow hierarchical equiaxed magnesium citrate template precursor material can be obtained from an aqueous magnesium citrate stock solution.

[0605] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a representative aqueous magnesium citrate stock solution with a concentration of 0.52 mol kg -1 Mg(aq) can be prepared by reacting an aqueous mixture of citric acid (supplied by Sigma Aldrich) with 0.52 mol kg -1 of Mg(OH)2 (Versamag, supplied by Akrochem).

[0606] The stock solution can then be spray dried. To demonstrate this, the stock solution can be pumped at a rate of 3.75 mL / min through the Buchi B-290 two-fluid nozzle of a Buchi B-191 spray dryer. With the aspirator air flow set at 18 scfm 空气 compressed air can be delivered to the nozzle at a flow rate of 0.6 scfm 空气 at 88 psig. The inlet temperature can be set at 220 °C, resulting in an outlet temperature of 110 °C.

[0607] The particles produced by spray drying the stock solution can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve the process water vapor discharged by spray drying.

[0608] The type of magnesium citrate template precursor material produced by this process is identified herein as C1. As shown by the SEM analysis of the C1 particles in the SEM micrographs in Figure 37 the magnesium citrate particles produced by spray drying include substantially hollow multi-stage equiaxed particles. Most include a solid shell and a hollow interior, with a wrinkled spheroid superstructure, as seen in Figure 37 . Some particles include a smooth unwrinkled spheroid superstructure; these particles may have a thicker and harder shell compared to the wrinkled particles. The spray-dried magnesium citrate precursor particles rarely fragment or break, although pinholes can be found, as indicated in Figure 37 .

[0609] Raman spectroscopic analysis confirms that the product of this reaction matches the product of magnesium citrate, as shown in Figure 208 .

[0610] Example E1: In another exemplary precursor stage procedure, an elongated template precursor material of epsom salt (magnesium sulfate heptahydrate MgSO4·7H2O) can be obtained from an aqueous magnesium sulfate stock solution.

[0611] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a representative aqueous magnesium sulfate stock solution with a concentration of 4.06 mol kg -1 Mg(aq) can be prepared by dissolving epsom salt in water at room temperature. This can be carried out with magnetic stirring at 700 RPM in a glass beaker.

[0612] Once dissolved, 410.86 g of acetone can be added dropwise via a separatory funnel, which can cause the immediate formation of crystals in the solution. While this represents generally an undesired anti-solvent precipitation, the solvent-free precipitation of epsom salt can be readily achieved by cooling or spray drying the stock solution. Besides demonstrating the engineered precursor morphology or demonstrating a scalable procedure, the procedure of Example E1 is more for the purpose of precipitating epsom salt so that the template materials and coating materials obtained from the epsom salt precursor compounds can be demonstrated and analyzed in the subsequent parts of this disclosure. In the full implementation of the general method, the mother liquor separated after the solvent-free precipitation can be saved for reuse in the separation stage.

[0613] After 22 minutes, the precipitation of epsom salt can be complete. The resulting mixture can be collected and filtered. The particles can be dried.

[0614] The type of epsom salt template precursor material produced by this process is identified herein as E1. By optical microscopy, the particles can be observed to be elongated rods with a hexagonal cross-section, as Figure 38 shown.

[0615] Raman spectroscopic analysis confirms that the product of this reaction matches the product of epsom salt (as seen in Figure 208 ).

[0616] Example H4: In another exemplary precursor stage procedure, Li-doped hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution that also contains a low concentration of aqueous Li2CO3.

[0617] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a representative aqueous Mg(HCO3)2 stock solution can be prepared with an additional step of adding lithium carbonate (Li2CO3). This can be done as follows. First, MgO powder (Akrochem Elastomag 170 calcined at 1050 °C for 1 hour) can be slurried into water at a solid concentration of 0.23 mol kg -1 of Mg. This can be done in a glass beaker with magnetic stirring. Lithium carbonate (Li2CO3, Sigma Aldrich) can be added to this mixture at a solid concentration of 2.71·10 -3 mol kg -1 of Li. The mixture can be carbonated with an ejector tube bubbling CO2 gas to generate aqueous H2CO3. After the complete dissolution of MgO and Li2CO3, the CO2 flow can be interrupted. Then the Mg(HCO3)2 stock solution can be filtered to remove any remaining undissolved impurities.

[0618] Next, the stock solution can be heated to 100 °C in an uncovered glass beaker under magnetic stirring. This condition can be maintained for 2 hours, during which hydromagnesite particles can precipitate. After 2 hours, the resulting mixture can be filtered, and the solid hydromagnesite can be dried at 100 °C in forced air circulation.

[0619] The type of Li-doped hydromagnesite template precursor material produced by this process is designated herein as H4. The particles are shown in the Figure 39 SEM micrographs. Their plates are thin (<100 nm along their short axis) and flat, and the surface is smooth.

[0620] Example H5: In an exemplary precursor stage procedure, a Li-doped hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution that also contains medium-concentration Li2CO3.

[0621] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, a representative aqueous Mg(HCO3)2 stock solution can be prepared, with the additional step of adding lithium carbonate (Li2CO3). This can be done as follows.

[0622] First, MgO powder (Akrochem Elastomag 170 calcined at 1050 °C for 1 hour) can be slurried in water at a solid concentration of 0.23 mol kg -1 of Mg. This can be done in a glass beaker under magnetic stirring. Li2CO3 (Sigma Aldrich) can be added to this mixture at a solid concentration of 2.74·10 -2 mol kg -1 of Li. The mixture can be carbonated with a sparging tube that bubbles CO2 gas to generate aqueous H2CO3. After the MgO and Li2CO3 are completely dissolved, the CO2 flow can be interrupted. Then the Mg(HCO3)2 stock solution can be filtered to remove any remaining undissolved impurities.

[0623] Next, the stock solution can be heated to 100 °C in an uncovered glass beaker under magnetic stirring. This condition can be maintained for 1 hour, during which hydromagnesite particles can precipitate. After 1 hour, the resulting mixture can be filtered, and the solid hydromagnesite can be dried at 100 °C in forced air circulation.

[0624] The type of Li-doped hydromagnesite template precursor material produced by this process is designated herein as H5. The particles are shown in the Figure 40 SEM micrographs. Their plates are thin (<120 nm along their short axis), and the surface is smoother thanFigure 39 The surface of the shown plate is rough. This roughness may indicate an increased Li doping level due to a higher concentration of Li2CO3 in the aqueous stock solution.

[0625] Example M3: In another exemplary precursor stage procedure, equiaxed magnesite (MgCO3) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0626] To demonstrate this acquisition on a small scale, a representative stock solution can be prepared first. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, the stock solution can be generated in a high-pressure reactor. First, a commercial hydromagnesite product (Akrochem light magnesium carbonate) can be slurried in water at a solid concentration of 0.74 mol kg -1 of Mg. This mixture can be placed in a circulating pressure vessel. Then the sealed container can be heated to 145 °C, at which temperature gaseous CO2 at ˉ800 psi can be introduced into the system. This reaction can continue at 145 °C for a duration of 139 minutes of recirculation, thereby reaching a maximum pressure of 900 psi. During this heat treatment, hydromagnesite can dissolve, thereby forming aqueous Mg(HCO3)2, and magnesite can precipitate out from Mg(HCO3)2. At this time, the container can be depressurized to release the CO2 process gas. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation and subsequent depressurization.

[0627] The resulting magnesite particle mixture can be discharged from the reactor and then filtered to separate the magnesite solid from the mother liquor. In the full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. The magnesite can be dried at 100 °C.

[0628] The type of magnesite template precursor material produced by this process is identified herein as M3. Equiaxed magnesite particles can be seen in the Figure 41 SEM micrograph of A. Based on a TGA mass loss of 51.7% (which closely matches the theoretical expectation of 52.2% in Figure 208 ), the structure indicates magnesite.

[0629] Example M4: In another exemplary precursor stage procedure, equiaxed magnesite (MgCO3) template precursor material can be obtained from an aqueous Na-rich Mg(HCO3)2 stock solution.

[0630] To demonstrate this acquisition on a small scale, a representative stock solution can be first prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, the stock solution can be generated in a high-pressure reactor. First, a commercial hydromagnesite product (Akrochem light magnesium carbonate) can be slurried in water at a solid concentration of 0.74 mol kg -1 Mg. Commercial NaHCO3 product (Arm&Hammer) can be added to this mixture at a concentration of 2.17·10 -3 mol kg -1 Na. This mixture can be placed in a circulating pressure vessel. Then the sealed container can be heated to 145 °C, at which temperature, gaseous CO2 at ˉ800 psi can be introduced into the system. This reaction can continue at 145 °C for a duration of 135 minutes of recirculation, reaching a maximum pressure of 840 psi. During this heat treatment, hydromagnesite can dissolve to form aqueous Mg(HCO3)2, and magnesite can precipitate out from the aqueous Mg(HCO3)2. At this time, the container can be depressurized to release the CO2 process gas. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during precipitation and subsequent depressurization.

[0631] The resulting magnesite particle mixture can be discharged from the reactor and then filtered to separate the magnesite solid from the mother liquor. In the full implementation of the general method, the separated mother liquor can be conserved for reuse in the separation stage. The magnesite can be dried at 100 °C.

[0632] The type of magnesite template precursor material produced by this process is identified herein as M4. Equiaxed magnesite particles can be seen in the Figure 41 SEM micrograph of B. Based on a TGA mass loss of 51.6% (which closely matches the theoretical expectation of 52.2% in Figure 208 ), the structure indicates magnesite.

[0633] Example M5: In another exemplary precursor stage procedure, equiaxed magnesite (MgCO3) template precursor material can be obtained from an aqueous Na-rich Mg(HCO3)2 stock solution.

[0634] To demonstrate this acquisition on a small scale, a representative stock solution can be first prepared. This stock solution represents the stock solution that can be generated in the separation stage of the full implementation of the general method. For this example, the stock solution can be generated in a high-pressure reactor. First, a commercial hydromagnesite product (Akrochem light magnesium carbonate) can be slurried in water at a solid concentration of 0.74 mol kg -1 Mg. It can be slurried at a concentration of 0.19 mol kg -1The concentration of Na: A commercial NaHCO₃ product (Arm&Hammer) is added to this mixture. This mixture can be placed in a circulating pressure vessel. Then the sealed container can be heated to 145 °C, at which temperature, gaseous CO₂ at -800 psi can be introduced into the system. This reaction can continue at 145 °C for a duration of 137 minutes of recirculation, thereby reaching a maximum pressure of 850 psi. During this heat treatment, hydromagnesite can dissolve, thereby forming aqueous Mg(HCO₃)₂, and magnesite can precipitate from the aqueous Mg(HCO₃)₂. At this point, the container can be depressurized to release the CO₂ process gas. In the full implementation of the general method, conventional techniques can be used to preserve the CO₂ process gas released during precipitation and subsequent depressurization.

[0635] The resulting mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solid from the mother liquor. In the full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. The magnesite can be dried at 100 °C.

[0636] The type of magnesite template precursor material produced by this process is identified herein as M5. Equiaxed magnesite particles can be seen in the Figure 41 SEM micrograph at C, as rhombohedral crystals of magnesite. Based on a TGA mass loss of 51.9% (which closely matches the Figure 208 theoretical expectation of 52.2% in), the structure indicates magnesite.

[0637] Comparing M3, M4, and M5, there are no obvious morphological differences that can be easily identified based on SEM analysis.

[0638] Example N2: In another exemplary precursor stage procedure, elongated trihydrate magnesite (MgCO₃·3H₂O) template precursor material can be obtained from an aqueous Mg(HCO₃)₂ stock solution.

[0639] To demonstrate this acquisition on a small scale, the procedure described in Example L2 can be used to generate polyhydrate magnesite from an aqueous stock solution of Mg(HCO₃)₂. This precipitation can cause the CO₂ process gas to be discharged. In the full implementation of the general method, conventional techniques can be used to preserve the CO₂ process gas released during precipitation. Similarly, in the full implementation of the general method, the separated mother liquor can be preserved.

[0640] Next, water can be heated to 35 °C in a glass beaker. Once the water reaches the temperature, polyhydrate magnesite can be added to produce a concentration of 0.74 mol kg -1A mixture of Mg. The mixture can be magnetically stirred at 600 RPM and maintained at 35 °C for 100 minutes. During this heat treatment, nesquehonite can dissolve and hydromagnesite can precipitate out. Then the mixture can be filtered to separate the mother liquor from the nesquehonite. In the full implementation of the general method, the separated mother liquor can be preserved.

[0641] The type of hydromagnesite template precursor material produced by this process is identified herein as N2. Figure 42 Optical micrographs are shown. Most of the hydromagnesite particles are individualized, thus forming a fine powder.

[0642] Example N3: In another exemplary precursor stage procedure, an elongated hydromagnesite (MgCO3·3H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0643] To demonstrate this acquisition on a small scale, nesquehonite can be generated from a stock solution of aqueous Mg(HCO3)2 using the procedure described in Example L2. This precipitation can cause the CO2 process gas to be discharged. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation. Similarly, in the full implementation of the general method, the separated mother liquor can be preserved.

[0644] Next, an aqueous solution of 10.84 mM SDS (TCI Chemical) can be heated to 35 °C in a glass beaker. Once the water reaches the temperature, nesquehonite can be added to produce a mixture with a concentration of 0.74 mol kg -1 A mixture of Mg. The mixture can be magnetically stirred at 600 RPM and maintained at 35 °C for 100 minutes. During this heat treatment, nesquehonite can dissolve and hydromagnesite can precipitate out. Then the mixture can be filtered to separate the mother liquor from the nesquehonite. In the full implementation of the general method, the separated mother liquor can be preserved.

[0645] The type of hydromagnesite template precursor material produced by this process is identified herein as N3. Figure 43 Optical micrographs are shown. Compare Figure 44 N2 in A and Figure 44 The optical micrographs of N3 in B show that the N3 particles are on average longer and have a smaller diameter. This demonstrates that the presence of a surfactant during precipitation can be used to control the size of the template precursor particles.

[0646] Example Li1: In another exemplary precursor stage procedure, a hollow hierarchical equiaxed Li2CO3 template precursor material can be obtained from an aqueous Li2CO3 stock solution.

[0647] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the stock solution that can be generated in the separation phase of the full implementation of the general method. For this example, a representative aqueous Li2CO3 stock solution can be prepared as follows. First, a commercial Li2CO3 product (supplied by FMC) can be slurried in water at a concentration of 0.54 mol kg -1 of Li. This mixture can be carbonated in a top - stirred reactor equipped with gas - dispersing blades and a sparger tube. CO2 gas can be flowed into the mixture through the sparger tube at a rate of 9 sfch 空气 for 175 minutes or until the solid is completely dissolved. At this point, the solution can be diluted with water to adjust the concentration to 0.27 mol kg -1 Li(aq).

[0648] This representative stock solution can then be spray - dried. To demonstrate this, the stock solution can be pumped at a rate of 7 mL / min through the Buchi B - 290 two - fluid nozzle of a Buchi B - 191 spray dryer. With the aspirator air flow set to 18 scfm 空气 and the compressed air delivered to the nozzle at a flow rate of 0.6 scfm 空气 at 88 psig. The inlet temperature can be set to 170 °C, resulting in an outlet temperature of 100 °C.

[0649] The particles produced by spray - drying the stock solution can be collected by a cyclone particle separator. In the full implementation of the general method, conventional techniques can be used to conserve both the CO2 process gas and the process water vapor discharged by spray - drying.

[0650] The type of lithium carbonate templated precursor material produced by this process is identified herein as Li1. The particles are hollow, hierarchical, equiaxed structures, as seen in the SEM micrographs from Figure 45 A to Figure 45 B. The hollow structure can be identified at different survival stages. The shell exhibits pinholes between the Li2CO3 subunits, which are indicated by the red arrow in Figure 45 A. In some shells, fragmentation and larger holes or cracks can be observed (which are indicated by the blue arrow in Figure 45 A). Wrinkled shells are present in the sample (which are indicated by the yellow arrow in Figure 45 A). In Figure 45 B, the sub - structure of the loosely packed subunits of the particles can be discerned. Their sizes are mainly between 200 and 700 nm, and the larger particles apparently consist of larger subunits. Raman peaks at around 1091 cm -1 , 195 cm -1 and 158 cm -1 confirm that the structure is Li2CO3.

[0651] V*. Template Stage - Examples

[0652] This section details the small - scale production of exemplary template materials using exemplary procedures. Thus, these procedures include partial implementations of the general method. Therefore, it should be understood that these procedures must be combined with other procedures in the full implementation of the general method. Additionally, it should be understood that these procedures only demonstrate similar larger - scale procedures that will be used in industrial - scale manufacturing.

[0653] This section describes multiple exemplary procedures for fabricating template materials. In some exemplary procedures, the template precursor material can be processed in separate and distinct template - stage procedures to form the template material, and the resulting template material can then be used in separate and distinct replication - stage procedures. In other cases, both the template - stage and replication - stage procedures can be performed in the same reactor. Some of these exemplary template - stage procedures use the template precursor materials previously named and described in Part V. Additionally, new template precursor materials are also used.

[0654] Example N1T1: In an exemplary template - stage procedure, the hydromagnesite template precursor material can be heat - treated to form a porous MgO template material.

[0655] To demonstrate this, the procedures described in Example N1 can first be used to generate N1 - type hydromagnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0656] Next, the template precursor material can be heat - treated. This can be performed in a TGA instrument under an Ar inert gas flow, as described in Scheme E of Part III. A sample of N1 - type hydromagnesite particles can be heated from room temperature to a final temperature of 1,000 °C at a rate of 10 °C / min under Ar gas. During this heat - treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. When 1,000 °C is reached, the sample can be cooled back to room temperature.

[0657] The type of porous MgO template material produced by this process is identified herein as N1T1. The template particles retain the elongated superstructure of the precursor particles, as Figure 46 shown by the SEM micrographs. The length of the particles ranges from 20 μm to 100 + μm. The unbroken rods can exhibit an average aspect ratio of approximately 15:1. Due to the porous sub - structure of the nanocrystalline MgO subunits, the ends of the particles have a fragile appearance.

[0658] Example H1T1: In another exemplary templating stage procedure, the hydromagnesite templating precursor material can be heat-treated to form a porous MgO templating material.

[0659] To demonstrate this, the procedure described in Example H1 can first be used to generate H1-type hydromagnesite particles. This material represents the templating precursor material that can be generated in the precursor stage of the overall implementation of the general method.

[0660] Next, the templating precursor material can be heat-treated. This can be carried out in a TGA instrument under an Ar inert gas flow, as described in Scheme E of Part III. A sample of the H1-type hydromagnesite particles can be heated from room temperature to a final temperature of 1,000 °C at a rate of 10 °C / min under Ar gas. During this heat treatment, CO2 gas can be released. In the overall implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during the decomposition of the templating precursor material. When 1,000 °C is reached, the sample can be cooled back to room temperature.

[0661] The type of porous MgO templating material produced by this process is designated as H1T1 herein. The templating particles retain the hierarchical equiaxed rose-like superstructure of the precursor particles, as Figure 47 shown in the SEM micrographs. The diameter of the individual plates generally ranges from 1 μm to 3 μm, with an average size between these values. The diameter of the particles generally ranges from 4 μm to 10 μm, with an average size between these values. The average plate thickness is less than 100 nm and structurally corresponds to a single layer of laterally interconnected nanocrystalline subunits. The plates exhibit a high thickness uniformity. The fragile appearance at the plate edges reflects the porous substructure of the nanocrystalline MgO subunits.

[0662] Example H2T1: In another exemplary templating stage procedure, the hydromagnesite templating precursor material can be heat-treated to form a porous MgO templating material.

[0663] To demonstrate this, the procedure described in Example H2 can first be used to generate H2-type hydromagnesite particles. This material represents the templating precursor material that can be generated in the precursor stage of the overall implementation of the general method.

[0664] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace according to Protocol B, as detailed in Part III. A sample of H2-type hydromagnesite particles can be placed in a ceramic boat and introduced into the tube furnace at room temperature. The furnace can then be heated to 1050 °C at a heating rate of 20 °C / min under an Ar flow of 2000 sccm. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can then be maintained at 1050 °C for two hours, after which the furnace can be cooled to room temperature.

[0665] The type of porous MgO template material produced by this process is designated herein as H2T1. The template particles retain the elongated rosette superstructure of the precursor particles, as Figure 48 shown by the SEM micrographs. The length of the particles ranges from 10 μm to 100 μm, and some particles have an aspect ratio exceeding 5:1. The diameter of the plates ranges from 0.5 μm to 1.5 μm. Compared to the H1T1 plates, the H2T1 plates have a rougher substructure, which includes more discrete subunits and larger pores between them. The subunits include cubic or polyhedral nanocrystals with a size range from ˉ40 nm to ˉ100 nm and an average size between these values. The roughening of the substructure can be attributed to the more intense heat treatment used to prepare the H2T1 template material.

[0666] In Figure 48 some of the subunits observed are joined laterally to their neighboring neighbors without any visible interstitial pores. These junctions can constitute grain boundaries. Other subunits are more discrete and, although still joined to the overall network, they are separated from their neighbors by pores. Since the plates are typically only one subunit in thickness, the interstitial pores between the subunits penetrate the thickness of the plate. These through-holes are important and desirable structural features in the thin template structure because they create more cross-linking in the coating framework formed through the template.

[0667] During the heat treatment in Example H2T1, the porous MgO template material obtained by the decomposition of the template precursor can undergo grain growth and sintering due to atomic diffusion. The distance over which diffusion can occur can be a function of temperature. Therefore, adjusting the temperature and duration of the template stage treatment may be useful for the fine engineering of the substructure of the template (and correspondingly, the substructure of the coating framework).

[0668] During roughening, the porous sub-structure of the template material can also densify. This can affect the fractional composition of the positive and negative template spaces. In extreme cases, the densification of the porous sub-structure can continue until the negative space (i.e., the pore structure of the template) is eliminated. When the particles sinter together, higher-order porosity can be obtained through the pores between these previously discrete particles. Workers have utilized this technique to produce template structures that include a macroporous network of sintered metal oxide particles. Macroporous monolithic template structures like this can be formed in the template stage and recycled using general methods.

[0669] Example H1T2: In another exemplary template stage procedure, the hydrotalcite template precursor material can be heat-treated to form a MgO template material.

[0670] To demonstrate this, the procedure described in Example H1 can first be used to generate H1-type hydrotalcite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0671] Next, the template precursor material can be heat-treated. This can be carried out in a TGA according to Scheme E, as detailed in Part III. A sample of H1-type hydrotalcite particles can be heated from room temperature to a final temperature of 1200 °C at a heating rate of 10 °C / min under Ar gas, during which CO2 gas is released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1200 °C for 10 minutes and then cooled.

[0672] The type of MgO template material produced by this process is identified herein as H1T2. The type of template particles produced by this procedure is shown in the Figure 49 SEM micrograph. The heat treatment not only transforms the subunits but also the template super-structure, which no longer appears to be hierarchical. Thus, the gradual coalescence of the nano-scale subunits and pores at the sub-structure level can ultimately transform the template's super-structure, and the individual particles can sinter together to form larger (up to macroscopic) template structures.

[0673] Example N1T2: In another exemplary template stage procedure, the nesquehonite template precursor material can be heat-treated to form a MgO template material.

[0674] To demonstrate this, the procedure described in Example N1 can first be used to generate N1-type nesquehonite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0675] Next, the template precursor material can be heat-treated. This can be carried out in a TGA under Ar gas according to Protocol E at a heating rate of 10 °C / min from room temperature to a final temperature of 1200 °C. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1200 °C for 10 minutes and then cooled.

[0676] The type of MgO template material produced by this process is designated herein as N1T2. Due to progressive sintering at high temperatures, the template particles have lost the porous substructure evolved during thermal decomposition.

[0677] Example N1T3: In another exemplary templating procedure, the hydromagnesite template precursor material can be heat-treated to form a porous MgO template material.

[0678] To demonstrate this, the procedure described in Example N1 can first be used to generate N1-type hydromagnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0679] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace according to Protocol B, as detailed in Part III. The sample can be heated from room temperature to 460 °C under an Ar gas flow of 1271 sccm. At this point, acetylene (C2H2) gas can be introduced into the system to initiate carbon deposition on the template surface. During this replication stage procedure, the template that may not have completed its thermal decomposition can continue to decompose in a high-temperature environment, and CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. This condition can be maintained for 3 hours. The acetylene flow can be terminated, and then the furnace can be cooled to room temperature under a continuous Ar flow.

[0680] The type of porous MgO template material produced by this process is designated herein as N1T3.

[0681] Example M1T1: In another exemplary templating procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0682] To demonstrate this, the procedure described in Example M1 can first be used to generate M1-type magnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0683] Next, the template precursor material can be heat-treated. This can be carried out in a TGA according to protocol E, as detailed in Part III. The sample can be heated from room temperature to 1050 °C at a rate of 50 °C / min under an Ar flow. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1050 °C for 1 minute and then cooled.

[0684] The type of porous MgO template material produced by this process is designated herein as M1T1. The template particles retain the equiaxed superstructure of the precursor particles, as shown by the SEM micrographs of Figure 50 The diameter of the template particles ranges from 5 μm to 20 μm. At lower magnifications, the surface appears to be substantially smooth and continuous. At higher magnifications, the surface appears rougher due to the porous substructure. Due to the ~5 nm iridium particles used to coat the surface for imaging, it is difficult to clearly resolve the exact nanoscale substructure, but the regular rugged appearance indicates the underlying MgO subunits.

[0685] Example M1T2: In another exemplary templating procedure, magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0686] To demonstrate this, the procedure described in Example M1 can be first used to generate M1-type magnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0687] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace according to protocol B, as detailed in Part III. The sample can be heated from room temperature to a final temperature of 1050 °C at a heating rate of 20 °C / min and under an Ar flow of 2360 sccm. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1050 °C for 4 hours and then cooled.

[0688] The type of MgO template material produced by this process is designated herein as M1T2. The template particles retain the equiaxed superstructure of the precursor particles, as shown by the SEM micrographs of Figure 51 The diameter of the template particles ranges from 5 μm to 20 μm. At low magnifications, the surface appears to be substantially smooth and continuous. At higher magnifications, the surface appears rougher due to the porous substructure. Due to the ~5 nm iridium particles used to coat the surface for imaging, it is difficult to clearly resolve the exact nanoscale substructure, but the regular rugged appearance indicates the underlying MgO subunits.

[0689] Example M1T3: In another exemplary templating stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0690] To demonstrate this, the procedure described in Example M1 can first be used to generate M1-type magnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0691] Next, the template precursor material can be heat-treated. This can be performed in a TGA according to Protocol E, as detailed in Part III. The sample can be heated from room temperature to a final temperature of 1200 °C at a rate of 50 °C / min under flowing Ar. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to conserve the CO2 process gas released during the decomposition of the template precursor material. The sample can then be held at 1200 °C for 1 minute and then cooled.

[0692] The type of MgO template material produced by this process is designated as M1T3 herein. The template particles retain the equiaxed superstructure of the precursor particles, as Figure 52 shown in the SEM micrographs. The diameter of the template particles in the template sample ranges from 5 μm to 20 μm. At low magnification, the surface appears to be substantially smooth and continuous. At higher magnification, the surface appears rougher due to the porous substructure. Due to the ~5 nm iridium particles used to coat the surface, it is difficult to clearly resolve the precise nanoscale substructure, but its regular rugged appearance indicates the underlying MgO subunits. Although the substructure cannot be easily distinguished from a comparable sample treated at only 1050 °C (described in Example M1T1 and shown in Figure 51 ), the subunits appear to start coalescing through sintering.

[0693] Example M1T4: In another exemplary templating stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0694] To demonstrate this, the procedure described in Example M1 can first be used to generate M1-type magnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0695] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace according to Protocol B, as detailed in Part III. The sample can be heated from room temperature to a final temperature of 1200 °C at a heating rate of 20 °C / min under an Ar flow of 2000 sccm. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1200 °C for 4 hours and then cooled.

[0696] The type of MgO template material produced by this process is designated herein as M1T4. The template particles retain the equiaxed superstructure of the precursor particles, as Figure 53 shown in the SEM micrograph of Figure 51 . The diameter of the template particles ranges from 5 μm to 20 μm. Compared to comparable samples treated at 1050 °C (as described in Example M1T1 and shown in Figure 52 ) or to comparable samples treated at 1200 °C for only 1 minute (as described in Example M1T2 and shown in

[0697] Example E1T1: In another exemplary template stage procedure, the epsomite template precursor material can be heat-treated to form a dehydrated basic MgSO4 template material.

[0698] To demonstrate this, epsomite particles can first be generated. The epsomite particles used in this exemplary procedure are generated as described in Example E1. This material represents a template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0699] Next, the template precursor material can be heat-treated. This can be carried out in a forced air circulation oven. The sample can be heated from room temperature to a final temperature of 215 °C. During this heat treatment, the aqueous epsomite particles can be dehydrated. The sample can be held at 215 °C for 2 hours and then cooled.

[0700] The resulting porous dehydrated MgSO4 sample is shown in Figure 54 A, which is an optical micrograph. In Figure 54 A, the smooth facets observable in the E1 crystals ( Figure 38 ) have been replaced by a rougher surface due to the evacuation of the crystalline H2O.

[0701] If a dehydrated MgSO4 material is used in the high-temperature replication stage program, the MgSO4 can initially undergo further thermal effects and sintering, and this can be considered part of the heat treatment for generating the template material. Such a program can be carried out in a tube furnace according to Scheme B, as detailed in Section III. This part of the heat treatment can include heating a sample of the dehydrated MgSO4 material from room temperature to 580 °C under Ar gas flowing at 1102 sccm. During this heat treatment, the MgSO4 can continue to roughen, and a part can decompose into MgO.

[0702] The type of MgSO4 template material produced by this process is identified herein as E1T1. Next, propylene (C3H6) gas can be introduced into the furnace to start surface replication. Insofar as the MgSO4 template material is still roughening, the template stage and the replication stage can overlap. At some point, the pyrolytic formation of the carbon-coated material on top of the E1T1 template material can stabilize the latter, thus preventing further roughening and indicating the true completion of the template stage. The CVD can last for 2 hours, and then the furnace can be cooled under a continuous Ar flow.

[0703] After the furnace has cooled to room temperature, the PC material (E1T1P 16 ) is collected. This PC material is shown in the SEM micrograph of Figure 54 B. From this, we can see that the E1T1-type template particles retain the superstructure of the epsomite precursor particles, although cracking can be observed. Figure 54 C and Figure 54 D are SEM micrographs of the P 16 -type carbon-coated framework formed on the E1T1-type template particles. In Figure 54 D, the unit cell substructure indicates the porous substructure of the template.

[0704] Example H4T1: In another exemplary template stage program, a Li-doped hydromagnesite precursor material can be heat-treated to form a porous MgO template material.

[0705] To demonstrate this, the procedure described in Example H4 can be first used to generate H4-type hydromagnesite particles. This material represents the template precursor material that can be generated in the precursor stage in the full implementation of the general method.

[0706] Next, the template precursor material can be heat-treated. This can be carried out in a tube furnace under an Ar flow of 2000 sccm according to Protocol B, as detailed in Part III. The sample can be heated from room temperature to a temperature of 1050 °C at a heating rate of 20 °C / min. During this heat treatment, CO2 gas can be released. In the full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. The sample can be held at 1050 °C for 20 minutes, after which the furnace can be cooled.

[0707] The type of porous MgO template material produced by this process is designated herein as H4T1. The template particles retain the plate-like superstructure of the precursor particles, as Figure 55 shown in the SEM micrograph of B. The diameter of the individual plates ranges from approximately sub-micron to several microns, with an average size of about 1 μm. The average plate thickness ranges from approximately 80 nm to 100 nm and structurally corresponds to a single layer of laterally interconnected subunits with an average diameter between 80 nm and 100 nm. The plates exhibit a high thickness uniformity between the particles. The subunits are discrete, and numerous pores separate the individual nanocrystals.

[0708] At diameters of 80 nm to 100 nm, the subunits of the template particles in H4T1 are Figure 55 considerably larger than the 50 nm to 60 nm subunits shown in the SEM micrograph of A. These subunits are obtained from undoped hydromagnesite particles that have undergone the same template stage procedure. As an approximation, the 90 nm subunits are 1.5 times larger in diameter and more than 3 times larger in volume than t...

Claims

1. A method for producing a hierarchically coated framework by the following means: Obtaining templated precursor particles from a first solution containing ionic species dissolved in process water by solvent-free precipitation, where the ionic species include metal cations and oxyanions, and a portion of the process water is preserved; And Evolving template particles from the template precursor particles, the evolution including at least partially decomposing the template precursor particles; And Adsorbing a carbonaceous adsorbent material onto the template surface of each template particle by chemical vapor deposition to form a first coating layer; And Conformally adsorbing one or more additional adsorbent materials onto the first coating layer to form one or more additional coating layers, the one or more additional coating layers encapsulating or shielding the first coating layer, at least one of the additional adsorbent materials being non-carbonaceous, and the encapsulating layer being impermeable to at least one of gases and liquids; Dissolving the template particles in a liquid extractant containing process water for preservation to form a hierarchically coated framework and a second solution, the second solution containing the ionic species and the process water for preservation, wherein the step of forming one or more additional coating layers is carried out before and / or after the step of dissolving the template particles, Wherein the first solution and the second solution comprise an aqueous metal bicarbonate solution.

2. The method according to claim 1, wherein the stratigraphic arrangement of the coating layers includes at least one of the following: AB, ABC, ABCD, BAB, CBABC, DCBABCD, CABC, DABCD.

3. The method according to claim 1, wherein adsorbing the carbonaceous adsorbent material by chemical vapor deposition further comprises growing carbonaceous radical condensates at a temperature of at least 350 °C and at most 950 °C, and the first coating layer is characterized by a 532 nm Raman spectrum having an average unfit D peak position between 1300 cm -1 and 1332 cm -1 -1.

4. The method according to claim 2, wherein the stratigraphic arrangement includes at least one of an electrically insulating coating layer and a semi-conductive coating layer.

5. The method according to claim 1, wherein at least one coating layer is stratigraphically shielded by at least one other coating layer.

6. The method according to claim 1, wherein at least one coating layer is a metal.

7. The method according to claim 6, wherein the metal is one of Group I and Group II metals.

8. The method according to claim 1, wherein at least one coating layer includes at least one of boron nitride, transition metal dichalcogenides, metal oxides, and silicon-containing compounds.

9. The method according to claim 1, wherein at least one coating layer includes a polymer.

10. The method according to claim 1, wherein The adsorption of one or more additional adsorbent materials includes liquid-phase adsorption; and The formation of the one or more additional coating layers includes pyrolyzing a polymer pre-ceramic material.

11. The method according to claim 10, wherein the adsorption of one or more additional adsorbent materials includes chemical vapor deposition.

12. The method according to any one of claims 1-11, wherein the method further includes annealing at least one coating layer.

13. The method according to claim 1, wherein the solventless precipitation includes at least one of heating, atomizing, and reducing the pressure of the first solution.

14. The method according to claim 1, wherein at least one coating layer includes a synthetic anthracite network.

15. The method according to claim 1, wherein the solventless precipitation includes one of spray drying or spray pyrolysis.

16. The method according to claim 15, wherein the template precursor particles include at least one of a rosette structure, a rod-like structure, or a hollow spherical structure.

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