Scalable synthesis of carbon-coated

Abstract

This disclosure relates to the scalable synthesis of carbonaceous coated materials, including carbonaceous coated frameworks, on recyclable templates and using recyclable process liquids. This disclosure also demonstrates novel coated architectures. In particular, it demonstrates coated frameworks comprising synthetic anthracite networks. Using these methods, three-dimensional architectures constructed from graphene carbon can be produced in a scalable manner.

Description

[0001] Matthew Bishop,David Brill,Christopher Carstens,Abhay Thomas,

[0002] Andrew Westle

[0003] Cross-referencing of related applications:

[0004] This application claims priority to U.S. Provisional Patent Application No. 63 / 075,918, entitled “SCALABLE SYNTHESIS OF PERIMORPHIC CARBONS”, filed September 9, 2020, the entire contents of which are incorporated herein by reference. The following applications are hereby incorporated, in their entirety, by reference for all purposes: U.S. Provisional Patent Application 63 / 075,918 ('918 application); U.S. Provisional Patent Application 63 / 121,308 ('308 application); U.S. Utility Model Application 16 / 758,580 ('580 application); U.S. Utility Model Application 16 / 493,473 ('473 application); PCT / US17 / 17537 ('17537 application); PCT / US21 / 37435 ('37435 application); and U.S. Patent 10,717,843B2 ('843B2 patent). Technical fields:

[0005] This disclosure relates to a method for the scalable production of carbonaceous coating materials. More specifically, this disclosure relates to a low-cost, waste-reducing method for producing carbonaceous coating materials, wherein process materials are recyclable. Background technology:

[0006] Compared to bulk materials, nanostructured materials can possess superior properties. The construction of three-dimensional ordered architectures with block structures by nanostructures facilitates the realization of these superior properties in bulk material forms. These "frameworked" materials can be produced by synthesizing nanoscale or microscale blocks and arranging them into fine assemblies. In particular, porous materials with frameworked porous structures are highly favored due to their low density, high specific surface area, and potential mechanical properties.

[0007] Existing methods exist for generating three-dimensional porous assemblies from nanostructured blocks. The preparation of three-dimensional aerogels can involve dispersing nanostructured ions in a liquid matrix. At sufficient concentrations, the nano-ions can self-assemble into a gel-like network that can serve as the basis for the aerogel. For example, three-dimensional aerogels constructed from carbon or silica can be formed by freeze-drying self-assembling hydrogels. However, non-directed self-assembly techniques can produce disordered architectures with micropores. While these aerogels may have impressively low densities, their disorder and pore size make them unsuitable for many applications.

[0008] Theoretical models indicate the need for porous architectures with controllable compaction and order. For example, the Buehler group applied a high level of compaction, i.e., reduced pore size, when modeling the mechanical properties of theoretical helices constructed from continuous monolayer graphene. When the quasi-segmented spaces within the helical architecture are sufficiently small, the predicted mechanical properties of the framework outperform those of some steels. This can likely be attributed to the compaction and order of the architecture.

[0009] To impart order, directed synthesis techniques have been used. One approach to directed synthesis involves using another structure as a sacrificial template, thereby endowing the desired three-dimensional morphology to the templated structure. The template is then removed. This method is essentially a mimicry of geography; natural “crust pseudo-contents,” also known as “coated bodies,” are formed by mineralization around the sacrificial scaffold, which dissolves later. For this reason, we describe the templated material as a coated body and the template as coated in this paper. In some template techniques, a porous template is required. The pores are filled and replicated by the coating material; these techniques are described as “negative replication.” In other template techniques, the coating material does not fill the pores of the template but only covers the surface of the template, similar to concrete paper being conformally applied to the molded body. These techniques are described as “surface replication” in this paper.

[0010] Template-directed deposition techniques (such as chemical vapor deposition (“CVD”) conformally replicate the surface of a template. CVD decomposes gaseous reactants at elevated temperatures; for this reason, the template compounds used in conjunction with CVD procedures are often thermally stable metal oxides. Template-directed CVD is commonly used to synthesize graphene carbon, which has a two-dimensional molecular structure suitable for fine applications. Surface defects in the metal oxide can catalyze the nucleation of the graphene lattice. Subsequent extraction of the template can leave a porous framework comprising thin nanostructured walls. These frameworks are described herein as “coated frameworks”, or simply “frameworks”.

[0011] Compared to other compounds with lower thermal stability, metal oxides are often insoluble or only minimally soluble. For this reason, they typically react with strong acids to form soluble salts that can then be extracted into solution. One notable exception is the use of cubic NaCl templates, which have been used in template-directed CVD synthesis of hollow carbon cubes. NaCl crystals are readily extracted by dissolution in water. For lower-temperature template-directed methods (such as liquid-phase coating), a wider range of template compounds with better solubility can be employed.

[0012] Another important factor in surface replication is the porosity of the template. Replicating the surface of a non-porous template results in a hollow coated framework. Shi has demonstrated the synthesis of cubic frameworks on a non-porous NaCl cubic template. Tian has demonstrated the synthesis of inorganic frameworks with tubular and cubic morphologies on non-porous magnesium carbonate rod-shaped and cubic templates. Hollow frameworks formed by templates with non-porous templates may be morphologically regular, but are typically macroporous and lack compaction. Furthermore, a reasonably sized non-porous template has almost no surface area to be replicated, meaning that the coating mass produced by surface replication techniques is small compared to the mass of template consumed.

[0013] In contrast, surface replication of porous templates can be used to create more ordered and compact coated frameworks than those synthesized on aerogels or non-porous templates. Cui describes a template-guided CVD procedure that uses a porous magnesium oxide (MgO) template derived from magnesium carbonate precursor crystals to synthesize mesoporous graphene fibers. Each mesoporous fiber comprises a coated framework with a labyrinthine pore structure inherited from the template's porous structure of bonded nanocrystalline subunits. Workers have also produced porous metal oxide templates derived from metal hydroxide or metal carbonate precursors.

[0014] Currently, surface replication techniques using porous metal oxide templates represent a powerful means of synthesizing three-dimensional porous architectures constructed from nanostructured blocks. However, industrial-scale processes using porous metal oxide templates remain uniquely challenging due to the large number of inputs and outputs associated with the produced products. While product yields associated with these porous templates may be higher than those associated with non-porous templates with lower surface areas, they can still be relatively low.

[0015] Cui's work on mesoporous graphene fibers provides an example. Although the porous MgO template used has a 36m³ diameter, which should increase product yield... 2 g -1The MgO template exhibits a relatively high surface area and mesopore size of 10-30 nm, yet the mass of MgO consumed is still more than 30 times that of the resulting coated product. Subsequently, the MgO template is dissolved in a 1 mol / L hydrochloric acid (HCl) solution, resulting in another 50-fold increase in mass. Without any rinsing, this synthesis process generates three orders of magnitude (OOM) more diluted magnesium chloride (MgCl2) liquid waste than the coated product. Even using fuming HCl, the aqueous waste stream will be 200M more than the coated product before rinsing, and the concentrated MgCl2 brine waste may require further treatment and input. Furthermore, more intensive rinsing of the coated product is required, generating even more diluted waste.

[0016] When these materials are produced on an industrial scale, cleaning the coated frameworks with their high specific porosity can present problems. To illustrate this, we note that even after filtration, the mass of water retained within the pores of the coated product (such as Cui's graphene nanofibers) can easily exceed the template mass by 200M. This is due to the latter's higher specific porosity. Assuming a difference of 200M, even with a MgCl2 concentration of 0.1% (by weight) in the retained water, a residual MgCl2 mass equivalent to approximately 10% of the coated mass would remain upon drying. This level of impurity can render the coated product unacceptable for many applications, including electrochemical applications where carbon frameworks (produced at high purity on a laboratory scale) have proven superior.

[0017] It is also noted that the rinsing and purification issues are more severe compared to coated frameworks produced by surface replication on non-porous templates (given their typically large-pore interiors). However, frameworks produced on porous templates remain problematic, and for these frameworks to be highly useful industrially, they should be able to be produced on an industrial scale at reasonable levels of purity. Achieving this purity requires rinsing with water, which generates significantly more rinsing fluid than with conventional materials, exacerbating the aforementioned problem of large inputs and outputs.

[0018] Some of these challenges can be addressed by recycling the template and the process liquids used to extract the template from the coating material. This could reduce the inputs and outputs associated with template synthesis and removal. Recycling the template involves harvesting the template compound by extracting ions of the template compound from the encapsulated coating phase, and then reconstructing the template to the desired chemical and morphological specifications from the harvested ion library. Recycling the process liquids used means reusing a significant portion of the process liquids without requiring energy-intensive distillation.

[0019] Recycled templates or template-like materials have been demonstrated. Of particular note, Tian demonstrated the recycling of a porous crystalline metal carbonate template. This procedure involves: (i) applying an inorganic compound liquid to the surface of a magnesium carbonate template; (ii) dissolving the magnesium carbonate template in carbonic acid to form a diluted metastable magnesium bicarbonate (Mg(HCO3)2) solution; and (iii) using an ethanol antisolvent to destabilize the metastable bicarbonate solution and precipitate new magnesium carbonate crystals. In another work, Tian utilized a similar method to recycle porous MgO adsorbent materials derived from thermally decomposed magnesium carbonate precursor crystals. Similar porous MgO materials form templates for synthesizing subcrystalline frameworks. This recycling procedure involves: (i) dissolving the porous MgO material in carbonic acid to form a diluted metastable Mg(HCO3)2 solution; (ii) using an ethanol antisolvent to destabilize the bicarbonate solution and precipitate magnesium carbonate crystals; and (iii) thermally decomposing the magnesium carbonate crystals to reconstruct the porous MgO adsorbent material. In a subsequent step, it was noted that ethanol was used to accelerate precipitation and also to control the morphology of the precipitated magnesium carbonate; this is likely the case in both of Tian's procedures. It was further noted that, in the absence of solvent, the precipitate was aggregated and irregular in shape.

[0020] Tien points out that while template compounds can be recycled without antisolvents, the template itself (including its chemical and morphological specifications) cannot. Although the template or template-like material is ultimately recycled in both methods, using antisolvents not only requires a large solvent input but also generates a diluted solvent waste stream that cannot be recycled without distillation. The solvent waste generated when the template is recycled can be worse than brine waste. Therefore, this approach may exacerbate the liquid waste problem. Summary of the Invention:

[0021] A method for producing carbonaceous coated materials using both recycled templates and process liquids is desired. This method will reduce the required material inputs and processes, thereby reducing costs and waste. The template can be extracted from the encapsulating phase of the carbonaceous coated material and then reconstituted to the desired chemical and morphological specifications. A method for recycling metal oxide templates or metal oxide-containing templates (including Group I and II metal oxides, such as MgO) without consuming strong acids or solvents is particularly desirable. This has not been demonstrated in the prior art.

[0022] It is also desirable to use methods that retain a significant portion of the process liquids used in extraction and precipitation to produce carbonaceous coating materials. This method will reduce liquid consumption and waste. In particular, it is desirable to preserve process liquids without requiring large-scale distillation of miscible solutions.

[0023] It is also desirable to use methods that avoid retaining large amounts of water within their porous architecture to produce carbonaceous coated materials. This would eliminate the need for excessive rinsing of the templated carbonaceous products and avoid generating large amounts of diluent liquid filtrate. It would also improve the purity of the templated carbonaceous products.

[0024] Furthermore, it is desirable to develop carbonaceous coated materials with novel architectural features. This may include novel particle geometries, sizes, and aspect ratios not yet synthesized, as well as rationally designed tunable pore structures. In particular, it is desirable to develop carbonaceous coated frameworks with regular equiaxed particle geometries using a method incorporating template recycling. It is also desirable to develop carbonaceous coated frameworks with hierarchical equiaxed particle geometries using a method incorporating template recycling.

[0025] It is also expected that recycled templates will be used to synthesize carbonaceous coated materials such as those described in '308, '580, '473, '37435 and '843B2 patents.

[0026] This disclosure discloses an industrially scalable method for synthesizing carbonaceous coated materials. The general method is described according to four stages (precursor stage, template stage, replication stage, and separation stage) combining template and liquid cycles. In the template cycle, a portion of the template material is preserved for reuse, and in the liquid cycle, a portion of the process liquid is preserved for reuse. While many potential variations of the general method exist, a notable variation is the preferred method in which a solvent-free precipitation technique is used to precipitate a magnesium carbonate template precursor, and a carbon-coated framework is prepared using an MgO template. The preferred method also incorporates a gas cycle, in which a portion of the CO2 process gas is preserved for reuse.

[0027] The methods disclosed herein can be used in conjunction with a variety of industrial separation techniques. Techniques that may be particularly useful in separating hydrophobic carbonaceous coated products from stock solutions include foam flotation and liquid-liquid separation. Therefore, it is anticipated that the methods disclosed herein can be extended to include the use of known industrial separation techniques.

[0028] This disclosure also illustrates novel coated material architectures and variations of novel methods that can be used to manufacture them. In particular, equiaxed carbon coated frames and hierarchical equiaxed carbon coated frames are shown.

[0029] The objective of this invention is to improve the scalability and economy of producing carbonaceous coated frameworks by providing a method for recycling template materials and process fluids. Another objective is to provide a method for minimizing the waste stream generated from template recycling. In particular, the objective of this invention is to provide a scalable method for creating three-dimensional, controllable, compact architectures constructed from graphene carbon.

[0030] Another objective of this invention is to broaden the range of synthesizable template morphologies and provide techniques for controlling architectural features. This allows for the rational design of template materials based on the requirements of specific applications. Attached image description:

[0031] Figure 1 It is a cross-sectional view showing the formation of the surface replication and the encapsulation framework.

[0032] Figure 2 This is a cross-sectional view showing the formation of a covering frame using a porous template.

[0033] Figure 3 It is a cross-sectional view showing the differences between the encapsulated frames in the native and non-native morphological states.

[0034] Figure 4 A is a cross-sectional view showing the synthetic labyrinthine framework. Figure 4 B is a SEM micrograph of the labyrinthine frame.

[0035] Figure 5 A is a TEM micrograph of (top) PC particles including the layered carbonaceous coated phase and MgO content phase, and (bottom) the coated framework after content extraction. Figure 5 B is an HRTEM micrograph showing a disordered nematic graphene layer comprising segments of coated walls in a synthetic anthracite network.

[0036] Figure 6 This is a cross-sectional view showing the different types of superstructure shapes that can be formed. Cross-hatching indicates smaller-scale cellular substructures.

[0037] Figure 7 This is a cross-sectional view showing the formation of a labyrinthine framework under both confined and unconfined diffusion conditions.

[0038] Figure 8 It is a cross-sectional view depicting four wrapped frames with similar overall volume but different degrees of compaction.

[0039] Figure 9 This is an illustration of shuttle technology, in which the dissolution of the contents, the formation of the reservoir solution, and the precipitation from the reservoir solution outside the coating framework are shown to occur simultaneously.

[0040] Figure 10 This is a diagram of the general method. The template circulation and liquid circulation are marked.

[0041] Figure 11 This is a diagram illustrating a general method with gas circulation. Process gases are used to generate extractants in the separation stage and are recaptured during the precursor and / or template stages.

[0042] Figure 12 This is a diagram illustrating a preferred method. In this preferred method, the stock solution comprises a Mg(HCO3)2 solution, the template precursor comprises magnesium carbonate, the template comprises MgO, and the coating material is carbonaceous.

[0043] Figure 13 A is a diagram illustrating the sequence of incorporation shuttle, concentration of the stock solution by increasing CO2 pressure, and solvent-free precipitation by decreasing CO2 pressure. Figure 13 B is a diagram illustrating the use of a pressure reactor for the extraction and concentration of Mg(HCO3)2 stock solutions.

[0044] Figure 14 SEM micrographs of template precursor particles (N1) including magnesite particles with elongated superstructures obtained from an aqueous Mg(HCO3)2 stock solution.

[0045] Figure 15 The image includes a SEM micrograph of template precursor particles (H1), which comprises hydromagnesite particles with an isometric, hierarchical isometric superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0046] Figure 16 The image includes a SEM micrograph of template precursor particles (H2), which comprises hydromagnesite particles with elongated hierarchical superstructures obtained from an aqueous Mg(HCO3)2 stock solution.

[0047] Figure 17 The image shows a SEM micrograph of template precursor particles (H3), which include hydromagnesite particles with a thin-plate-like superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0048] Figure 18 The image is a SEM micrograph of template precursor particles (L1), which include hydrous magnesite particles with an isometric superstructure obtained from an aqueous Mg(HCO3)2 stock solution.

[0049] Figure 19 This is a SEM micrograph of template precursor particles (M1), which include magnesite particles with an isometric superstructure.

[0050] Figure 20 This is a SEM micrograph of template precursor particles (M2), which include magnesite particles with an isometric superstructure.

[0051] Figure 21SEM micrographs of template precursor particles (A1) are included, which comprise amorphous magnesium carbonate particles with a hollow hierarchical isometric superstructure obtained from an aqueous Mg(HCO3)2 stock solution. Some particles comprise thin fragments of hollow spherical shells.

[0052] Figure 22 The images include SEM images of template precursor particles with a hollow hierarchical isometric superstructure (images A to D), and TEM images of a carbon-coated framework with a hollow hierarchical isometric superstructure (image E). Image A shows A2-type precursor particles. Image B shows A3-type precursor particles. Image E shows the coated framework synthesized on a template obtained from A2-type particles.

[0053] Figure 23 The image includes a SEM micrograph of template precursor particles (C1), which comprises magnesium citrate particles with a hollow hierarchical isometric superstructure obtained from an aqueous magnesium citrate stock solution.

[0054] Figure 24 This is an optical micrograph of template precursor particles (E1), which include esperidone salt (magnesium sulfate heptahydrate) with a slender superstructure obtained from an aqueous magnesium sulfate stock solution.

[0055] Figure 25 SEM micrographs of template precursor particles (H4), including self-dissolved lithium carbonate at 2.71·10⁻⁶. -3 mol kg -1 The concentration of Li is present in the aqueous Mg(HCO3)2 stock solution of hydromagnesite particles.

[0056] Figure 26 SEM micrographs of template precursor particles (H5), including self-dissolved lithium carbonate at 2.74·10⁻⁶. -2 mol kg -1 Hydromagnesite particles with a hierarchical isometric superstructure are present in an aqueous Mg(HCO3)2 stock solution containing Li concentrations.

[0057] Figure 27 The image includes SEM micrographs of template precursor particles, which include magnesite particles with an isometric superstructure obtained from an aqueous Mg(HCO3)2 stock solution. Figure 27 A includes M3 type precursor particles. Figure 27 B includes M4 type precursor particles. Figure 27 C includes M5 type precursor particles.

[0058] Figure 28Optical micrographs of template precursor particles (N2) comprising magnesite trihydrate particles with elongated superstructures are included. The precursor material was obtained from an aqueous Mg(HCO3)2 stock solution, which was first used to precipitate magnesite hydrous. The magnesite hydrous was then recrystallized into magnesite trihydrate.

[0059] Figure 29 Optical micrographs of template precursor particles (N3) comprising trihydrate magnesite particles with elongated superstructures are included. The precursor material was obtained from an aqueous Mg(HCO3)2 stock solution, which was first used to precipitate polyhydrate magnesite. The polyhydrate magnesite was then recrystallized into trihydrate magnesite in the presence of sodium dodecyl sulfate as a surfactant.

[0060] Figure 30 The images include optical micrographs of template precursor particles, which include trihydrate magnesite particles precipitated from hydrated magnesite. Image A is a micrograph of trihydrate magnesite particles precipitated without a surfactant. Image B is a micrograph of trihydrate magnesite particles precipitated in the presence of a surfactant.

[0061] Figure 31 SEM micrographs of template precursor particles (Li1) including lithium carbonate particles with a hollow hierarchical isometric superstructure obtained from an aqueous Li2CO3 stock solution. Colored arrows indicate various observable features such as pinholes (red), cracks (blue), and wrinkled (yellow) spheres.

[0062] Figure 32 SEM images of porous MgO template particles (N1T1) made from N1 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0063] Figure 33 SEM micrographs of porous MgO template particles (H1T1) made from H1 template precursor particles. The template particles have inherited the hierarchical isometric superstructure of the precursor.

[0064] Figure 34 SEM micrographs of porous MgO template particles (H2T1) made from H2 template precursor particles. The template particles have inherited the hierarchical isometric superstructure of the precursor.

[0065] Figure 35 SEM micrographs of porous MgO template particles (H1T2) made from H1 template precursor particles. Due to sintering, most of the hierarchical isometric superstructure of the precursor has been lost.

[0066] Figure 36SEM images of porous MgO template particles (M1T1) made from M1 template precursor particles. The template particles have inherited the isometric superstructure of the precursor.

[0067] Figure 37 SEM images of porous MgO template particles (M1T2) made from M1 template precursor particles. The template particles have inherited the isometric superstructure of the precursor.

[0068] Figure 38 SEM images of porous MgO template particles (M1T3) made from M1 template precursor particles. The template particles have inherited the isometric superstructure of the precursor.

[0069] Figure 39 SEM images of porous MgO template particles (M1T4) made from M1 template precursor particles. The template particles have inherited the isometric superstructure of the precursor.

[0070] Figure 40 Optical micrographs of porous MgSO4 template particles (E1T1) made from E1 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0071] Figure 41 SEM micrographs of porous MgO template particles are shown. In image A, the porous MgO template particles are made from undoped magnesite particles. The average size of the joint subunits is 50 nm to 60 nm. In image B, the porous MgO template particles (H4T1) are made from Li-doped magnesite particles. The template particles include joint subunits with an average size of 80 nm to 100 nm, and some subunits are as large as 200 nm. The template particles have inherited the plate-like morphology of the precursor. In image C, the porous MgO template particles (H5T1) are made from Li-doped magnesite particles. The average size of the joint subunits is 100 nm to 300 nm. The template particles have inherited the plate-like morphology of the precursor.

[0072] Figure 42 SEM images of porous MgO template particles (H6T1) made from H6 template precursor particles. The template particles have inherited the elongated superstructure of the precursor.

[0073] Figure 43 This is a set of SEM micrographs comparing carbon-coated frameworks. Image A shows a P1-type framework made of M3T1P1 PC particles. Image B shows a P... 19 The frame is of the type M4T1P. 19 Made of PC particles. In image C, P is shown. 20 The frame is of the type M5T1P. 20 Made of PC particles.

[0074] Figure 44 SEM images of porous MgO template particles (M1T4) made from M1 template precursor particles. The template particles have inherited the isometric superstructure of the precursor.

[0075] Figure 45 Including PC particles (N2T1P) 21 SEM micrograph of the template particles (N2T1). The template particles were made by treating the N2 template material with heat and steam.

[0076] Figure 46 The TGA mass loss rate (% / ℃) of the N2 template precursor material is shown. Screen A shows the mass loss rate at a sample heating rate of 5℃ / min and 20℃ / min under Ar flow at 100 sccm. Screen B shows the mass loss rate at a sample heating rate of 5℃ / min and 20℃ / min under CO2 flow at 100 sccm.

[0077] Figure 47 SEM micrographs of porous MgO template particles (N2T4) made from N2 template precursor particles. The N2 template precursor material was heated in flowing Ar at a rate of 5 °C / min.

[0078] Figure 48 SEM images of porous MgO template particles (N2T5) made from N2 template precursor particles were included. The N2 template precursor material was heated in flowing Ar at a step rate of 20 °C / min. In image A, red arrows indicate the expansion regions of the elongated superstructures characteristic of these template particles. These expansion regions are associated with the internal macropores generated during heat treatment. Image B shows the internal macropores.

[0079] Figure 49 SEM micrographs of porous MgO template particles (N2T6) made from N2 template precursor particles are included. The N2 template precursor material was heated to 350°C under flowing CO2 at a heating rate of 20°C / min, and then further heated at a heating rate of 5°C / min.

[0080] Figure 50 SEM micrographs of porous MgO template particles (N2T7) made from N2 template precursor particles. Red arrows indicate fractures associated with the formation and expansion of large pores within the template particles.

[0081] Figure 51 SEM micrograph of a carbon-coated framework fabricated on porous MgO template particles (L2T1). The framework comprises elongated and thin features due to uncontrolled localized recrystallization during the template stage. These elongated and thin features are indicated by red arrows.

[0082] Figure 52 SEM images of the PC structure and the carbon-coated framework fabricated on porous MgO template particles (L3T1).

[0083] Figure 53 This includes SEM micrographs of PC particles obtained from L3T1 template particles. Images A and B show typical superstructures associated with the PC structure. Image C shows a magnified surface.

[0084] Figure 54 Includes SEM micrographs of porous MgO template particles (A1T1) made from A1 template particles. The yellow box and magnified inset show the porous substructure of the shell of the hollow spherical particles.

[0085] Figure 55 SEM micrographs of porous MgO template particles (A3T1) made from A3 template particles are included. The shell contains macropores, which are inherited features also present in the superstructure of the A3 template precursor. Several macropores are circled in yellow dashed circles. In addition, the shell contains mesopores generated by the decomposition of the A3 template precursor.

[0086] Figure 56 Through Ca1T1P 17 Content extraction of PC material yields a carbon-encapsulated framework (P) 17 SEM micrographs of the framework. The framework almost retains its original morphology and reflects the template surface of the template material Ca1T1.

[0087] Figure 57 Through Li1T1P 18 Content extraction of PC material yields a carbon-encapsulated framework (P) 18 SEM micrographs of the template. The framework retains its original morphology and reflects the template surface of the removed template particles.

[0088] Figure 58 This includes optical micrographs of mixtures produced through content extraction via shuttle technology. The micrograph in image A reveals two distinct phases: magnesite particles and a carbon-coated framework. The framework is sometimes distorted, as indicated by the yellow arrows. The micrograph in image B reveals one of the carbon-coated frameworks. The area within the yellow square is magnified in the micrograph in image C.

[0089] Figure 59 The images include SEM micrographs of the spray-dried MgSO4 template precursor (in image A) and SEM micrographs of the carbon-coated framework obtained from these precursor particles (in images B and C). The cellular substructure of the framework indicates the formation of a porous template by the MgSO4 precursor during the template stage.

[0090] Figure 60 This is a photograph of the liquid-liquid separation results, in which hexane is blended into an aqueous mixture of a carbon-coated framework and magnesite trihydrate. The carbon-coated framework migrates to the black hexane phase at the top of the scintillation vial, while the magnesite trihydrate remains in the aqueous phase at the bottom, appearing mostly white (although some carbon particles are mixed in and adhere to the sides of the scintillation vial).

[0091] Figure 61 The photograph shows the initial mixing of the carbon-coated frame and its subsequent flotation when the flask is placed under partial vacuum.

[0092] Figure 62 SEM micrographs of the carbon-coated framework, generated by surface replication on a pre-trihydrate magnesite template particle followed by content extraction, are included. The substructure comprises mesoporous unit cell subunits with a consistent isometric morphology and size throughout the superstructure. Image A shows the particle imaged at 250,000x magnification. Image B shows the particle at 100,000x magnification. Image C shows the particle at 25,000x magnification.

[0093] Figure 63 SEM images of a carbon-coated framework formed from pre-trihydrate magnesite and porous MgO template particles are included. The framework comprises fibrous and tubular elongated superstructures and cellular substructures, including conjoint subunits, mesoporous subunits, and macroporous subunits.

[0094] Figure 64 SEM images of carbon-coated frameworks formed from pre-hydromagnesite and porous MgO template particles are included. The frameworks comprise both thin, hierarchical isometric superstructures and mesoporous cellular substructures.

[0095] Figure 65 This is a SEM micrograph of a carbon-coated framework generated from pre-magnesite template particles. Mechanical agitation during content extraction produced individualized thin particles stacked on top of each other.

[0096] Figure 66 This is a SEM micrograph of a carbon-coated framework generated from pre-magnesite template particles. Prolonged heat treatment during the template stage and mechanical agitation during content extraction produced smaller subunit clusters without obvious higher-order structures.

[0097] Figure 67 This is a SEM image of a carbon-coated framework formed from pre-saturated magnesite and sintered MgO template particles. The framework consists of quasi-polyhedral unit cell subunits with a diameter greater than 100 nm.

[0098] Figure 68Optical micrographs of carbon-coated frames that spring back from their native architecture to a non-native shrinkage state produced by evaporation drying.

[0099] Figure 69 SEM images include carbon-coated frameworks generated by elongated template particles (N2T4). These carbon frameworks comprise flexible porous carbon fibers, as shown in image A. The cellular substructure is blurred due to the deformation of the thin coating walls, as shown in image B.

[0100] Figure 70 SEM images of carbon-coated frameworks generated from elongated template particles (N2T8) are included. These carbon frameworks show damage and fuzzing.

[0101] Figure 71 Including via N2T1P 21 Carbon-encapsulated framework (P) generated from PC particle content extraction 21 SEM micrographs of the N2T1 template particles. The framework wrinkles and cohedes with each other through van der Waals interactions between the coating walls. The N2T1 template particles were prepared by treating the N2 template material with heat and steam.

[0102] Figure 72 SEM micrographs of carbon-coated frameworks are included. Image A shows the framework generated on porous MgO template particles (N2T4). Image B shows the framework generated on porous MgO template particles (N2T1). The N2T1 template particles were generated after treatment with heat and steam, resulting in an increase in subunit size relative to the N2T4 subunits. This difference in templates can be observed after content extraction, based on the smoother appearance of the framework in Image A and the wrinkled appearance of the framework in Image B.

[0103] Figure 73 The images include SEM micrographs of template precursor particles and the carbon-coated framework from which they were obtained. Image A shows precipitated calcium carbonate (CaCO3) template precursor particles. Image B shows the carbon framework from which the template was obtained using these precursors.

[0104] Table summary:

[0105] Table 1 is a collection of samples discussed in this disclosure. Table 1 is arranged to show the progress of the material in the four stages of the general approach.

[0106] Table 2 is a collection of Raman peak positions obtained from the average Raman spectrum of the hydrated magnesium carbonate template precursor and the theoretical TGA mass loss.

[0107] Table 3 provides an overview of the N2 adsorption analysis of the template particles in the Na-doped magnesite template precursor. It shows the template material, the template precursor material used to generate the template material, the Na molality of the stock solution used to generate the template precursor material, and the furnace scheme and temperature used to convert the template precursor material into the template material. The Brunauer–Emmett–Teller (BET) surface area, BJH pore volume, template space (%), and template porosity (%) of the template material are also shown.

[0108] Table 4 provides an overview of the N2 adsorption analysis of the template materials generated from the N2 template precursor material with and without H2O during heat treatment. It shows the template material, the template precursor material used to generate the template material, the furnace scheme and temperature used to convert the template precursor material into the template material, and the treatment atmosphere. It also shows the BET surface area, BJH pore volume, template space (%), and template porosity (%) of the template material.

[0109] Table 5 is an overview of exemplary template-stage procedures and materials for understanding pod formation during the thermal decomposition of template precursor particles in Ar and CO2 atmospheres.

[0110] Table 6 is an overview of the template stage processing protocol used to generate all templates used as templates in the replication stage embodiments. It lists the template precursors, furnace schemes, and temperature-time-gas conditions for each stage.

[0111] Table 7 is an overview of the CVD synthesis protocols used to generate all PC materials for the replication stage examples. It lists the templates, furnace schemes, and temperature-time-gas conditions for each stage.

[0112] Table 8 provides an overview of the Raman data for the carbon framework and the relevant CVD parameters for carbon at all replication stages. The CVD parameters include temperature, gas type, and yield for each replication stage. The Raman data includes the laser power used and Ig. D / I G -I Tr / I G Peak intensity ratio, G peak position and D peak position, and GD peak wavenumber span. Detailed implementation method:

[0113] The detailed description begins with the initial section on "Terminology and Concepts," which provides the language and concepts used to describe and understand the invention. Subsequent sections are organized according to four methodological phases: "Precursor Phase," "Template Phase," "Replication Phase," and "Separation Phase." Several exemplary procedures and materials relating to each of the four phases are shown. Numerous potential variations of each phase can be readily conceived by those skilled in the art and can be combined to form a multitude of variations without departing from the methodology.

[0114] The detailed description is organized according to the following sections:

[0115] I. Terminology and Concepts

[0116] II. Description of General Methods and Variations

[0117] III. Furnace design, analytical techniques, and material nomenclature

[0118] IV. Precursor Stage – Examples

[0119] V. Template Phase – Example

[0120] VI. Replication Phase – Examples

[0121] VII. Separation Stage – Example

[0122] VIII. Envelope Frame Implementation

[0123] I. Terminology and Concepts

[0124] As defined in this paper, a “template” is a potential sacrificial structure that imparts a desired morphology to another material formed therein or on. Related to surface replication technology are the surface on which the template is positively replicated (i.e., the “template surface”) and the bulk phase on which it is negatively replicated (i.e., the “template body”). Templates can also play other roles, such as catalyzing the formation of coated materials. A “template-based” structure is a structure that replicates a feature of the template.

[0125] "Covered" or "covered" material is a material formed within or on top of a solid or "hard" template material.

[0126] As defined herein, “surface replication” includes template techniques in which the surface of a template is used to guide the formation of a thin coating wall of the adsorbed material, the wall substantially encapsulating and replicating the template surface formed thereon. Subsequently, upon displacement, the template body is negatively replicated by the intracellular space within the coating wall. Surface replication produces a coating framework with a templated pore wall architecture.

[0127] As defined herein, a “coated framework” (or “framework”) is a nanostructured coating formed during surface replication. A coated framework comprises nanostructured “coated walls” (or “walls”) with thicknesses ranging from less than 1 nm to 100 nm, but preferably between 0.6 nm and 5 nm. Because the coated walls essentially encapsulate and replicate the template surface, they can be described as “conformal.” Coated frameworks can be fabricated into diverse structures, ranging from simple hollow architectures formed on non-porous templates to labyrinthine architectures formed on porous templates. They can also comprise different chemical compositions. Typical frameworks can be constructed from carbon and may be referred to as “carbon-coated frameworks.”

[0128] As defined herein, “content” includes the template because it exists within a substantially enclosed envelope phase. Therefore, once an envelope phase has been formed around the template, the template can be described as content or “content-based.”

[0129] As defined herein, a “coated complex” or “PC” material is a composite structure comprising a content and a coating. A 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 comprising a carbon coating on MgO content can be represented as C@MgO.

[0130] The term "positive" is used herein to describe the space occupied by a block of solid material. The space occupied by the contents of a coated composite (i.e., "content space") is an example of positive space. Poreless templates include only positive space. Coated frames do not include positive space except for the space occupied by their thin walls.

[0131] The term "negative" is used herein to describe spaces not occupied by solid or liquid material. Negative spaces can be empty, gas-filled, or liquid-filled. The pores within an unimpregnated porous template include negative spaces. Porous templates include both positive and negative spaces. Encased frames, apart from the space occupied by their thin walls, consist only of negative spaces.

[0132] The term "cellular" is used herein to describe the pore wall morphology associated with a coated framework. "Cell" or "cell subunit" includes the region specifying the pores within the cell and the coating walls surrounding those pores.

[0133] The term "intracellular" is used herein to describe the negative space within a coated framework, which is formed by removing contents from the coated complex. Like the contents it acquires, the intracellular space is essentially enclosed by the coating walls.

[0134] The term "extracellular" is used in this paper to describe the negative space within the coating framework, which is inherited from the pore space of the coating composite, which in turn is inherited from the pore space of the porous template. We note that despite the "-extra" prefix, the extracellular space can be substantially located within the coating framework.

[0135] The intracellular and extracellular spaces of the coated framework are essentially separated by the coating walls. However, the ability to remove contents from the template composite means that the walls are either open or incomplete barrier layers at some point, as perfectly encapsulated contents cannot be removed. Therefore, although the coated body is described herein as essentially encapsulating the template surface, the encapsulation may still be incomplete or have gaps.

[0136] The term "native" is used in this paper to describe the morphological state of the coating structure in the coating complex. "Native" features include features that are essentially in their native state, and we can say that the structure "natively" possesses certain features (e.g., a natively 1 nm thick coating wall). After the contents are removed from the coating complex, the coating body may substantially retain its native properties, or it may be altered.

[0137] The term "non-primary" is used herein to describe a morphological state of a coated structure that has significantly changed from its primary morphological state (i.e., its original state within the coated complex). This change can occur at the substructure or superstructure level. For example, during the evaporation and drying of the internal liquid, the coating walls can be pulled inward by the liquid, causing a portion of the space within the unit cell to collapse. The deformation of the framework to a non-primary collapsed morphology can be reversible—that is, the framework may be able to substantially recover its primary morphology.

[0138] The terms "labyrinth" or "labyrinthine" are used herein to describe a network of interconnecting pores in a template or coating framework. The labyrinth can be intracellular or extracellular. A coating framework formed on a porous template can natively include both intracellular and extracellular labyrinths; therefore, a framework formed on a porous template can be described as a "labyrinthine framework." While the intracellular and extracellular labyrinths of a labyrinthine framework do not overlap, they can interweave. Labyrinthine frameworks comprise a preferred class of coating frameworks.

[0139] As defined herein, a “template precursor” or “precursor” is a material from which a template is obtained through some process that may include decomposition, grain growth, and sintering. The template may retain a pseudo-morphological similarity to the template precursor; therefore, engineering the precursor provides a way to engineer the template. The precursor is formed in a process liquid and is obtained from a stock solution.

[0140] The term "superstructure" is defined herein as the overall size and geometry 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 geometry of the framework will affect its properties, including how it interacts with other particles. Some superstructures facilitate the drying of a wet paste of a coated framework into a fine powder, while others cause the wet paste to dry into macroscopic particles that may require subsequent grinding. Superstructures can include the following shapes:

[0141] • “Isoaxial” is defined in this paper as a shape that is similar in size (with a size difference of less than 5 times) along its major axis, middle axis and minor axis.

[0142] • “Slender” is defined in this paper as a shape whose size along its long axis is significantly larger (5 to 50 times) than its size along its medium and short axes.

[0143] • "Thin" is defined in this paper as a shape that is more than 5 times longer along its major and middle axes than along its minor axis.

[0144] • “Grading” is defined in this paper as an equiaxed or elongated shape with thin features.

[0145] The term "substructure" is defined herein as the local morphology—that is, the internal architecture—of a porous template or coated framework. Some porous templates or coated frameworks have substructures comprising repeating joint substructure bases or "subunits". Different substructures may be characterized by subunits that differ in shape, size, and spacing from each other.

[0146] The term "acellular" is used herein to describe the internal negative space, which is not considered templated or part of the enclosing framework, but is still essentially surrounded by and located within the framework. Acellular 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 appears when surface replication cannot occur on a portion of the template surface (typically an inaccessible internal region).

[0147] Amorphous spaces may be desirable for density reduction in some applications and can be engineered using a combination of well-designed template engineering and diffusion-limited synthesis techniques. In particular, large template precursors can be used to generate large templates that combine long diffusion paths with small pores with minimal sintering. Rational design of surface replication parameters can also be helpful. For example, during CVD, low concentrations of carbonaceous vapor can be more easily removed from reaction sites and prevented from permeating into the entire porous substructure of the porous template.

[0148] Another way to achieve density reduction is by using porous template precursor materials. This produces extracellular porosity superior to amorphous spaces because it is more engineerable and does not require diffusion constraints. Porous template precursors can be made by using blowants (e.g., hollow microspheres produced during spray drying) or by using sacrificial materials during the preparation of template precursors (e.g., around sacrificial micelles or polymer-synthesized template precursors).

[0149] The concept of “compaction” in this paper refers to the area of ​​the coating walls contained within a given volume of a coated framework—that is, the volumetric surface area. Frameworks with a more compact substructure will have a finer, denser arrangement of coating walls within a given volume, while frameworks with a less compact substructure will have a coarser, more spatially diffuse arrangement of coating walls within a given volume. Porous templates and the labyrinthine frameworks formed thereon can be engineered to have varying degrees of compaction. Compaction includes a measure of the framework’s mesoscale crosslinking—that is, crosslinking at a higher scale than the molecular scale—where crosslinking originates from the topology of the template surface.

[0150] The compaction of the coating framework and the porous phase can be tuned by engineering the positive and negative spaces of the template. For example, a porous MgO structure produced by decomposing a magnesium carbonate precursor has a positive space comprising a network of interconnected MgO microcrystals. Its negative space comprises a porous network extending between MgO microcrystals and throughout the structure. It is known that microcrystals can grow at elevated temperatures, thereby roughening the grain structure. The same process can also lead to the growth and roughening of pores. This roughening of the positive and negative spaces will reduce the surface area of ​​the porous MgO template and thus reduce the compaction of the coating framework formed on the template. Simultaneously with the roughening of the template, it will become denser, and this densification will reduce the amount of extracellular space in the coating framework formed on the template.

[0151] For many reasons, the roughness of the template can be important. For example, increasing the pore size of the template and reducing its surface area allows reactive vapors to diffuse more quickly and deeply throughout the pores during CVD. If sufficient diffusion kinetics can be achieved, the coated walls synthesized in such processes can be more uniform in thickness.

[0152] The compaction and porous phase of the coated framework can also be tuned by selecting different template precursors. Different precursors will have different proportions of variable mass. The negative space of the template will depend on the degree to which the initial mass of the template precursor is lost during its decomposition. Calcination of template precursors containing a large proportion of variable material (e.g., highly hydrated salts) can produce porous templates with high specific porosity, which are more open to diffusion flow during CVD. Such templates may also be desirable if a larger extracellular space is desired in the coated framework.

[0153] The term "recycled" is used herein to describe the use of process materials previously used in a given step of a production process. Since actual losses of process materials may occur during the production of the coated product (e.g., process liquid losses due to evaporation or filtration), these losses can be compensated with pure raw process materials, and "recycled" process materials may include, in part, pure raw materials.

[0154] As defined herein, “process material” includes potentially recyclable non-coating materials used to generate coating materials. Process materials may include process liquids, process gases, extractants, template precursor materials, and template materials.

[0155] As defined herein, a “reservoir solution” comprises solvated cations and anions, as well as a process liquid, with the solvated ions carried by the process liquid (referred to herein as the “host”). The reservoir solution is formed during the separation phase. Precursors are obtained from the reservoir solution through one or more precipitation, dissolution, or decomposition reactions.

[0156] As defined herein, a “process liquid” is a feedstock of liquid water (“process water”) or solvent (“process solvent”) used in the precursor and separation stages. Process liquids can play several different roles in these stages. In the precursor stage, the formation of the template precursor is carried out by the process liquid, and the precursor can incorporate the process liquid into its crystal structure—for example, hydrated salts can be formed in process water and some of the process water can be incorporated into their crystal structure. In the separation stage, the extractant is carried out by the process liquid, and solvated ions generated by the reaction between the template, process liquid, and extractant are carried out by the process liquid. The process liquid can participate in the generation of the extractant and can itself react with the template during the separation stage.

[0157] As defined herein, “residual liquid” is a portion of a process liquid that may or may not carry solvated ions, and which remains inseparable from the solid (e.g., precursor or coated product) when the solid is separated from the main portion of the process liquid. Residual liquid may be contained within the coated product or wetted to its surface. Residual liquid may constitute a very small portion of the total process liquid. If a dry solid is desired, retention of residual liquid by the solid may require further separation.

[0158] As defined herein, an "extractant" includes an acid carried by the process liquid; these two phases together constitute an "extractant solution." The extractant can exist in an extremely dilute concentration in the extractant solution. In some cases, the extractant can be generated from (and within) the process liquid. For example, according to the reaction H₂O… (l) +CO 2(aq) →H2CO 3(aq) Carbonic acid (H2CO3) extractant can be generated from process water (and within the process water).

[0159] As defined herein, “content extraction” includes the selective removal of a portion of content from a content complex. Content extraction involves a reaction between the content and an extractant solution that produces solvated ions that efflux from the surrounding content, resulting in the simultaneous removal of the content, consumption of the extractant from the extractant solution, and the formation of a reserve solution. Typically, it is desirable to remove substantially all content blocks. Sometimes, partial removal of content blocks may be desired, or only partial removal of content blocks may be achievable.

[0160] As defined herein, “coating separation” includes the separation of coated products from uncoated, preserved process materials after content extraction. The preserved uncoated phase may include process liquids, stock solutions, and precipitates of stock solutions. Coating separation may include many different industrial separation techniques (e.g., filtration, centrifugation, foam flotation, solvent-based separation, etc.).

[0161] As defined herein, “solvent-free precipitation” includes the precipitation of template precursors in the precursor stage, where precipitation is primarily driven by a solution instability mechanism that does not require the introduction of miscible antisolvents into the process liquid. As a first example of solvent-free precipitation technology, the stock solution can be spray-dried. As a second example, a metastable metal bicarbonate stock solution can be depressurized to reduce CO2 solubility, resulting in the release of CO2 gas and the precipitation of the metal carbonate. We note that the term “solvent-free precipitation” does not imply the absolute absence of miscible solutions or solvents during precipitation, but rather indicates that precipitation is not primarily driven by mixing miscible solutions into the stock solution. One conceivable scenario is that the miscible solutions mixed with the process liquid maintain substantially the same concentration throughout the liquid cycle.

[0162] As defined herein, “shuttle” includes content extraction techniques that can be used during the separation phase, wherein simultaneously: (i) an extractant is generated by reacting process gas with process liquid; (ii) the contents are reacted with the extractant solution; (iii) the extractant is consumed; (iv) solvated ions in a reservoir solution are expelled from the contents; and (v) a precipitate is formed outside the contents from the reservoir solution. For example, shuttle may include simultaneously: (i) forming an H2CO3 extractant by dissolving CO2 in process water; (ii) reacting MgO contents with the H2CO3 extractant solution; (iii) consuming H2CO3; and (iv) forming MgO expelled from the coating. 2+ and (HCO3) - Ions; and (v) the precipitation of magnesium carbonate in the surrounding process water.

[0163] "MgCO3·xH2O" is used in this document to describe magnesium carbonate. It can include any hydrated or anhydrous magnesium carbonate, as well as basic magnesium carbonate, such as hydromagnesia.

[0164] As defined in this article, a “template loop” includes loops that construct, utilize, and reconstruct templates.

[0165] As defined herein, “liquid circulation” includes a circulation loop in which liquid-phase extraction of contents and liquid-phase formation of precursors are carried out using process liquids.

[0166] As defined herein, “gas circulation” includes a loop in which process gas is dissolved in a process liquid to produce an extractant solution, and then the process gas is subsequently released and recaptured. The release may be associated with the formation of a template precursor or template.

[0167] The “yield” of the coating material, or the process used to prepare the coating material, is defined herein as the coating mass divided by the sum of the content mass and the coating mass. Yield can be used to understand the amount of template material required to produce a given amount of coating material.

[0168] Figure 1 This is a cross-sectional view illustrating surface replication. The first structure in the sequence represents a simple, non-porous template comprising a template body and a template surface. The second structure in the sequence represents a PC structure comprising contents and a coating body. This complex is formed by applying conformal coating walls to the template surface. The third structure in the sequence comprises a coated framework in a liquid. This represents the framework after the contents have been removed via liquid-phase extraction. The fourth structure in the sequence represents the framework in its native state after drying. The walls of the coated framework substantially replicate the template surface, and its pores substantially replicate the template body.

[0169] Figure 2 This is a cross-sectional view illustrating the formation of a coated framework using a porous template. The first structure in the sequence represents a template with several pores leading to a central pore. The entire pore space is not occupied by solid or liquid material and includes negative space. The second structure in the sequence represents a PC structure comprising contents and a coating. This composite is formed by applying a conformal coating to the template surface. The PC structure includes positive space associated with the contents and negative space associated with the pores of the porous template. The third structure in the sequence represents a coated framework formed by removing the contents. The framework includes negative intracellular space corresponding to the contents of the PC structure and negative extracellular space corresponding to the pores of the PC structure. Both the intracellular and extracellular spaces are located within the coated framework.

[0170] Figure 3 This is a cross-sectional view illustrating the differences between the native and non-native morphological states of the encapsulated framework. The first structure in the sequence represents a PC structure comprising the contents and the encapsulated body. The morphology of the encapsulated body in the PC structure represents its native morphology. The second structure in the sequence represents an encapsulated framework formed by removing the contents. The morphology of the framework is essentially unchanged from its original morphology in the PC structure, and therefore the framework is in its native state. The third structure in the sequence represents an encapsulated framework that has been deformed and collapsed. In this non-native state, the walls no longer represent replicas of the template surface, and the intracellular space no longer represents negative replicas of the contents. If elastic deformation occurs, the framework may reversibly deform back to its native morphology.

[0171] Figure 4A is a cross-sectional view showing the synthesis of the labyrinthine framework. From left to right, the first structure in the sequence represents the template precursor. The second structure represents the porous template. The porous template includes a labyrinth of interconnected template pores (but their connectivity is not shown in the cross-section). The surface of this porous structure guides the formation of the coating. The third structure in the sequence represents the PC structure comprising the contents and the coating. The labyrinth of template pores in the template is inherited from the PC structure. The fourth structure in the sequence represents the labyrinthine framework formed by removing the contents. The framework natively includes an intracellular labyrinth reflecting the positive space of the template and an extracellular labyrinth reflecting its negative space. Although the intracellular and extracellular labyrinths do not overlap, they can permeate the volumetric interweaving of the framework.

[0172] Figure 4 Image B is a SEM micrograph of a labyrinthine carbon framework synthesized on a porous MgO template. The contents have been removed, and the framework retains its original morphology. From the main image, we can see that the framework comprises a rhombohedral superstructure. This superstructure is inherited from the rhombohedral magnesite precursor. From the magnified inset, we can see the cellular substructure of the unit cell subunits. Two such subunits are outlined and labeled in the magnified inset. Each unit cell subunit includes an encapsulated portion of intracellular pores and a coating wall. We can also see extracellular pores in the magnified inset, and two such pores are labeled. The extracellular labyrinth traverses the interior of the framework, interweaving with the intracellular labyrinth.

[0173] Figure 5 A is a TEM micrograph of (top) PC particles including the graphene-coated phase and the MgO content phase, and (bottom) the graphene-coated framework after content extraction. Figure 5 B is an HRTEM micrograph showing a disordered nematic graphene layer including segments of the coating wall.

[0174] Figure 6 This is a cross-sectional view showing four types of superstructure shapes: elongated, thin, equiaxed, and hierarchical equiaxed. Cross-hatching indicates smaller-scale cellular substructures present throughout the superstructure. Figure 6 The exemplary “hierarchical equiaxed” superstructure shown is a hollow sphere with a thin shell.

[0175] Figure 7 This illustrates how density reduction of the coated framework can be achieved through hierarchical pore engineering. This is a cross-sectional representation, so the template subunits, though appearing disconnected, are actually connected. Figure 7 A illustrates the generation of reduced-density acellular spaces within a coated framework via a diffusion-restricted surface replication procedure. In this case, the template precursor can be non-porous. Diffusion restriction prevents the adsorbate material from being uniformly distributed throughout the porous substructure. This can be advantageous for generating coated walls with a certain thickness and integrity gradient, and in some cases, it can even generate hollow acellular spaces within the coated framework, such as... Figure 7 As shown in Figure A. Figure 7 B illustrates how a porous template precursor material, generated around the trapped gas region, creates a reduced-density extracellular space within the coated framework. This can occur due to the effect of internal inflators or due to the formation around the bubbles. Figure 7 C illustrates the creation of a reduced-density extracellular space within the coated framework by a porous template precursor material generated around the subsequently removed sacrificial material.

[0176] Figure 8 This diagram shows cross-sectional views of three labyrinthine frames with different substructures. The substructure shown on the left is the least compact of the three. Its volume is similar to the others, but it contains less encapsulated area within this volume. The substructure shown in the center is slightly more compact than the one on the left because its volume contains a larger encapsulated area. The substructure shown on the right is the most compact—its volume is similar to the other two substructures, but it contains the largest encapsulated area. This diagram illustrates that the compaction of the encapsulated frame is imparted by the volumetric surface area of ​​the porous template—that is, the total internal and external surface area per unit template volume, where the template volume includes both the positive and negative spaces of the template.

[0177] Figure 9 This is a cross-sectional view showing the shuttle process. The first image in the sequence represents PC material immersed in the extractant solution. The second image in the sequence represents a coated framework containing incompletely extracted contents. In this second image, the reaction between the contents and the extractant solution is underway. The solvated ions formed by this reaction are diffusely effluxing from the coated framework, as indicated by the arrows, and precipitating in the surrounding process liquid. In other words, the contents are "shuttling" out of the coating as solvated ions, some of which then reprecipitate outside the framework. We note that the precipitate and the contents may not contain the same compounds.

[0178] II. Description of General Methods and Variations

[0179] The "general method" is the most basic form of the method. It includes methods for synthesizing coated products in which a large portion of the template material and process fluids are preserved and reused. Therefore, the general method can be performed cyclically. All variations of the methods disclosed in this disclosure include some variation of the general method.

[0180] The general approach includes a series of steps presented in this paper in four phases (i.e., precursor phase, template phase, replication phase, and separation phase) for ease of description. Each phase is defined by one or more steps, as described below:

[0181] Precursor stage: Precursor materials are obtained from the stock solution through solvent-free precipitation. A portion of the process liquid is preserved.

[0182] Template stage: Processing the precursor material formed in the precursor stage in one or more procedures to form template material.

[0183] Replication stage: Adsorbent material is adsorbed onto the template surface to form PC material.

[0184] Separation stage: Perform content extraction and coating separation. Content extraction produces a stock solution. Coating separation separates the coated product from the preserved process material.

[0185] In practice, each step within these stages may itself include multiple subsidiary steps. Furthermore, each of these steps may occur simultaneously with a step from another stage, allowing different stages to overlap in time sequence in practice. This is particularly anticipated in variations employing a one-pot technique. As a hypothetical example of this, a stock solution may be continuously injected into a furnace along with the adsorbent material. In this hypothetical furnace, precursor particles may be precipitated from the stock solution continuously and simultaneously, template particles may be formed by heating the precursor particles, and the coating material may be adsorbed onto the template particles. This corresponds to the steps categorized herein as the precursor stage, template stage, and replication stage, respectively.

[0186] Similarly, it is envisioned that, in practice, many variations of the general method may be incorporated into the steps described in the four stages in different orders. Moreover, in some variations, steps that by definition belong to one of the four stages herein may instead occur in different stages. Such variations are contemplated herein and do not depart from the method of the invention, which, for the purpose of describing the entire cycle, is presented herein only as a discrete sequence with four stages.

[0187] Ancillary processing steps (e.g., rinsing, drying, blending, condensing, spraying, stirring, etc.) may also be incorporated into each stage of the method. As a hypothetical example of this, the replication stage may involve coating the template material with a coating material via a liquid-phase adsorption process, followed by filtering, rinsing, and drying the resulting PC material. It will be apparent to those skilled in the art that these processing steps are incorporated into many variations, and therefore, they are not enumerated herein.

[0188] The input and output of a general method are in Figure 10 As shown in the figure. General methods include template circulation, which allows for the preservation and reuse of template material, and liquid circulation, which allows for the preservation and reuse of process liquids.

[0189] Variations of the general method

[0190] The following discussion explores the various ways in which enumerations can implement the general method differently. The omission of variations in this discussion should not be interpreted as restrictive, as an exhaustive list of ways to implement the general method is impractical.

[0191] The general approach aims to provide a way to circulate coated products while preserving process materials. In each cycle of the general approach, a portion of the process materials used are preserved and reused. In some variations, essentially 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 loss of process liquids through evaporation from an open tank or wet filter.

[0192] In some variations of the general approach, process steps may correspond to batch processes. In other variations, process steps may correspond to continuous processes.

[0193] In some variations of the general method, solvent-free precipitation may include at least one of the following techniques: heating or cooling the stock solution to change the solubility of the solute in the stock solution; evaporating dissolved gases in the stock solution; depressurizing the stock solution; atomizing the stock solution; spray drying the stock solution or spray pyrolysis.

[0194] In some variations of the general approach, the precursor structure may include at least one of the following: an elongated, thin, isometric or hierarchically isometric 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 spherical or spherical superstructure; a hollow superstructure; a fragmented superstructure comprising fragments of another parent superstructure; or a bent fragmented superstructure comprising fragments of a hollow superstructure.

[0195] In some variations of the general method, the precursor structure may precipitate around one or more other sacrificial structures, which may exist as inclusions in the precursor structure after precipitation. In some variations, these inclusions in the precursor structure may subsequently be removed, thereby creating voids.

[0196] In some variations of the general method, the measurement of the precursor structure along its long axis may be less than 1 μm. In some variations, the measurement of the precursor along its long axis may be between 1 μm and 100 μm. In some variations, the measurement of the precursor along its long axis may be between 100 μm and 1,000 μm.

[0197] In some variations of the general method, the precursor material may comprise at least one of the following: hydrate; metal bicarbonate or carbonate; Group I or Group II metal bicarbonate or carbonate; mixture of salts. In some variations, the precursor may comprise MgCO3·xH2O in the form of at least one of the following: hexahydrate, polyhydrated magnesite, trihydrated magnesite, hydromagnesite, spheroidal magnesite, magnesite, and nanocrystalline or amorphous MgCO3·xH2O.

[0198] In some variations of the general method, the stock solution may contain at least one of the following: a metal cation and an oxoanion; an aqueous solution of a metal bicarbonate; a Group I or Group II metal bicarbonate; an organic salt; or Mg(HCO3)2. In some variations, the stock solution may contain at least one of a dissolved gas, an acid, and a base. In some variations, the stock solution may be metastable.

[0199] In some variations of the general method, the process liquid preserved in the precursor stage may include a distillate. In some variations, the distillate may be formed by condensing process liquid vapors formed during spray drying or spray pyrolysis. In some variations, the process liquid preserved in the precursor stage may carry solvated ions, with the process liquid and ions together constituting the mother liquor.

[0200] In some variations of the general method, the treatment performed on the precursor material during the template stage may include at least one of the following: decomposition of the precursor; partial or localized decomposition of the precursor; decomposition of the precursor surface; thermal decomposition; and oxidation of the organic phase present within the precursor structure. In some variations, the treatment may include flash drying, spray drying, spray pyrolysis, vacuum drying, rapid heating, slow heating, or sublimation. In some variations, 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 products of the precursor; exposure to reactive vapors; exposure to water vapor; sintering; or sintering with the assistance of a dopant.

[0201] In some variations 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 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.

[0202] In some variations of the general approach, the template structure may include at least one of the following: an elongated, thin, isometric or hierarchically isometric 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 spherical or spherical superstructure; a hollow superstructure; a fragmented superstructure comprising fragments of another parent superstructure; and a curved fragmented superstructure comprising fragments of a hollow superstructure.

[0203] In several variations of the general method, adsorbing the coating material onto the template surface may include at least one of the following: coating techniques, physical vapor deposition, and chemical vapor deposition. In some variations, the coating technique may include applying a liquid or solid organic coating to the template surface, followed by the formation of a carbon coating from the master coating. In some variations, deposition may include the pyrolytic decomposition of a vapor-phase organic compound at a temperature between 350°C and 950°C. In some variations, the coated carbon may be annealed after adsorption onto the template surface.

[0204] In some variations of the general method, content extraction may utilize an extractant solution containing a weak acid as the extractant. In some variations, the extractant solution may be formed by dissolving a process gas in process water. In some variations, the extractant solution may be an aqueous solution of H₂CO₃ formed by dissolving liquid or gaseous CO₂ in process water. In some variations, content extraction may include shuttle techniques. In some variations, content extraction may be performed under elevated pressure or temperature conditions.

[0205] In several variations of the general method, coated separation may include at least one of the following: decantation, hydrocyclone, settling, sedimentation, flotation, foam flotation, centrifugation, filtration, and liquid-liquid extraction. In some variations, coated separation may separate the coated product from substantially all process liquids. In some variations, the coated product may retain a residual portion of the process liquid. In some variations, the coated product may float naturally due to the retention of its internal gas. In some variations, the internal gas of the coated product may expand by reducing the pressure of the surrounding process liquid, increasing the buoyancy of the coated product, and inducing flotation. In some variations, a portion of the internal gas of the coated product may permeate by reducing the pressure of the surrounding process liquid and then repressurizing the surrounding process liquid, causing hydrostatic pressure to force the process liquid into the coated product.

[0206] In some variations of the general approach, the encapsulation framework may include at least one of the following: carbonaceous materials, pyrolytic carbon, carbon anthracite networks, carbon sp. x Networks and helical networks of carbon.

[0207] In some variations of the general approach, under 532 nm excitation, the carbonaceous coated framework may include at least one of the following: Raman spectra between 4.0 and 1.5. D / I G Ratio; Raman spectrum between 1.5 and 1.0 I D / I G Ratio; Raman spectrum between 1.0 and 0.1 I D / I G Ratio; Raman spectrum between 0.0 and 0.1 I Tr / I G Ratio; Raman spectrum between 0.1 and 0.5 I Tr / I G Ratio; Raman spectrum between 0.5 and 1.0 I Tr / I G Ratio; Raman spectrum between 0 and 0.15 I 2D / I G Ratio; Raman spectrum between 0.15 and 0.3 I 2D / I G Ratio; and Raman spectra between 0.30 and 2.0 I 2D / I G Compare.

[0208] In some variations of the general approach, under 532 nm excitation, the carbonaceous coating framework may include at least one of the following: located at 1345 and 1375 cm⁻¹. -1 The unfitted Raman spectrum D peak is located at 1332 and 1345 cm⁻¹. -1 The unfitted Raman spectrum D peak is located between 1300 and 1332 cm⁻¹. -1 The unfitted Raman spectrum D peak is located at 1520 cm⁻¹. -1 With 1585cm -1 The unfitted Raman spectrum G peak is located at 1585 cm⁻¹. -1 With 1600cm -1 The unfitted Raman spectrum G peak between; and the peak located at 1600 cm⁻¹ -1 With 1615cm -1 The unfitted Raman spectrum G peak between them.

[0209] In some variations of the general method, the coating product may include a coating framework. In some variations, the coating framework may include at least one of the following: native morphology, non-native morphology, internal gas, hydrophobic surface, hydrophilic surface, mesopores, one or more macropores, and hierarchical porosity.

[0210] In some variations of the general approach, the measurement along the long axis of the coating framework may be less than 1 μm. In some variations, the measurement along the long axis of the coating framework may be between 1 μm and 100 μm. In some variations, the measurement along the long axis of the coating framework may be between 100 μm and 1,000 μm. In some variations, the coating framework may comprise an elongated, thin, equiaxed, or hierarchically equiaxed superstructure. In some variations, the elongated coating framework may comprise an aspect ratio between 50:1 and 200:1. In some variations, the equiaxed superstructure of the coating framework may be spherical or globular. In some variations, the equiaxed superstructure of the coating framework may be hollow. In some variations, the coating framework may comprise fragments of hollow shells. In some variations, the coating framework may comprise non-cellular spaces.

[0211] In some variations of the general approach, the envelope frame may include 1,500 to 3,000 m. 2 / g BET surface area. In some variations of the general method, the coating framework may include 10 to 1,500 m². 2 / g BET surface area.

[0212] In some variations of the general method, the coated product may undergo further processing after coating separation. In some variations, further processing after coating separation may include at least one of the following: flash drying, spray drying, spray pyrolysis, decomposition, chemical reaction, annealing, and chemical functionalization.

[0213] In some variations of the general approach, liquid circulation may also incorporate the recapture and preservation of process liquids released or evaporated (potentially in vapor phase) during the template stage, although this is not presented as an output. Figure 10 This is reflected in the data. It is not reflected because in most (but not all) variations of the conceived general approach, the amount of process fluid retained during the template stage will be significantly less than the amount retained during the precursor stage.

[0214] In some variations of the general method, gas circulation can be incorporated into the method. The inputs and outputs of the general method with gas circulation are... Figure 11 As shown in the diagram. In the gas cycle, the process gas is released during the precursor stage and / or template stage. This released gas is preserved. Then, during the separation stage, the preserved process gas can be dissolved in a preserved process liquid to generate an extractant solution.

[0215] The preferred method described below includes variations of the general method, wherein the MgCO3·xH2O template precursor material is obtained from an aqueous Mg(HCO3)2 stock solution, and a portion of the CO2 process gas is preserved via gas recycling. The inputs and outputs of the preferred method are as follows: Figure 12 As shown in the figure. Preferred methods include:

[0216] Precursor stage: Obtain MgCO3·xH2O precursor material from an aqueous Mg(HCO3)2 stock solution, wherein the acquisition includes solvent-free precipitation of MgCO3·xH2O and emission of CO2 process gas. A portion of the released CO2 process gas is preserved. The MgCO3·xH2O precursor material and process water are separated. The process water is preserved.

[0217] Template stage: The MgCO3·xH2O precursor material formed in the precursor stage is thermally decomposed in one or more processes to form a porous MgO template material. This allows for the preservation of released CO2 process gases.

[0218] Replication stage: Organic or carbonaceous coating materials are adsorbed onto the template surface of the porous MgO template to form PC material.

[0219] Separation stage: The preserved CO2 process gas is dissolved in the preserved process water to form an aqueous H2CO3 extractant solution. Content extraction involves the reaction between the content MgO and the aqueous H2CO3 extractant solution to generate 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 can be used to separate the carbon coatings.

[0220] Certain variations of the preferred method may employ pressure regulation to form a concentrated stock solution and improve the precipitation process. Concentrated stock solutions can be associated with numerous benefits, including superior precipitation kinetics, reduced process water consumption, smaller containers, and improved energy efficiency. Two exemplary methods for achieving this are described in... Figure 13 It is shown in the figure and described below.

[0221] exist Figure 13 In the first frame of A, shuttle technology has been used to extract content. The shuttle technology produces a mixture containing an aqueous Mg(HCO3)2 stock solution, one or more coated frameworks, and a MgCO3·xH2O precipitate. This precipitate... Figure 13 The first image of A shows a mixture of trihydrate magnesite rods and needle-like trihydrate magnesite agglomerates. Next, the coated product is separated from other process liquids and solids. Following this, the MgCO3·xH2O precipitate is dissolved by increasing the CO2 pressure, which increases the dissolved CO2, H2CO3, and HCO3. - The concentration is thus adjusted to form a concentrated stock solution, such as... Figure 13 As shown in 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).

[0222] Another way to obtain a concentrated stock solution is to perform content extraction in a pressurized reactor. A schematic diagram illustrating this method is shown in [the diagram]. Figure 13 As shown in B. Similar to Figure 13 The procedure shown in A, Figure 13 The procedure shown in B uses increased CO2 pressure to increase the dissolved CO2, H2CO3, and HCO3. - The concentration. In Figure 13 In step B, PC material, CO2, and H2O (possibly, aqueous Mg(HCO3)2 mother liquor) are fed into a pressurized reactor. Content extraction and the formation of a concentrated stock solution occur within the pressurized reactor. The mixture of the coated product and the concentrated stock solution is discharged from the pressurized reactor, where coating separation can then occur. 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).

[0223] III. Furnace design, analytical techniques, and material nomenclature

[0224] Certain furnace schemes have been detailed in the description of the procedures for generating exemplary materials as described in the following sections. These schemes can be used in the exemplary template stage procedure detailed in Part V and the exemplary copy stage procedure detailed in Part VI.

[0225] Option A: In Option A, a Thermcraft tube furnace modified into a rotary furnace with a quartz tube can be used. 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 furnace has a wattage of 6800 W and a maximum operating temperature of 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. Quartz baffles inside the belly 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 on the outside of the belly on each side of the heating zone of the furnace. Glass wool can be used to fix the position of the ceramic blocks.

[0226] For the exemplary procedure performed using scheme A, a material sample can be placed inside the abdomen, causing it to agitate within the reactor. Loosely fitted ceramic blocks located on the exterior of the abdomen section on each side of the furnace's heating zone allow gas flow and block the powder. Glass wool filling can be used to fix the ceramic blocks in place while also acting as a permeable layer. The ends of the tube can be fitted with two stainless steel flanges to allow gas flow through the system.

[0227] Option B: An MTI rotary tube furnace with a quartz tube can be used. The furnace has a clamshell design including a cylindrical heating chamber with a diameter of 120 mm and a heating length of 440 mm. The furnace has a wattage of 2500 W and a maximum operating temperature of 1150 °C. The OD of the quartz tube can be 60 mm. The tube can be substantially horizontal. For an exemplary procedure performed using Option B, a material sample can be placed in a ceramic boat. It can then be placed in the quartz tube within the heating zone, after which heating can begin. A loosely fitted ceramic block located outside the heating zone of the furnace allows gas flow. Glass wool filling can be used to fix the position of the ceramic block while also acting as a permeable layer. Two stainless steel flanges can be fitted to the ends of the tube.

[0228] Option C: A Lindberg Blue-M tube furnace with a quartz tube can be used. The quartz tube's OD can be 150 mm. The furnace has a clamshell design with a cylindrical heating chamber having a diameter of 190 mm and a heating length of 890 mm. The furnace has a wattage of 11,200 W and a maximum operating temperature of 1200 °C. The tube can be substantially horizontal. For an exemplary procedure performed using Option C, the sample can be placed in a ceramic boat. It can then be placed in the quartz tube within the heating zone, after which heating can begin. A loosely fitted ceramic block located outside the heating zone of the furnace allows gas flow. Two aluminum flanges can be fitted to the ends of the tube to allow gas flow through the system.

[0229] Option D: A Vulcan 3-550 muffle furnace can be used. The furnace has a rectangular heating chamber with dimensions of 190mm x 240mm x 228mm. The furnace has a wattage of 1440W and a maximum operating temperature of 1100°C. For an exemplary procedure performed using Option D, a material sample can be placed in a ceramic boat. It can then be placed inside the muffle furnace, and heating can then be initiated.

[0230] Option E: A TA Instruments Q600 TGA / DSC can be used. For the exemplary procedure performed using Option E, a 90 μL alumina disk 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 Option E.

[0231] Various analytical techniques were used to characterize the procedures and materials presented in this paper. These are described in detail below.

[0232] Electrolytic conductivity (“conductivity”) is used to measure solution concentration. Conductivity is a measurement of the electrical response of a solution. The electrical response of a solution can be correlated with the concentration of ions dissolved in the solution, and the conductivity value decreases as ions in the solution precipitate. A similar measurement is total dissolved solids (“TDS”), which correlates conductivity measurements with a reference ion concentration (typically potassium chloride), which depends on the dissolved salt compound.

[0233] Thermogravimetric analysis (TGA) was used to analyze the thermal stability and composition of the materials. All TGA characterizations were performed on a TA Instruments Q600 TGA / DSC. During TGA analysis, samples were held in 90 μL alumina trays. Unless otherwise specified, all TGA procedures were performed at 20 °C / min. Unless otherwise specified, air or Ar (Ar) was used as the carrier gas during the TGA procedures.

[0234] Raman spectroscopy was performed using a ThermoFisher DXR Raman microscope equipped with a 532 nm excitation laser. For each sample analyzed, a 16-point spectrum was generated using measurements taken on a 4x4 rectangular grid with a point-to-point spacing of 5 μm. The 16-point spectra were then averaged to produce an average spectrum. The reported Raman peak intensity ratios and Raman peak positions for each sample were derived from the average spectrum of the sample. No line-fitting software was used; therefore, the reported peak intensity ratios and peak positions are correlated with unfitted peaks related to the overall Raman line shape.

[0235] Gas adsorption measurements were performed using a Micromeritics Tristar IIPlus. Nitrogen adsorption was measured across a pressure (p) range at a temperature of 77 K, where... Pressure increment range is Until The BET specific surface area was calculated using Micromeritics MicroActive software, where the specific surface area is assumed to be σ. m (N2, 77K) = 0.162nm 2 The data were derived from the BET monolayer capacity. Samples were pretreated by degassing with a continuous flow of dry nitrogen at 100°C prior to analysis.

[0236] Pore ​​size distribution (PSD) and pore volume accumulation are another technique that can be performed based on gas adsorption data to gain deeper insights into the sintering behavior of particles. Data were collected by Micromeritics Tristar II Plus at 77 K. The pressure is between and within a range Until Incremental measurements were performed on nitrogen adsorption and desorption. Samples were pretreated by degassing with a continuous flow of dry nitrogen at 100°C prior to analysis.

[0237] The adsorption-desorption PSD and pore volume accumulation were calculated using the Micromeritics MicroActive software by applying the Barrett, Joyner, and Halenda (BJH) method. This method provides a comparative evaluation of the mesopore size distribution in gas adsorption data. Faas correction and Harkins and Jura thickness curves can be applied to all BJH data. The pore volume accumulation V can be measured for both the adsorption and desorption portions of the isotherm. PORE (cm 3 / g).

[0238] Various exemplary materials are described in this disclosure. To aid in the identification and tracking of these exemplary materials, a material naming system has been adopted and is described below. All names of exemplary materials are in bold; in this document, N2 describes an exemplary material, and N2 refers to nitrogen gas.

[0239] An exemplary type of template precursor material is designated as S. x S specifies the first one or two letters of the template precursor material (i.e., N represents trihydrate magnesite, L represents polyhydrate magnesite, Li represents lithium carbonate, C represents magnesium citrate, A represents amorphous or non-crystalline MgCO3·xH2O, H represents hydromagnesite, M represents magnesite, E represents esperidium salt, and Ca represents calcium carbonate), and x specifies the different types of precursor compounds (e.g., H1 and H2 represent two different types of hydromagnesite precursors).

[0240] Exemplary types of template materials in format S x T y Naming. S x Named components specify the template type S used to generate template S x T y The precursor type, and T y Named components specify the template type S used to generate template S x T y Specific processing. For example, N1T1 and N1T2 indicate two different template types formed through two different processing of precursor type N1. It should be noted that although the complete S x T y The name indicates a specific template type, but T y The name component itself is specific only to a given S x Precursor type. For example, the processing used to create template types N1T1 and N2T1 is different, even though these template types share the same T1 name component.

[0241] Exemplary types of PC materials are shown in format S x T y P z Naming, where S x T y The name component specifies the template type, and P z The name composition specifies a particular carbon encapsulation type. For example, M3T1P1 and M3T1P2 indicate two different PC materials formed from the same M3T1 template material. x T y P z P in the name z The name components are unique - that is, each P z The name component specifies a unique coating body type, regardless of the S used to prepare the coating body. x T y What is the template type?

[0242] An exemplary type of the wrapping framework (i.e., the porous wrapping product generated through content extraction) is in format P z Naming, where P z The name of the component is not based on S x T y Begins with the template type. Used to name the frame type. z Name components and the S from which the frame type is obtained x T y P z PC material type P z The names and components match.

[0243] Exemplary types of template precursor materials, template materials, coating composites, and coating materials in this disclosure are enumerated in Table 1. Table 1 is arranged to illustrate the progression of synthesized materials starting from the template precursor material. While not every exemplary material is tracked in all four stages, it should be understood that any exemplary material may be tracked if desired. Table 1 also follows the material naming system described above.

[0244] IV. Precursor Stage - Examples

[0245] This section details the small-scale production of exemplary template precursor materials using exemplary procedures. Therefore, these procedures include partial implementations of the general method. It should be understood that these procedures must be combined with other procedures in a full implementation of the general method. Furthermore, it should be understood that these procedures only demonstrate similar, larger-scale procedures that will be used for industrial-scale manufacturing.

[0246] Various techniques can be used to precipitate precursor materials. For example, the stock solution can be heated to evaporate the process liquid, thereby 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 precursor particles in the precipitation template. For example, the stock solution can be spray-dried to produce discrete or hollow spheres. Other techniques that will be apparent to those skilled in the art can be utilized.

[0247] Example N1: In the exemplary precursor stage procedure, slender trihydrate magnesite (MgCO3·3H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0248] 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 during the separation phase of a full implementation of a general method. For this example, water, CO2 gas, and MgO can be used to generate a representative aqueous Mg(HCO3)2 stock solution.

[0249] First, 0.24 mol kg of Akrochem Elastomag 170 containing deionized water and commercial magnesium oxide (MgO) can be prepared. -1 A Mg mixture. This mixture can be carbonated in a circulating tank using a jet nozzle that bubbles CO2 to produce carbonic acid. The CO2 bubbling can be interrupted after the MgO has completely dissolved to form a stock solution. The stock solution can be at approximately 14.5°C.

[0250] Next, it can be injected through the nozzle at approximately 12 scfm. 空气 The flow rate initiates air bubbling within the reserve solution in the circulation tank. This bubbling leads to the precipitation of magnesite particles and associated emissions of CO2 process gases. Bubbling and circulation can continue until the conductivity of the solution stabilizes. At this point, the aqueous mixture of magnesite particles can be filtered, thus separating the particles from the aqueous Mg(HCO3)2 filtrate. This filtrate contains the mother liquor and essentially all of the process water. In a full implementation of the general method, the separated process water can be preserved for reuse, such as... Figure 12 As shown. Additionally, in the full implementation of general methods, conventional techniques can be used to preserve emitted CO2 process gases for reuse.

[0251] The trihydrate magnesite template precursor particles generated by this procedure can be identified as N1 in this paper, and can be... Figure 14 The SEM micrographs show that the elongated morphology and 70.4% TGA mass loss (which is very consistent with the expected 70.9% mass loss of trihydrate magnesite as shown in Table 2) confirm that the template precursor is trihydrate magnesite.

[0252] Aside from the presence of some small debris, the crystals have smooth, thin surfaces. The elongated shape of these crystals can be valuable. In applications requiring interlocking particles (such as filter membranes), elongated shapes can be useful. In applications requiring the assembly of percolation networks (such as for electron transport), elongated particles can achieve percolation using fewer particles compared to equiaxed particle shapes. In applications requiring mechanical reinforcement, elongated particles can provide excellent tensile properties.

[0253] Example H1: In another exemplary precursor stage procedure, graded isometric magnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0254] 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 phase of a fully implemented general method. For this example, a stock solution with an approximate weight molality of 0.14 mol / kg can be prepared first. -1 An aqueous Mg(HCO3)2 stock solution of Mg(aq) was used as a representative stock solution.

[0255] Next, the stock solution can be placed in a 1L Buchi rotary evaporator container and then rotated in a 100°C water bath at 280 RPM. Crystallization can be allowed to continue until most of the Mg ions have precipitated as hydromagnesite precursor particles. Accompanying this precipitation, CO2 process gas can be released. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation.

[0256] The resulting hydrated magnesite mixture can then be filtered to separate the solids from the aqueous Mg(HCO3)2 filtrate. This filtrate contains the mother liquor and essentially all the process water. In a full implementation of the general method, the separated mother liquor can be preserved for reuse.

[0257] The type of magnesite template precursor particles generated by this procedure are identified as H1 in this paper and can be... Figure 15 The particles were observed in representative SEM micrographs. The TGA mass loss of these particles was 56.6%, which is highly consistent with the expected mass loss of 56.9% for hydromagnesite (Table 2). Thin (thickness <100 nm) hydromagnesite plates were arranged in a hierarchical equiaxed superstructure. This template precursor morphology is of interest due to the combination of thin and equiaxed morphological features. In applications requiring high surface area, the hierarchical equiaxed morphology prevents the surface of thin crystals from being obscured, whereas simple planar particles tend to stack on top of each other and obscure each other's surfaces.

[0258] Example H2: In another exemplary precursor stage procedure, elongated, graded hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0259] To demonstrate this acquisition on a small scale, trihydrate magnesite 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 phase of a full-scale implementation of a general method. For this embodiment, the representative stock solution and an aqueous mixture of precipitated trihydrate magnesite can be obtained using the procedure described in Example N1. Accompanying this trihydrate magnesite precipitation, CO2 process gas can be released. In a full-scale implementation of a general method, conventional techniques can be used to preserve the released CO2 process gas.

[0260] Next, the trihydrate magnesite 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 be completely evaporated, thereby separating it from the solid residue of elongated hydromagnesite particles. In a full implementation of a general method, conventional techniques can be used to preserve the released process water.

[0261] The type of magnesite template precursor particles generated by this procedure are identified as H2 in this paper and can be... Figure 16 This can be seen in representative SEM micrographs. This template precursor material combines the advantages of the aforementioned elongated and thin morphologies.

[0262] Example H3: In another exemplary precursor stage procedure, a plate-like hydromagnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0263] To demonstrate this acquisition on a small scale, fractionated 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 phase of a full-scale implementation of a general method. For this embodiment, 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 released. In a full-scale implementation of a general method, conventional techniques can be used to preserve the released CO2 process gas. Additionally, in a full-scale implementation of a general method, the separated process water can be preserved.

[0264] Next, the graded magnesite particles can be mechanically broken up. This can be achieved in various ways using known milling techniques. For demonstration purposes, the particles can be slurried in process water. The mixture can then be agitated using high-shear techniques to break down the finely graded magnesite particles into their constituent individualized plates. The plate-like magnesite particles can then be filtered out of the process water. In a full implementation of the general method, the separated process water can be preserved for reuse.

[0265] The hydromagnesite template precursor particles generated by this procedure are identified as H3 in this paper, and can be... Figure 17 The TGA mass loss of these particles is 56.6%, which is very consistent with the expected mass loss of 56.9% for hydromagnesite as seen in Table 2.

[0266] Example L1: In another exemplary precursor stage procedure, equiaxed hydrous magnesite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0267] 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 during the separation phase of a fully implemented general method. For this example, a concentration of approximately 0.25 mol / kg can be prepared. -1 A representative aqueous Mg(HCO3)2 stock solution of Mg(aq) was prepared and cooled to 2°C.

[0268] The cooled reserve solution can then be cooled at 4 scfh. 空气 The flow rate is subjected to N2 bubbling. The resulting precipitation can cause CO2 process gas to be released. In a typical implementation, conventional techniques can be used to retain the CO2 process gas released during precipitation.

[0269] After 67 minutes, the N2 bubbling can be interrupted. Following the interruption of N2 bubbling, the formed crystals can be stirred for another 50 minutes, after which the mixture can be filtered to separate the solids from the mother liquor. The solids can be washed with deionized water at 5°C. In a full implementation of the general method, the separated mother liquor can be preserved for reuse.

[0270] The hydrous magnesite template precursor particles generated by this procedure are designated L1 in this paper, and can be used to... Figure 18The template precursor particles exhibit a characteristic prismatic isometric morphology typical of hydrated magnesite, as seen in representative SEM micrographs. These particles show a TGA mass loss of 76.4%, which is highly consistent with the expected 76.9% mass loss of hydrated magnesite as seen in Table 2. This prismatic isometric morphology is likely desirable for applications where the coated product must be liquid-bound and viscosity effects must be minimized. Furthermore, due to the relatively high hydration state of hydrated magnesite, the generated template precursor volume is greater for a given mass of Mg than that achievable using MgCO3·xH2O with lower hydration, and more template pore volume is obtained upon precursor material decomposition. This can be used to generate a coated framework with more extracellular space.

[0271] Raman spectroscopy can be used to characterize the chemical composition of template precursor materials. This Raman spectroscopy method was applied to produce spectra at 1083 cm⁻¹, as shown in Table 2. -1 Matching of peak positions consistent with the hydrous magnesite.

[0272] Example L2: In another exemplary precursor stage procedure, equiaxed hydrous magnesite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0273] 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 during the separation phase of a fully implemented general method. For this example, the representative stock solution can be obtained as follows: First, an aqueous mixture of precipitated hydrated magnesite 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. The mixture can then be added to a high-pressure baffle reactor equipped with a self-priming stirrer. The system can be stirred at 700 RPM and cooled to 5°C while CO2 process gas is injected into the top space of the reactor until a pressure of 850 psi is reached, or until all solids have dissolved, thus producing a representative pressurized stock solution.

[0274] 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 flows through the top space. The resulting precipitation of hydrated magnesite particles can lead to the release of CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation.

[0275] After 228 minutes, the mixture of hydrous magnesite particles can be discharged from the reactor and then filtered to separate the hydrous magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse. For analytical purposes, the hydrous magnesite solids can be washed with deionized water, resuspended in ethanol, filtered again, and dried in a vacuum oven at room temperature up to 29 inHg.

[0276] The hydrous magnesite template precursor particles generated by this procedure are designated L2 in this paper. Raman spectroscopy analysis confirmed that the products of this reaction matched those of hydrous magnesite (as shown in Table 2).

[0277] Compared to other equiaxed MgCO3·xH2O type precursors (e.g., magnesite), hydrous magnesite offers significantly greater industrial scalability and lower cost. For applications where the coated product must be bound to a liquid and viscosity effects must be minimized, the prismatic equiaxed morphology may be desirable. Furthermore, due to the relatively high hydration state of hydrous magnesite, for a given mass of Mg, the generated template precursor volume is greater than that achievable using MgCO3·xH2O with lower hydration, and more template pore volume is obtained upon precursor material decomposition. This can be used to generate a coating framework with more extracellular space.

[0278] Example L3: In another exemplary precursor stage procedure, equiaxed partially dehydrated template hydrated magnesite (MgCO3·5H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0279] To demonstrate this acquisition on a small scale, an aqueous hydrated magnesite 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 phase of a full-scale implementation of a general method. For this embodiment, the representative stock solution and the aqueous hydrated magnesite mixture can be obtained using the procedure described in Example L2. As described in Example L2, precipitation of the hydrated magnesite particles can result in the release of CO2 process gas. In a full-scale implementation of a general method, conventional techniques can be used to retain the CO2 process gas released during precipitation.

[0280] The concentration of the hydrous magnesite mixture can be adjusted to a solids concentration of 7% by weight. The mixture can then be spray-dried, resulting in partial dehydration of the hydrous magnesite material. To demonstrate this on a small scale, a Sinoped LPG-5 spray dryer can be used. The hydrous magnesite particles in the 7% by weight mixture can be kept in continuous suspension by stirring in the container. The mixture can be pumped from this container into the BETE XAER250 air atomizing nozzle of the spray dryer at a rate ranging from 116 mL / min to 162 mL / min. A flow rate of 1.2 scfm at 20 psig is also possible. 空气 3.6 scfm at 59 psig 空气 The flow rate between these points delivers compressed air into the nozzles. The inlet temperature of the spray dryer can be set to 300°C, resulting in an outlet temperature ranging from 111°C to 123°C.

[0281] The dried, partially dehydrated, hydrated magnesite particles can be collected using a cyclone separator. In a full implementation of the general method, conventional techniques can be used to preserve the process water vapor generated by spray drying.

[0282] The partially dehydrated, hydrous magnesite template precursor particles generated by this procedure are designated L3 in this paper. The process liquids and gases can be recovered using typical industrial methods for reuse in the separation stage.

[0283] The 67.1% TGA mass loss of the L3 template precursor material generated according to the above procedure confirms partial dehydration (the theoretical mass loss for hydrous magnesite is 76.9%, as shown in Table 2). This partial dehydration is due to the increased temperature experienced during the spray drying process.

[0284] Example M1: In another exemplary precursor stage procedure, equiaxed magnesite (MgCO3) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0285] 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 during the separation phase of a fully implemented general method. For this example, a concentration of 0.25 mol / kg can be prepared. -1A representative aqueous Mg(HCO3)2 stock solution is used. This stock solution can then be slurried with additional MgO to provide more Mg ions. In a full implementation of the general method, additional Mg ions can be provided using MgCO3·xH2O precipitated from the stock solution. However, for the purposes of this demonstration, the additional MgO may include a commercially available 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.

[0286] 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 air from 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 heated stirring plate. Under magnetic stirring and heating, the vessel reaches 193.7 °C and 975 psi after 291 minutes. Inside the vessel, magnesite precipitates during this heat treatment, and the CO2 process gas can be vented into the top space of the vessel. The vessel can then be depressurized and cooled over a 30-minute process, continuously releasing vapors and CO2. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation and subsequent depressurization.

[0287] The mixture of magnesite particles can then be discharged from the reactor and filtered to separate the magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. Magnesite can be dried at 100°C.

[0288] The magnesite template precursor particles generated by this procedure are designated M1 in this paper. The particles exhibit an isometric rhombohedral morphology and... Figure 19 The results are shown in the SEM micrographs. Thermogravimetric analysis of the samples reveals the magnesite composition due to the absence of any thermal decomposition 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 Table 2. Raman spectroscopy analysis also confirms that the particles are magnesite, as seen in Table 2. This experiment demonstrates the use of additional Mg enrichment through MgO and CO2 gases, respectively. 2+ and HCO3 - A Mg(HCO3)2 stock solution of ions is used to generate equiaxed magnesite template precursor particles.

[0289] Example M2: In another exemplary precursor stage procedure, equiaxed magnesite (MgCO3) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0290] To demonstrate this acquisition on a small scale, trihydrate magnesite can be generated from an aqueous Mg(HCO3)2 stock solution using the procedure described in Example N1. This precipitation results in the release of CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation. Similarly, in a full implementation of the general method, the separated mother liquor can be preserved.

[0291] In this exemplary procedure, hydrous magnesite can then be combined with water to prepare a solution with a concentration of 1.5 mol / kg. -1 A mixture of Mg. The mixture can be placed in a pressure vessel equipped with a magnetic stirrer, a high-pressure gas inlet, and a purge needle valve. The top space of the pressure vessel can contain ambient pressure air, with no additional gas input. The pressure vessel can then be sealed.

[0292] The mixture can be magnetically stirred in the container for 10 minutes. The container can then 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 the magnesite during the reaction can become supercritical. The pressure vessel can then be cooled for 199 minutes.

[0293] The resulting mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. Magnesite can be dried at 100°C.

[0294] The magnesite template precursor particles generated by this procedure are designated M2 in this paper. The particles exhibit an isometric rhombohedral morphology and... Figure 20 The SEM micrographs show this. Raman spectroscopy analysis confirmed that the products of this reaction matched those of magnesite, as shown in Table 2.

[0295] Example A1: In another exemplary precursor stage procedure, a hollow, non-crystalline MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0296] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the one that can be generated during the separation phase of a fully implemented general method. For this example, a concentration of 0.43 mol / kg can be prepared. -1 A representative aqueous Mg(HCO3)2 stock solution of Mg(aq). This can be prepared by adding a commercially available MgCO3·xH2O product (“light magnesium carbonate” supplied by Akrochem Corporation) at a concentration equivalent to 0.43 mol kg.-1 The solid concentration of Mg is determined by mixing it 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 solids dissolve. At this point, the vessel can be depressurized and stored at atmospheric pressure at 4°C.

[0297] 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 the Sinoped LPG-5 spray dryer. This can be achieved at 2.8 scfm at 45 psig. 空气 The flow rate delivers compressed air into the nozzle. The inlet temperature of the spray dryer can be set to 165°C, resulting in an outlet temperature of 110°C.

[0298] Particles generated by spray drying of a stock solution can be collected using a cyclone particle separator. In a full implementation of the general method, conventional techniques can be used to preserve both process water vapor and CO2 process gases discharged through spray drying.

[0299] The MgCO3·xH2O template precursor material produced through this process is designated as A1 in this paper. Figure 21 SEM image analysis of the A1 particles shown in the SEM micrographs indicates that the amorphous MgCO3·xH2O particles produced by spray drying consist of largely hollow, multi-level isometric particles with smooth outer surfaces. Shell fragments are also present, indicating large pores within the shell.

[0300] Raman spectroscopy analysis showed that the products of this reaction do indeed have a region located at 1106 cm⁻¹. -1 The Raman peak at the location could be associated with crystalline carbonates. However, it did not match any typical MgCO3·xH2O peaks (Table 2). Furthermore, TGA analysis of the template precursor failed to match the common crystalline form of MgCO3·xH2O with a mass loss of 66.3%, as seen in Table 2. Therefore, it is considered amorphous.

[0301] Example A2: In another exemplary precursor stage procedure, hollow hierarchical equiaxed amorphous MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0302] 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 during the separation phase of a fully implemented general method. For this example, a concentration of 1.39 mol kg can be prepared. -1A representative aqueous Mg(HCO3)2 stock solution of Mg(aq). This can be prepared by adding a commercial Mg(OH)2 product (“Versamag” supplied by Akrochem Corporation) at an amount equivalent to 1.49 mol kg. -1 The solid concentration of Mg is determined by mixing it 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%) solids dissolve. At this point, the contents can be depressurized and stored at atmospheric pressure at 4-10°C.

[0303] 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 dual-fluid air atomizing nozzle in the Buchi B-191 spray drying system. This can be achieved at 0.6 scfm at 88 psig. 空气 The flow rate delivers compressed air into the nozzle. The inlet temperature of the spray dryer can be set to 130°C, resulting in an outlet temperature between 85-89°C. The intake can be set to 18 scfm. 空气 .

[0304] Particles generated by spray drying of a stock solution can be collected using a cyclone particle separator. In a full implementation of the general method, conventional techniques can be used to preserve both process water vapor and CO2 process gases discharged through spray drying.

[0305] The MgCO3·xH2O template precursor material produced through this process is designated as A2 in this paper. Figure 22 A to Figure 22 SEM image analysis of the A2 particles shown in SEM micrographs in Figure B indicates that the amorphous MgCO3·xH2O particles produced by spray drying consist of largely hollow, multi-level isometric particles with smooth outer surfaces. Shell fragments are also present. The shell fragments indicate that, in addition to the central cavity, the shell also possesses a closed-pore macroporous structure. Compared to the shells of A1 particles, the shells of A2 particles are thicker due to their increased shell porosity. The spheres are also smaller, with 95% or more of the population having a diameter of less than 10 μm.

[0306] Raman spectroscopy analysis showed that the MgCO3·xH2O spheres did not exhibit distinct Raman peaks associated with crystalline carbonates. Furthermore, TGA analysis of the template precursor failed to match the common crystalline form of MgCO3·xH2O with a mass loss of 68.4%, as seen in Table 2. Therefore, it is considered amorphous.

[0307] Example A3: In another exemplary precursor stage procedure, hollow hierarchical equiaxed amorphous MgCO3·xH2O template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0308] 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 during the separation phase of a fully implemented general method. For this example, a concentration of 1.08 mol / kg can be prepared. -1 A representative aqueous Mg(HCO3)2 stock solution of Mg(aq). This can be prepared by adding a commercial Mg(OH)2 product (“Versamag” supplied by Akrochem Corporation) at a concentration equivalent to 1.12 mol kg. -1 The solid concentration of Mg is achieved by mixing it 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 substantially all (i.e., >90%) of the solids dissolve. At this point, the contents can be depressurized and stored at atmospheric pressure at 4-10°C.

[0309] 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 dual-fluid air atomizing nozzle in the Buchi B-191 spray drying system. This can be achieved at 0.6 scfm at 88 psig. 空气 The flow rate delivers compressed air into the nozzle. The inlet temperature of the spray dryer can be set to 90°C, resulting in an outlet temperature between 56-58°C. The intake can be set to 18 scfm. 空 gas.

[0310] Particles generated by spray drying of a stock solution can be collected using a cyclone particle separator. In a full implementation of the general method, conventional techniques can be used to preserve both process water vapor and CO2 process gases discharged through spray drying.

[0311] The MgCO3·xH2O template precursor material produced through this process is designated as A3 in this paper. Figure 22 C to Figure 22SEM image analysis of the A3 particles shown in SEM micrograph D indicates that the amorphous MgCO3·xH2O particles produced by spray drying consist of largely hollow, multi-level isometric particles with smooth outer surfaces. Shell fragments are also present. The shell fragments indicate that, in addition to the central cavity, the shell also has a closed-pore macroporous structure. Compared to the shells of A1 and A2 particles, the shells of A3 are thicker due to their increased shell porosity. This indicates a lower average aspect ratio of particle radius to shell thickness. The particles circled in solid yellow have an aspect ratio of approximately 5:1, while those circled in dashed yellow have an aspect ratio of approximately 2:1.

[0312] Macropores are present throughout the shell, which can be seen in the carbon-encapsulated framework that grows on it. Figure 22 E is a TEM image of a carbon-coated framework grown on a template derived from A3 particles. The shell's mottled appearance, corresponding to its porosity, extends throughout the entire shell. Macropores in the shell are sandwiched between two surface layers—an outer surface layer and an inner surface layer (representing the inner and outer surfaces of the shell, respectively). These surface layers appear darker in the TEM image. The macroporous shell is part of a coated superstructure; the cellular substructure is more refined, such as... Figure 22 The illustration for E (i.e., a TEM micrograph showing the substructure of the mesoporous unit cell) is shown.

[0313] Raman spectroscopy analysis showed that the MgCO3·xH2O spheres did not exhibit distinct Raman peaks associated with crystalline carbonates. Furthermore, TGA analysis of the template precursor failed to match the common crystalline form of MgCO3·xH2O with a mass loss of 72.9%, as seen in Table 2. Therefore, it is considered amorphous.

[0314] Example C1: In another exemplary precursor stage procedure, hollow graded equiaxed magnesium citrate template precursor material can be obtained from an aqueous magnesium citrate stock solution.

[0315] 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 during the separation phase of a fully implemented general method. For this example, it can be prepared by mixing citric acid (supplied by Sigma Aldrich) with 0.52 mol kg... -1 A 0.52 mol kg concentration was prepared by reacting an aqueous mixture of Mg(OH)₂ (Versamag, supplied by Akrochem). -1 A representative aqueous magnesium citrate stock solution of Mg(aq).

[0316] 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 dual-fluid nozzle of the Buchi B-191 spray dryer. The getter airflow is set to 18 scfm. 空气 In this case, it can be administered at 0.6 scfm at 88 psig. 空气 The flow rate delivers compressed air into the nozzle. The inlet temperature can be set to 220°C, resulting in an outlet temperature of 110°C.

[0317] Particles generated by spray drying of a stock solution can be collected using a cyclone particle separator. In a full implementation of the general method, conventional techniques can be used to preserve the process water vapor discharged during spray drying.

[0318] The magnesium citrate template precursor material produced by this process is designated as C1 in this paper. Figure 23 SEM micrographs of the C1 particles, as shown in the images, indicate that the magnesium citrate particles produced by spray drying consist of largely hollow, multi-level isometric particles. Most comprise a solid shell and a hollow interior, exhibiting a wrinkled, spherical superstructure, as seen in... Figure 23 As observed, some particles include smooth, unwrinkled spherical superstructures; these particles can have a thicker and more rigid shell compared to wrinkled particles. Spray-dried magnesium citrate precursor particles rarely fragment or break, although pinholes can be observed, such as... Figure 23 As indicated in the document.

[0319] Raman spectroscopy analysis confirmed that the product of this reaction matched the product of magnesium citrate, as shown in Table 2.

[0320] Example E1: In another exemplary precursor stage procedure, an elongated template precursor material of esperidone salt (magnesium sulfate heptahydrate MgSO4·7H2O) can be obtained from an aqueous magnesium sulfate stock solution.

[0321] To demonstrate this acquisition on a small scale, a representative stock solution can first be prepared. This stock solution represents the one that can be generated during the separation phase of a fully implemented general method. For this example, a concentration of 4.06 mol / kg can be prepared by dissolving esperidone in water at room temperature. -1 A representative aqueous magnesium sulfate stock solution of Mg(aq). This can be prepared in a glass beaker with magnetic stirring at 700 RPM.

[0322] Once dissolved, 410.86 g of acetone can be added dropwise through a separatory funnel, which results in the immediate formation of crystals in the solution. While this represents an antisolvent precipitation that is generally undesirable, solvent-free precipitation of esperidone can be easily achieved by cooling or spray drying the stock solution. The procedure in Example E1 is primarily intended for precipitating esperidone, rather than demonstrating the precursor morphology of an engineered design or showcasing a scalable procedure, so that template and coating materials obtained from the esperidone precursor compound can be demonstrated and analyzed in later sections of this disclosure. In a full implementation of the general method, the mother liquor separated after solvent-free precipitation can be preserved for reuse in the separation stage.

[0323] After 22 minutes, the precipitation of espresso salts is complete. The resulting mixture can be collected and filtered. The particles can be dried.

[0324] The esperidone salt template precursor material produced through this process is designated E1 in this paper. Under an optical microscope, the particles can be observed as slender rods with a hexagonal cross-section, such as... Figure 24 As shown.

[0325] Raman spectroscopy analysis confirmed that the products of this reaction matched those of esperidone (as shown in Table 2).

[0326] Example H4: In another exemplary precursor stage procedure, a Li-doped hydrated magnesite (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.

[0327] 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 during the separation phase of a fully implemented 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. First, MgO powder (Akrochem Elastomag 170 calcined at 1050°C for 1 hour) can be added at 0.23 mol kg... -1 The solid concentration of Mg is slurried and added to water. This can be done in a glass beaker with magnetic stirring. (2.71·10) -3 mol kg -1 Li₂CO₃ (Sigma Aldrich) is added to this mixture to achieve a solid concentration of Li. The mixture can be carbonized using a jet nozzle that bubbles CO₂ gas to produce aqueous H₂CO₃. The CO₂ flow can be interrupted after MgO and Li₂CO₃ have completely dissolved. The Mg(HCO₃)₂ stock solution can then be filtered to remove any remaining undissolved impurities.

[0328] Next, the stock solution can be heated to 100°C in an open glass beaker with magnetic stirring. This condition can be maintained for 2 hours, during which time hydrated magnesite particles will precipitate. After 2 hours, the resulting mixture can be filtered, and the solid hydrated magnesite can be dried at 100°C in a forced air circulation system.

[0329] The Li-doped hydrated magnesite template precursor material produced through this process is designated H4 in this paper. Figure 25 As shown in the SEM micrographs, their plates are thin (<100 nm along their short axis) and flat with smooth surfaces.

[0330] Example H5: In the exemplary precursor stage procedure, Li-doped hydrated magnesite (Mg5(CO3)4(OH)2·4H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution that also contains a medium concentration of Li2CO3.

[0331] 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 during the separation phase of a fully implemented 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.

[0332] First, MgO powder (Akrochem Elastomag 170 calcined at 1050℃ for 1 hour) can be added at a rate of 0.23 mol / kg. -1 The solid concentration of Mg is slurried and added to water. This can be done in a glass beaker with magnetic stirring. (2.74·10) -2 mol kg -1 Li₂CO₃ (Sigma Aldrich) is added to this mixture to achieve a solid concentration of Li. The mixture can be carbonized using a jet nozzle that bubbles CO₂ gas to produce aqueous H₂CO₃. The CO₂ flow can be interrupted after MgO and Li₂CO₃ have completely dissolved. The Mg(HCO₃)₂ stock solution can then be filtered to remove any remaining undissolved impurities.

[0333] Next, the stock solution can be heated to 100°C in an open glass beaker with magnetic stirring. This condition can be maintained for 1 hour, during which time hydrated magnesite particles will precipitate. After 1 hour, the resulting mixture can be filtered, and the solid hydrated magnesite can be dried at 100°C in a forced air circulation system.

[0334] The Li-doped hydrated magnesite template precursor material produced through this process is designated H5 in this paper. Figure 26 The SEM micrographs show that their plates are thin (<120 nm along their short axis) and have a surface area greater than that of the plates shown. Figure 25 The surface of the plate shown is rough. This roughness indicates the increased Li doping due to the higher concentration of Li₂CO₃ in the aqueous stock solution.

[0335] 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.

[0336] 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 during the separation phase of a fully implemented general method. For this example, the stock solution can be generated in a high-pressure reactor. First, commercially available magnesite product (Akrochem light magnesium carbonate) can be used at 0.74 mol kg... -1 The solid concentration of Mg is slurried in water. This mixture can be placed in a circulating pressure vessel. The sealed vessel can then be heated to 145°C, at which point ~800 psi of gaseous CO2 can be introduced into the system. This reaction can be continued at 145°C for a duration of 139 minutes, thus reaching a maximum pressure of 900 psi. During this heat treatment, hydromagnesite dissolves to form aqueous Mg(HCO3)2, and magnesite precipitates from Mg(HCO3)2. At this point, the vessel can be depressurized, thereby releasing the CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation and subsequent depressurization.

[0337] The resulting mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. Magnesite can be dried at 100°C.

[0338] The magnesite template precursor material produced through this process is designated M3 in this paper. Equiaxed magnesite particles can be... Figure 27 The structure is observed in the SEM micrograph of A. Based on a TGA mass loss of 51.7% (which closely matches the theoretical expectation of 52.2% in Table 2), the structure indicates magnesite.

[0339] 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.

[0340] 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 during the separation phase of a fully implemented general method. For this example, the stock solution can be generated in a high-pressure reactor. First, commercially available magnesite product (Akrochem light magnesium carbonate) can be used at 0.74 mol kg... -1 The solid concentration of Mg is slurry-like in water. It can be 2.17·10. -3 mol kg -1 The concentration of Na is increased by adding a commercial NaHCO3 product (Arm & Hammer) to this mixture. This mixture can then be placed in a circulating pressure vessel. The sealed vessel can then be heated to 145°C, at which point ~800 psi of gaseous CO2 can be introduced into the system. This reaction can be continued at 145°C for a duration of 135 minutes, achieving a maximum pressure of 840 psi. During this heat treatment, hydrated magnesite dissolves to form aqueous Mg(HCO3)2, and magnesite precipitates from the aqueous Mg(HCO3)2. At this point, the vessel can be depressurized, releasing the CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation and subsequent depressurization.

[0341] The resulting mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. Magnesite can be dried at 100°C.

[0342] The magnesite template precursor material produced through this process is designated M4 in this paper. Equiaxed magnesite particles can be... Figure 27 The structure of B is seen in the SEM micrograph. Based on a TGA mass loss of 51.6% (which closely matches the theoretical expectation of 52.2% in Table 2), the structure indicates magnesite.

[0343] 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.

[0344] 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 during the separation phase of a fully implemented general method. For this example, the stock solution can be generated in a high-pressure reactor. First, commercially available magnesite product (Akrochem light magnesium carbonate) can be used at 0.74 mol kg... -1 The solid concentration of Mg can be slurried in water. It can reach 0.19 mol / kg. -1The concentration of Na is increased by adding a commercial NaHCO3 product (Arm & Hammer) to this mixture. This mixture can then be placed in a circulating pressure vessel. The sealed vessel can then be heated to 145°C, at which point ~800 psi of gaseous CO2 can be introduced into the system. This reaction can be continued at 145°C for a duration of 137 minutes, achieving a maximum pressure of 850 psi. During this heat treatment, hydrated magnesite dissolves to form aqueous Mg(HCO3)2, and magnesite precipitates from the aqueous Mg(HCO3)2. At this point, the vessel can be depressurized, releasing the CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation and subsequent depressurization.

[0345] The resulting mixture of magnesite particles can be discharged from the reactor and then filtered to separate the magnesite solids from the mother liquor. In a full implementation of the general method, the separated mother liquor can be preserved for reuse in the separation stage. Magnesite can be dried at 100°C.

[0346] The magnesite template precursor material produced through this process is designated M5 in this paper. Equiaxed magnesite particles can be... Figure 27 The SEM micrograph of C shows rhombohedral crystals of magnesite. Based on a TGA mass loss of 51.9% (which closely matches the theoretical expectation of 52.2% in Table 2), the structure indicates magnesite.

[0347] Comparing M3, M4, and M5, there are no obvious morphological differences that can be easily identified based on SEM analysis.

[0348] Example N2: In another exemplary precursor stage procedure, slender trihydrate magnesite (MgCO3·3H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0349] To demonstrate this acquisition on a small scale, the procedure described in Example L2 can be used to generate hydrous magnesite from a stock solution of aqueous Mg(HCO3)2. This precipitation results in the release of CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation. Similarly, in a full implementation of the general method, the separated mother liquor can be preserved.

[0350] Next, heat the water in a glass beaker to 35°C. Once the water reaches the desired temperature, add hydrated magnesite 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, hydrated magnesite dissolves and trihydrated magnesite precipitates. The mixture can then be filtered to separate the mother liquor from the hydrated magnesite. In a full implementation of the general method, the separated mother liquor can be preserved.

[0351] The type of magnesite template precursor material produced by this process is designated as N2 in this paper. Figure 28 The image shown is an optical micrograph. Most of the magnesite particles are individually distributed, thus forming a fine powder.

[0352] Example N3: In another exemplary precursor stage procedure, slender trihydrate magnesite (MgCO3·3H2O) template precursor material can be obtained from an aqueous Mg(HCO3)2 stock solution.

[0353] To demonstrate this acquisition on a small scale, the procedure described in Example L2 can be used to generate hydrous magnesite from a stock solution of aqueous Mg(HCO3)2. This precipitation results in the release of CO2 process gas. In a full implementation of the general method, conventional techniques can be used to preserve the CO2 process gas released during precipitation. Similarly, in a full implementation of the general method, the separated mother liquor can be preserved.

[0354] Next, the 10.84 mM SDS (TCI Chemical) aqueous solution can be heated to 35°C in a glass beaker. Once the water reaches the desired temperature, hydrated magnesite can be added to produce a solution 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, hydrated magnesite dissolves and trihydrated magnesite precipitates. The mixture can then be filtered to separate the mother liquor from the hydrated magnesite. In a full implementation of the general method, the separated mother liquor can be preserved.

[0355] The type of magnesite template precursor material produced by this process is designated as N3 in this paper. Figure 29 The image shown is an optical micrograph. (Comparison) Figure 30 N2 in A and Figure 30 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 surfactant during precipitation can be used to control the size of the template precursor particles.

[0356] Example Li1: In another exemplary precursor stage procedure, hollow graded equiaxed Li2CO3 template precursor material can be obtained from an aqueous Li2CO3 stock solution.

[0357] 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 during the separation phase of a fully implemented general method. For this example, a representative aqueous Li₂CO₃ stock solution can be prepared as follows: First, a commercially available Li₂CO₃ product (supplied by FMC) can be used at a concentration of 0.54 mol kg… -1 The concentration of Li is slurry-like in water. This mixture can be carbonated in a top-stirred reactor equipped with gas dispersion blades and an injector. CO2 gas can be injected at a rate of 9 sf / ch. 空气 The solution is added to the mixture at a rate of 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).

[0358] 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 dual-fluid nozzle of the Buchi B-191 spray dryer. The getter airflow is set to 18 scfm. 空气 In this case, it can be administered at 0.6 scfm at 88 psig. 空气 The flow rate delivers compressed air into the nozzle. The inlet temperature can be set to 170°C, resulting in an outlet temperature of 100°C.

[0359] Particles generated by spray drying of a stock solution can be collected using a cyclone separator. In a full implementation of the general method, conventional techniques can be used to preserve both the CO2 process gas and process water vapor emitted during spray drying.

[0360] The lithium carbonate template precursor material produced through this process is designated Li1 in this paper. The particles are hollow, hierarchical, equiaxed structures, as shown in... Figure 31 As seen in the SEM micrographs. The hollow structure can be identified at different survival stages. The shell exhibits pinholes between the Li2CO3 subunits, which is... Figure 31 A is indicated by a red arrow. In some shells, fragmentation and larger holes or cracks can be observed (this is in...). Figure 31 (Indicated by the blue arrow in section A). A wrinkled shell is present in the sample (this is in...). Figure 31 (Indicated by the yellow arrow in section A). Figure 31 In B, the substructure of loosely packed subunits of particles can be identified. Their sizes are primarily between 200 and 700 nm, and larger particles clearly include larger subunits. (1091 cm⁻¹) -1 195cm -1 and 158cm -1 The Raman peaks on the left and right confirm that the structure is Li2CO3.

[0361] V. Template Stage - Example

[0362] This section details the small-scale production of exemplary template materials using exemplary procedures. Therefore, these procedures include partial implementations of the general method. It should be understood that these procedures must be combined with other procedures in a full implementation of the general method. Furthermore, it should be understood that these procedures only demonstrate similar, larger-scale procedures that will be used for industrial-scale manufacturing.

[0363] This section describes several exemplary procedures for preparing template materials. In some exemplary procedures, the template precursor material may be processed in a separate and distinct template stage procedure to form the template material, and the resulting template material may then be used in a separate and distinct replication stage procedure. In other cases, both the template stage and replication stage procedures may be performed in the same reactor. Some of these exemplary template stage procedures use template precursor materials previously named and described in Part V. Additionally, new template precursor materials may be used.

[0364] Example N1T1: In the exemplary template stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0365] To demonstrate this, N1-type trihydrate magnesite particles can first be generated using the procedure described in Example N1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0366] Next, the template precursor material can be heat-treated. This can be performed in a TGA instrument under an inert Ar gas flow, as described in Scheme E in Part III. A sample of N1 type magnesite trihydrate 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 a 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. Upon reaching 1,000°C, the sample can be cooled back to room temperature.

[0367] The porous MgO template material produced through this process is designated N1T1 in this paper. The template particles retain the elongated superstructure of the precursor particles, such as... Figure 32 The SEM micrographs are shown. The particle lengths range from 20 μm to 100+ μm. Unbroken rods exhibit an average aspect ratio of approximately 15:1. Due to the porous substructure of the nanocrystalline MgO subunits, the ends of the particles have a brittle appearance.

[0368] Example H1T1: In another exemplary template stage procedure, the hydromagnesite template precursor material may be heat-treated to form a porous MgO template material.

[0369] To demonstrate this, H1-type hydromagnesite particles can first be generated using the procedure described in Example H1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0370] Next, the template precursor material can be heat-treated. This can be performed in a TGA instrument under an inert Ar gas flow, as described in Scheme E in Part III. A sample of H1-type magnesite 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 a 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. Upon reaching 1,000°C, the sample can be cooled back to room temperature.

[0371] The porous MgO template material produced through this process is designated H1T1 in this paper. The template particles retain the hierarchical equiaxed rose superstructure of the precursor particles, such as... Figure 33 The SEM micrographs are shown. The diameter of individual plates typically ranges from 1 μm to 3 μm, with an average size between these values. The diameter of particles typically 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 monolayer of laterally networked nanocrystalline subunits. The plates exhibit high thickness uniformity. The brittle appearance of the plate edges reflects the porous substructure of the nanocrystalline MgO subunits.

[0372] Example H2T1: In another exemplary template stage procedure, the hydromagnesite template precursor material may be heat-treated to form a porous MgO template material.

[0373] To demonstrate this, H2-type hydromagnesite particles can first be generated using the procedure described in Example H2. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0374] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme B, as detailed in Part III. A sample of H2-type magnesite 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 a 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.

[0375] The porous MgO template material produced through this process is designated H2T1 in this paper. The template particles retain the elongated rosette superstructure of the precursor particles, such as... Figure 34 The SEM micrographs are shown. The particle lengths range from 10 μm to 100 μm, with some particles having aspect ratios exceeding 5:1. The plate diameters range from 0.5 μm to 1.5 μm. Compared to the H1T1 plate, the H2T1 plate exhibits a coarser substructure, comprising more discrete subunits and larger pores between them. The subunits comprise cubic or polyhedral nanocrystals ranging in size from ~40 nm to ~100 nm, with an average size between these values. The coarsening of the substructure can be attributed to the more intense thermal treatment used to prepare the H2T1 template material.

[0376] exist Figure 34 Some of the subunits observed are laterally bonded to their nearest neighbors without any visible interstitial pores. These bonds can form grain boundaries. Other subunits are more discrete and, while still bonded to the overall network, are separated from their nearest neighbors by pores. Since the plate typically consists of only one subunit in thickness, the interstitial pores penetrate the thickness of the plate. These penetrating pores are an important and desirable structural feature in thin-templated structures because they generate more crosslinks within the encapsulated framework formed by the template.

[0377] During the heat treatment in Example H2T1, the porous MgO template material obtained through the decomposition of the template precursor can undergo grain growth and sintering due to atomic diffusion. The diffusion distance can be a function of temperature. Therefore, adjusting the temperature and duration of the template stage treatment can be useful for the fine engineering design of the template substructure (and correspondingly, the substructure of the encapsulated framework).

[0378] During roughening, the porous substructure of the template material can also be densified. This can affect the fractional composition of the positive and negative template spaces. In extreme cases, the densification of the porous substructure can continue until the negative space (i.e., the pore structure of the template) is eliminated. Higher-order porosity can be obtained through the pores between these previously discrete particles when the particles are sintered together. This technique has been used to produce template structures comprising macroscopic porous networks of sintered metal oxide particles. Such macroscopic monolithic template structures can be formed during the template stage and recycled using general methods.

[0379] Example H1T2: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form MgO template material.

[0380] To demonstrate this, H1-type hydromagnesite particles can first be generated using the procedure described in Example H1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0381] Next, the template precursor material can be heat-treated. This can be performed in the TGA according to Scheme E, as detailed in Part III. A sample of H1-type hydromagnesite particles can be heated from room temperature to a final temperature of 1200°C under Ar gas at a heating rate of 10°C / min, during which CO2 gas can be released. In a 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 allowed to cool.

[0382] The type of MgO template material produced by this process is designated H1T2 in this paper. The type of template particles produced by this procedure... Figure 35 As shown in the SEM micrographs, heat treatment not only transforms the subunits but also the template superstructure, which no longer appears hierarchical. Therefore, the gradual aggregation of nanoscale subunits and pores at the substructural level can ultimately lead to the superstructural transformation of the template, and individual particles can be sintered together to form larger (even macroscopic) template structures.

[0383] Example N1T2: In another exemplary template stage procedure, the magnesite template precursor material can be heat-treated to form MgO template material.

[0384] To demonstrate this, N1-type trihydrate magnesite particles can first be generated using the procedure described in Example N1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0385] Next, the template precursor material can be heat-treated. This can be done in a TGA according to scheme E, heating from room temperature to a final temperature of 1200°C under Ar gas at a heating rate of 10°C / min. During this heat treatment, CO2 gas can be released. In a 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 allowed to cool.

[0386] The MgO template material produced by this process is designated as N1T2 in this paper. Due to gradual sintering at high temperature, the template particles have lost the porous substructure that evolved during thermal decomposition.

[0387] Example N1T3: In another exemplary template stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0388] To demonstrate this, N1-type trihydrate magnesite particles can first be generated using the procedure described in Example N1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0389] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme 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 begin carbon deposition on the template surface. During this replication phase of the procedure, the template, which may not have completed its thermal decomposition, can continue to decompose at high temperatures, releasing CO2 gas. In a 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 stopped, and then the furnace can be cooled to room temperature under a continuous Ar flow.

[0390] The porous MgO template material produced by this process is designated as N1T3 in this paper.

[0391] Example M1T1: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0392] To demonstrate this, M1-type magnesite particles can first be generated using the procedure described in Example M1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0393] Next, the template precursor material can be heat-treated. This can be performed in the TGA according to Scheme 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 a 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 allowed to cool.

[0394] The porous MgO template material produced through this process is designated M1T1 in this paper. The template particles retain the equiaxed superstructure of the precursor particles, such as... Figure 36 The SEM micrographs are shown. The diameters of the template particles range from 5 μm to 20 μm. At lower magnifications, the surface appears largely 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 precise nanoscale substructures, but the regular, rugged appearance indicates the underlying MgO subunits.

[0395] Example M1T2: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0396] To demonstrate this, M1-type magnesite particles can first be generated using the procedure described in Example M1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0397] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme 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 a 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 allowed to cool.

[0398] The MgO template material produced through this process is designated M1T2 in this paper. The template particles retain the equiaxed superstructure of the precursor particles, such as... Figure 37 The SEM micrographs are shown. The diameters of the template particles range from 5 μm to 20 μm. At low magnification, the surface appears substantially smooth and continuous. At higher magnification, the surface appears rougher due to the porous substructure. Due to the ~5 nm iridium particles required for imaging the coated surface, it is difficult to clearly resolve the precise nanoscale substructures, but the regular, rugged appearance indicates the underlying MgO subunits.

[0399] Example M1T3: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0400] To demonstrate this, M1-type magnesite particles can first be generated using the procedure described in Example M1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0401] Next, the template precursor material can be heat-treated. This can be performed in the TGA according to Scheme E, as detailed in Part III. The sample can be heated from room temperature to a final temperature of 1200°C in flowing Ar at a rate of 50°C / min. During this heat treatment, CO2 gas can be released. In a 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 held at 1200°C for 1 minute and then allowed to cool.

[0402] The MgO template material produced through this process is designated M1T3 in this paper. The template particles retain the equiaxed superstructure of the precursor particles, such as... Figure 38 The SEM micrographs are shown. The diameters of the template particles in the template samples range from 5 μm to 20 μm. At low magnification, the surface appears 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 distinguish the precise nanoscale substructure, but its regular, rugged appearance indicates the underlying MgO subunits. Although the substructure cannot be easily compared with comparable samples treated at only 1050 °C (described in Example M1T1 and...), the surface appears smooth and continuous. Figure 37 (as shown in the image) can be distinguished, but the subunits appear to be able to begin coalescing through sintering.

[0403] Example M1T4: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0404] To demonstrate this, M1-type magnesite particles can first be generated using the procedure described in Example M1. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0405] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme 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 a 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 allowed to cool.

[0406] The MgO template material produced through this process is designated M1T4 in this paper. The template particles retain the equiaxed superstructure of the precursor particles, such as... Figure 39 The SEM micrographs are shown. The diameter of the template particles ranges from 5 μm to 20 μm. Comparable samples treated at 1050 °C (as described in Example M1T1 and...) are also shown. Figure 37 (as shown in) or a comparable sample treated at 1200°C for only 1 minute (as described in Example M1T2 and) Figure 38 Compared to (shown in the image), the particles in the sample appear to have a rougher surface at low magnification. At higher magnification, significant grain growth can be seen during the 1200°C isotherm. The porosity that evolved during thermal decomposition also appears to have been eliminated, similar to other exemplary template samples (e.g., H1T2 and N1T2) that have been treated at 1200°C for extended periods.

[0407] Example E1T1: In another exemplary template stage procedure, the esperidone salt template precursor material may be heat-treated to form a dehydrated alkaline MgSO4 template material.

[0408] To demonstrate this, esperidone salt particles can be generated first. The esperidone salt 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 of a full implementation of the general method.

[0409] Next, the template precursor material can be heat-treated. This can be performed in a forced-air circulating oven. The sample can be heated from room temperature to a final temperature of 215°C. During this heat treatment, the aqueous Epsom salt particles can be dehydrated. The sample can be held at 215°C for 2 hours and then allowed to cool.

[0410] The obtained porous dehydrated MgSO4 samples are shown in optical micrographs. Figure 40 As shown in A. In Figure 40 In A, it can be found in E1 crystal (see Figure 24 The smooth facets observed in the study have been replaced by rougher surfaces due to the evacuation of crystalline H2O.

[0411] If dehydrated MgSO4 material is used in the high-temperature replication stage of the procedure, 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. This procedure can be performed in a tube furnace according to scheme B, as detailed in Section III. This part of the heat treatment may involve 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 portion can decompose into MgO.

[0412] The MgSO4 template material produced by this process is designated E1T1 in this paper. Next, propylene (C3H6) gas is introduced into the furnace to initiate surface replication. The template and replication stages can overlap, as the MgSO4 template material is still roughening. At some point, the pyrolysis of the carbon-coated material on top of the E1T1 template material stabilizes the latter, preventing further roughening and indicating the true completion of the template stage. CVD can be performed for 2 hours, after which the furnace can be cooled under a continuous Ar flow.

[0413] After the furnace has cooled to room temperature, collect the PC material (E1T1P). 16 This PC material is in Figure 40 The image is shown in the SEM micrograph of B. From it we can see that the E1T1 type template particles retain the superstructure of the esperidone precursor particles, although cracks can be observed. Figure 40C and Figure 40 D is P formed on E1T1 type template particles. 16 SEM micrographs of a carbon-coated framework. Figure 40 In D, the cell substructure indicates the porous substructure of the template.

[0414] Example H4T1: In another exemplary template stage procedure, Li-doped hydrated magnesite precursor material may be heat-treated to form a porous MgO template material.

[0415] To demonstrate this, H4-type hydromagnesite particles can first be generated using the procedure described in Example H4. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0416] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace at an Ar flow of 2000 sccm, as detailed in Part III, according to Scheme B. The sample can be heated from room temperature to 1050°C at a heating rate of 20°C / min. During this heat treatment, CO2 gas can be released. In a 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.

[0417] The porous MgO template material produced through this process is designated H4T1 in this paper. The template particles retain the plate-like superstructure of the precursor particles, such as... Figure 41 The SEM micrograph of plate B is shown. The diameter of the individual plates ranges from approximately submicrometers to several micrometers, 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 monolayer of laterally networked subunits with an average diameter between 80 nm and 100 nm. The plates exhibit high thickness uniformity between particles. The subunits are discrete, with numerous pores separating the individual nanocrystals.

[0418] When the diameter is between 80 nm and 100 nm, the subunits of the template particles in H4T1 and Figure 41 The SEM micrographs of A show that the 50 nm to 60 nm subunits are considerably larger. These subunits were obtained from undoped hydromagnesite particles that underwent the same template stage procedure. As an approximation, the 90 nm subunit is 1.5 times larger in diameter and more than 3 times larger in volume than the 60 nm subunit.

[0419] Example H5T1: In another exemplary template stage procedure, the Li-doped hydrated magnesite precursor material may be heat-treated to form a porous MgO template material.

[0420] To demonstrate this, H5-type hydromagnesite particles can first be generated using the procedure described in Example H5. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0421] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace at an Ar flow of 2000 sccm, as detailed in Part III, according to Scheme B. The sample can be heated from room temperature to 1050°C at a heating rate of 20°C / min. During this heat treatment, CO2 gas can be released. In a 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.

[0422] The porous MgO template material produced through this process is designated H5T1 in this paper. The template particles retain the plate-like superstructure of the precursor particles, but have much larger interstitial gaps between the subunits, such as... Figure 41 The SEM micrographs of C are shown. The lateral dimensions of the plate particles range from 2 μm to 8 μm, and the thickness ranges from 100 nm to 300 nm. As with other Li-doped and pure water magnesite-derived MgO templates, the thickness of the plates is typically a single subunit.

[0423] Similar to H4T1 type template particles produced through the same heat treatment (see...) Figure 41 In contrast to B), the H5T1 type template particles exhibit much larger subunits, with lateral diameters ranging from 150 nm to 500 nm. The subunits are comparable in volume to the undoped pre-hydrated magnesite MgO template (see [link to template]). Figure 41 The subunits in A) are 1 to 200 MHz in size. Furthermore, unlike the undoped subunits, the subunits are not cubic and exhibit increased elongation along the plane of the plate. This suggests that increasing the dopant concentration enhances the roughening effect during heat treatment and also alters the geometry of the subunits. Given these results, doping with a variety of heteroatoms is expected to be useful for template engineering design.

[0424] Example H6T1: In another exemplary template stage procedure, the hydromagnesite template precursor material may be heat-treated to form a porous MgO template material.

[0425] To demonstrate this, a commercially available magnesite product consisting primarily of plate-like particles (“light magnesium carbonate” supplied by Akrochem Corporation) was used. This commercial product was chosen because it provides similar chemical and morphological properties to the magnesite template precursor; for this reason, the precursor material is described herein as H6. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0426] Next, the template precursor material can be heat-treated. This can be performed in a muffle furnace according to Scheme D, as detailed in Part III. The sample can be placed in a ceramic boat inside the muffle furnace. The sample can be heated from room temperature to 750°C at a heating rate of 5°C / min. During this heat treatment, CO2 gas can be released. In a 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 750°C for 1 hour and then allowed to cool to room temperature.

[0427] The porous MgO template material produced through this process is designated H6T1 in this paper. The template particles retain the plate-like superstructure of the precursor particles, such as... Figure 42 The SEM micrographs are shown. Individual plates range from approximately 0.5 μm to 2 μm along their principal and intermediate axes, with average diameters between these values. The average plate thickness is less than 100 nm and structurally corresponds to a monolayer of lateral networking subunits. The plates exhibit high thickness uniformity across particles.

[0428] Examples M3T1, M4T1, M5T1: In another set of exemplary template stage procedures, magnesite template precursor materials may be heat-treated to form porous MgO template materials.

[0429] To demonstrate this, M3-type magnesite particles can first be generated using the procedures described in Examples M3, M4, and M5. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0430] Next, the template precursor material can be heat-treated. This can be performed in a muffle furnace according to scheme D, as detailed in Part III. The sample (M3, M4, or M5) can be placed in a ceramic boat within the muffle furnace. The sample can be heated from room temperature to 580°C at a heating rate of 5°C / min. The sample can then be maintained at up to 580°C for 1 hour. During this heat treatment, CO2 gas can be released. In a 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. Next, the sample can be heated from 580°C to 1050°C at a heating rate of 5°C / min and maintained at this temperature for 3 hours. It can then be cooled to room temperature.

[0431] The porous MgO template materials produced through this process are designated in this paper as M3T1, M4T1, and M5T1 (corresponding to variants based on the M3, M4, and M5 template precursor materials). The M3T1, M4T1, and M5T1 template materials can be compared to demonstrate the use of dopants in enhancing the roughening effect during heat treatment. Observing the carbon-coated frameworks formed on these templates is enlightening, as the frameworks in their native morphology are replicas of the template surface (and negative replicas of the template body). Furthermore, the carbon frameworks are also partially electronically transparent, thus allowing visualization of the template's internal substructure.

[0432] PC materials made using M3T1, M4T1, and M5T1 template materials are designated as M3T1P2, M4T1P, and M5T1, respectively, in this paper. 19 and M5T1P 20 (These exemplary replication stage procedures are described in Part VI). The MgO content in these PC materials can then be extracted using an aqueous H₂CO₃ extractant solution, leaving carbon-coated products P₁ and P₂. 19 and P 20 These coating materials can be examined to determine the substructure of the template.

[0433] P1, P 19 and P 20 The coating materials are respectively in Figure 43 A, Figure 43 B and Figure 43 The carbon-coated framework (P) fabricated on the template material with the highest Na doping degree (M5T1) is shown in the SEM micrograph. 20 The unit cell subunits of the doped template material (M3T1) can be 1 to 200 nm larger in volume than the unit cell subunits of the framework (P1) fabricated on the undoped template material (M3T1). Therefore, the framework fabricated on the doped template material is significantly less compact than the framework fabricated on the undoped template material.

[0434] PC material made from M5T1 (M5T1P) 20 )exist Figure 44 As shown in the figure. These particles retain the isometric superstructure of the precursor particles, and the particle size is typically about 1 μm to 5 μm. The substructure of the particles is very coarse, including subunits ranging from 100 nm to 400 nm.

[0435] Table 3 summarizes the N2 gas adsorption analysis of template materials M3T1, M4T1, and M5T1. After heat treatment at 1050 °C, the BET surface area of ​​the Na-doped template materials decreased by 31% (M4T1) and 57% (M5T1) compared to the undoped template material (M3T1). Furthermore, after heat treatment at 1050 °C, the Na-doped samples exhibited porosity that was 13% (M4T1) and 30% (M5T1) lower than the undoped template material (M3T1). Roughening and densification increased with increasing dopant levels in the template materials.

[0436] Similar to observations of Li-doped magnesite template precursors, this suggests that Na doping can help roughen the template and reduce the compaction of the coated framework. Other dopants may have similar effects.

[0437] Examples M3T2, M4T2, M5T2: In another set of exemplary template stage procedures, magnesite template precursor materials may be heat-treated to form porous MgO template materials.

[0438] To demonstrate this, the procedures described in Examples M3, M4, and M5 can be used to generate M3, M4, and M5 type magnesite particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0439] Next, the template precursor material can be heat-treated. This can be performed in a muffle furnace according to scheme D, as detailed in Part III. The sample (M3, M4, or M5) can be placed in a ceramic boat inside the muffle furnace. The sample can be heated from room temperature to 580°C at a heating rate of 5°C / min. The sample can then be maintained at up to 580°C for 1 hour. During this heat treatment, CO2 gas can be released. In a 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. Next, the sample can be heated from 580°C to 900°C at a heating rate of 5°C / min and maintained at this temperature for 1 hour. It can then be cooled to room temperature.

[0440] The porous MgO template materials produced by this process are identified in this paper as M3T2, M4T2 and M5T2 (corresponding to variants based on M3, M4 and M5 template precursor materials).

[0441] Table 3 summarizes the N2 gas adsorption analysis of template materials M3T2, M4T2, and M5T2. After heat treatment at 900 °C, the surface area of ​​the Na-doped template materials decreased by 8% (M4T2) and 78% (M5T2) compared to the undoped materials (M3T1). Their reduced surface area is consistent with the relatively rougher substructure of the Na-doped template materials compared to the undoped template materials.

[0442] For this N2 gas adsorption method, BJH results are limited to pore size ranges of 1.70 nm and 300 nm. The porosity of the template particles can be determined using the calculated BJH cumulative pore volume. Porosity can be defined as the ratio of specific pore volume to specific template volume, and can be considered as the percentage of the total space occupied by pores relative to the entire particle. The BJH desorption cumulative pore volume (V...) PORE It can be used as a measure of the specific pore volume of template particles. Specific MgO volume (V MhO The specific volume (V) of the MgO component in the porous MgO template can be the reciprocal of the theoretical density of MgO. TRM The porosity can be the sum of the specific pore volume and the specific MgO volume. The following formula can be used to determine the porosity of the template particles:

[0443]

[0444] Template Space(%)=1-Porosity(%)

[0445] Following heat treatment at 900°C, the doped samples exhibited porosities that were 1.5% (M4T2) and 58% (M5T2) lower than those of the undoped template material (M3T2). As in the previously exemplary procedures, this demonstrates that the level of dopant in the template material can be used to influence both roughening and densification effects. Combined with the Li doping results already described, this showcases the ability to adjust the compaction of the coated framework, the size and morphology of its subunits, and the ratio of its intracellular to extracellular space.

[0446] Example M3T3: In another exemplary template stage procedure, the magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0447] To demonstrate this, M3-type magnesite particles can first be generated using the procedure described in Example M3. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0448] Next, the template precursor material can be heat-treated. This can be performed in a muffle furnace according to scheme D, as detailed in Part III. The template precursor sample can be placed in a ceramic boat within the muffle furnace. The sample can be heated from room temperature to 580°C at a heating rate of 5°C / min. The sample can then be maintained at up to 580°C for 13.5 hours. During this heat treatment, CO2 gas can be released. In a 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. Next, the sample can be heated from 580°C to 1050°C at a heating rate of 5°C / min and maintained at this temperature for 1 hour. It can then be cooled to room temperature.

[0449] The porous MgO template material produced by this process is designated as M3T3 in this paper.

[0450] Example N2T1: In another exemplary template stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0451] To demonstrate this, N2-type magnesite particles can first be generated using the procedure described in Example N2. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0452] Next, the template precursor material can be heat-treated using steam as a roughening aid. This can be performed in a rotary tube furnace according to scheme A, as detailed in Part III. The quartz tube can be rotated at 1 rpm. Under a dry Ar flow, the N2 sample can be heated in the furnace from room temperature to 450°C at a heating rate of 5°C / min. Once the furnace reaches 450°C, an Ar flow can be started through the bubbler at a flow rate of 2360 sccm. The bubbler chamber can be maintained at a slight positive pressure of 0.23 psig, and the external temperature can be maintained at 100°C to fill the top space of the bubbler with water vapor. The furnace can be maintained at 450°C for 1 hour, and then heated to 500°C at a heating rate of 5°C / min. After 1 hour at 500°C, the furnace can be heated to a final temperature of 1000°C at a heating rate of 5°C / min and maintained at 1000°C for 1 hour. CO2 gas can be released during this heat treatment. In a full implementation of the general approach, conventional techniques can be used to preserve the CO2 process gas released during the decomposition of the template precursor material. At this point, the dry Ar flow can be resumed, and the sample can be cooled to room temperature under the flowing dry Ar.

[0453] The porous MgO template material produced by this process is designated N2T1 herein. The template particles retain the elongated superstructure of the precursor particles. This can be demonstrated in the exemplary PC material (N2T1P) produced by surface replication on N2T1 template particles.21 Observed in SEM micrographs. N2T1P includes a thin, electron-transparent carbon-coated phase and an N2T1 internal phase. 21 PC material in Figure 45 As shown in the SEM micrographs. Imaging PC materials, where the carbon coating walls are sufficiently thin, is a good way to understand the template substructure and superstructure, since PC materials consist of content template particles coated with a conformal conductive layer.

[0454] exist Figure 45 In the middle, it is obvious that the N2T1 template material is better than the N1T1 template material (see Figure 32 Roughness. The size of the subunits ranges from 50 to 400 nm. This demonstrates the use of water vapor during the template stage to enhance roughening. Of particular note is the apparent significant reduction in template porosity and the distinct slit-like morphology of the pores between the subunits.

[0455] Example N2T2: In another exemplary template stage procedure, the magnesite template precursor material can be heat-treated to form a porous MgO template material.

[0456] To demonstrate this, N2-type magnesite particles can first be generated using the procedure described in Example N2. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0457] Next, the template precursor material can be heat-treated. This can be performed in a rotary tube furnace according to scheme A, as detailed in Part III. The quartz tube can be rotated at 1 rpm. Under a dry Ar flow, the N2 sample can be heated in the furnace from room temperature to 450°C at a heating rate of 5°C / min. Once the furnace reaches 450°C, a dry Ar flow can be started through the bubbler at a flow rate of 2360 sccm. The furnace can be maintained at 450°C for 1 hour, and then heated to 500°C at a heating rate of 5°C / min. After 1 hour at 500°C, the furnace can be heated to a final temperature of 1000°C at a heating rate of 5°C / min and maintained at 1000°C for 1 hour. During this heat treatment, CO2 gas can be released. In a 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. At this point, the dry Ar flow can be resumed, and the sample can be cooled to room temperature under flowing dry Ar.

[0458] The porous MgO template material produced by this process is designated as N2T2 in this paper. N2 gas adsorption can be performed on these templates using the previously described methods. As seen in Table 4, the N2T1 template material produced by steam-assisted treatment of the N2-type precursor material at 1000°C exhibits a 59% reduction in surface area compared to the N2T2 template material produced by drying the N2-type precursor material at 1000°C. This indicates that roughening can be enhanced by utilizing water vapor.

[0459] Examples N2T3, N2T4, N2T5 and N2T6: In another set of exemplary template stage procedures, the trihydrate magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0460] To demonstrate this, N2-type magnesite particles can first be generated using the procedure described in Example N2. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0461] Next, the template precursor material can be heat-treated in several ways outlined in Table 5. Each of these heat treatments can be performed in a tube furnace according to Scheme B, as detailed in Part III. In short, all procedures involve initiating a carrier gas flow at the desired rate and treating the template precursor sample under the desired thermal conditions. Each heat treatment may involve a single isothermal section or multiple isothermal sections. During this heat treatment, CO2 gas may be released. In a full implementation of the general method, conventional techniques can be used to retain the CO2 process gas released during the decomposition of the template precursor material. The template precursor material, carrier gas, furnace scheme, heating rate, temperature setting, and isothermal duration for each section are specified in Table 5. After all sections related to the heat treatment have passed, the furnace can be cooled to room temperature under a continuous carrier gas flow.

[0462] The porous MgO template materials produced by these processes are designated as N2T3, N2T4, N2T5, and N2T6 in this paper. These variants were performed to test how heat treatment parameters affect the resulting template morphology.

[0463] During the heat treatment of the hydrated MgCO3·xH2O template precursor material, H2O and CO2 are the two main gases released. The thermogravimetric mass loss linearity of the N2-type template precursor material in Ar is shown in... Figure 46 Figure A shows the derivatives (% / ℃) of mass loss of the N2 type template precursor material at heating rates of 5℃ / min and 20℃ / min. Dehydration is substantially completed at 300-350℃. Decarboxylation is substantially completed at 500-550℃, resulting in MgO. At the faster heating rate of 20℃ / min, the mass loss linearity shifts to higher temperatures. Figure 46B shows the thermogravimetric mass loss curve of the N2-type template precursor material in CO2. Compared with the mass loss in Ar, the mass loss in CO2 is delayed until higher temperatures and occurs more abruptly, as indicated by the height of the derivative curve.

[0464] N2T3 type template material in Figure 47 The SEM micrographs show that this template material, generated by heating from room temperature to 640°C at a heating rate of 5°C / min under Ar flow, retains the elongated superstructure of N2-type precursor particles. The porous substructure consists of uniform repeating subunits and lacks significant macropores.

[0465] N2T4 type template material in Figure 48 The SEM micrographs show that this template material, generated by heating from room temperature to 640°C at a heating rate of 20°C / min under Ar flow, retains the elongated superstructure of N2-type precursor particles. In addition to the mesopores between subunits, the porous substructure also includes macropores. These macropores are internal and visible as bulbous protrusions, except where the template particles break down to allow the interior to be seen. These protrusions create a wavy surface, as... Figure 48 The red arrows in the diagram indicate these cavities. These cavities are formed by the expansion of volatile CO2 gas produced during thermal decomposition. This gas acts as a blower, creating large pores and plastically deforming the surrounding phase of the amorphous MgCO3·xH2O.

[0466] N2T5 type template material in Figure 49 The SEM micrographs show that the template material produced by heating from room temperature to 350°C at a heating rate of 20°C / min under Ar flow, followed by heating from 350°C to 640°C at a heating rate of 5°C / min, does not form internal macropores and associated bulbous protrusions. Instead, the template particles retain the prismatic superstructure of the elongated magnesite precursor particles. The substructure includes regular repeating subunits and mesopores. The absence of macropores indicates that the increased heating rate during decarboxylation exacerbates the accumulation of CO2 trapped in the particle bulk.

[0467] The PC particles generated during the replication stage and the coating framework generated during the separation stage inherit the internal macropores of the template particles. These internal macropores are clearly observed in Cui's mesoporous graphene fibers. The elimination of these macropores in the template material results in the absence of macropores in the coating material, such as... Figure 69 A and Figure 69 The SEM micrograph of B is shown. The presence of these uncontrolled macropores may be undesirable in many applications; therefore, the N2T3 and N2T5 type template materials without these internal macropores represent preferred variants for obtaining porous MgO template materials from trihydrate magnesite.

[0468] PC material (N2T6P) made on N2T6 type template material 22 )exist Figure 50 The image is shown in the SEM micrograph. Imaging the PC material provides a good representation of the template morphology when the carbon coating wall is sufficiently thin, as the PC material comprises content template particles coated with a conformal conductive layer. Based on this, it can be concluded that the N2T6 type template particles generated by heating from room temperature to 640°C at a heating rate of 5°C / min under a CO2 flow undergo catastrophic fracture during the template stage. These fractures occur in… Figure 50 The red arrows indicate this. This embodiment highlights the role that heating rate and gas environment can play during the template stage process.

[0469] Example L2T1: In another exemplary template stage procedure, the hydrous magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0470] To demonstrate this, L2-type hydrous magnesite particles can first be generated using the procedure described in Example L2. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0471] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme B, as described in Part III. The L2 sample can be placed in the tube furnace. Under an Ar flow of 1220 sccm, the furnace can be heated from room temperature to 640°C at a heating rate of 20°C / min and maintained at 640°C for 2 hours. During this heat treatment, CO2 gas can be released. In a 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 furnace can then be cooled to room temperature under a continuous Ar flow.

[0472] The porous MgO template material produced through this process is designated L2T1 in this paper. The morphology of L2T1 template particles can be distinguished from the original morphology of the carbon-coated framework synthesized on them. This type of framework... Figure 51 The SEM micrographs show that the hydrated magnesite template precursor material undergoes recrystallization during the template stage procedure, forming both hydrated and trihydrated magnesite phases before the formation of the L2T1 template material. The recrystallization of the precursor during this period can be attributed to the release of a large amount of water in the early stages of heat treatment.

[0473] Example L3T1: In another exemplary template stage procedure, a partially dehydrated hydrous magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0474] To demonstrate this, the procedure described in Example L3 can be used first to generate L3-type partially dehydrated hydrous magnesite particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0475] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme B, as described in Part III. The L3 type template precursor material can be placed in a tube furnace. The furnace can be heated from room temperature to 640°C at a flow rate of 1220 sccm of Ar and maintained at 640°C for 2 hours. During this heat treatment, CO2 gas can be released. In a 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. After this heat treatment, the furnace can be cooled to room temperature under a continuous Ar flow.

[0476] The porous MgO template material produced through this process is designated L3T1 in this paper. The morphology of the L3T1 template particles can be distinguished from the original morphology of the carbon-coated framework synthesized on them. Figure 52 The image shows a SEM micrograph of a mixture of C@MgO PC particles and a carbon-coated framework made of L3T1 type template particles. These particles show no signs of recrystallization into hydromagnesite or trihydrate magnesite, suggesting that the L3 template precursor material did not undergo sufficiently extensive recrystallization during the aforementioned heat treatment. This indicates that, like the L3 template precursor material, their superstructures can be better preserved if rapid techniques such as flash drying or spray drying are used to partially or completely dehydrate hydromagnesite and other highly hydrated template precursor materials.

[0477] Example L3T2: In another exemplary template stage procedure, a partially dehydrated hydrous magnesite template precursor material may be heat-treated to form a porous MgO template material.

[0478] To demonstrate this, the procedure described in Example L3 can be used first to generate L3-type partially dehydrated hydrous magnesite particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0479] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme B, as described in Part III, with some modifications. The furnace can be heated to 540°C and maintained at that temperature under a CO2 flow of 815 sccm. Before heat treatment, the L3 sample can be temporarily stored inside the quartz tube, but outside the heating zone. The template precursor material can then be rapidly introduced into the preheating zone via a propulsion mechanism and maintained at 540°C for 30 minutes. During this heat treatment, CO2 gas can be released. In a 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. Finally, the treated template can be removed from the heating zone and allowed to cool to room temperature under a continuous CO2 flow.

[0480] The porous MgO template material produced by this process is designated L3T2 in this paper. C@MgO PC materials prepared by forming a thin carbon coating on the L3T2 template material... Figure 53 The image is shown in the SEM micrograph. Imaging the PC material provides a good representation of the template morphology when the carbon coating walls are sufficiently thin, because the PC material comprises content template particles coated with a conformal conductive layer. Based on this, it can be concluded that the L3T2 type template particles did not undergo sufficiently extensive recrystallization during heat treatment to degrade their superstructure.

[0481] Example A1T1: In another exemplary template stage procedure, a spray-dried MgCO3·xH2O template precursor material comprising hollow spherical particles may be heat-treated to form a porous MgO template material.

[0482] To demonstrate this, the procedure described in Example A1 can be used to generate A1-type spray-dried MgCO3·xH2O particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0483] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace at a tube speed of 1 RPM according to Scheme A, as detailed in Part III. The sample can be placed in the tube furnace. When under an Ar flow of 1271 sccm, the furnace can be heated from room temperature to 100°C at a heating rate of 20°C / min and maintained at 100°C for 1 hour. Then, the furnace can be heated to 500°C at a heating rate of 20°C / min and maintained at 500°C for 1 hour. Finally, the furnace can be heated to 640°C at a heating rate of 20°C / min and maintained at 640°C for 3 hours. During this heat treatment, CO2 gas can be released. In a 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 furnace can then be cooled to room temperature under a continuous Ar flow.

[0484] The porous MgO template material produced through this process is designated A1T1 in this paper. The template particles retain the hollow, hierarchical, equiaxed superstructure of the precursor particles; some particles include shell fragments, such as... Figure 54 The SEM micrographs are shown. At higher magnification, a porous MgO substructure including the joint subunits can be identified. This porous substructure... Figure 54 It is clearly visible in the enlarged illustration.

[0485] Example A3T1: In another exemplary template stage procedure, a spray-dried MgCO3·xH2O template precursor material comprising hollow spherical particles may be heat-treated to form a porous MgO template material.

[0486] To demonstrate this, the procedure described in Example A3 can be used first to generate A3-type spray-dried MgCO3·xH2O particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0487] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to Scheme A, as detailed in Part III. The sample can be placed in a ceramic boat in the tube furnace. The furnace can be heated from room temperature to 200°C at a heating rate of 20°C / min under a N2 flow of 2408 sccm, and maintained at 200°C for 1 minute. Then, the furnace can be heated to 500°C at a heating rate of 5°C / min and maintained at 500°C for 1 minute. Finally, the furnace can be heated to 900°C at a heating rate of 20°C / min and maintained at 900°C for 15 minutes. During this heat treatment, CO2 gas can be released. In a 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 furnace can then be cooled to room temperature under a continuous N2 flow.

[0488] The porous MgO template material produced through this process is designated A3T1 in this paper. The template particles retain the hollow hierarchical equiaxed superstructure of the precursor particles (e.g., Figure 55 As shown in A) and their macroporous shell structures (such as...) Figure 55 (As shown in B). At higher SEM magnification, porous MgO substructures including joint subunits can be identified.

[0489] Example C1T1: In another exemplary template stage procedure, a spray-dried template precursor material comprising hollow graded equiaxed particles may be heat-treated to form a porous MgO template material.

[0490] To demonstrate this, the procedure described in Example A1 can be used to generate C1 type spray-dried particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0491] Next, the template precursor material can be heat-treated. This can be performed in a muffle furnace according to scheme D, as detailed in Part III. The C1 type template precursor material can be placed in a ceramic boat within the muffle furnace. The sample can then be heated from room temperature to 650°C at a heating rate of 5°C / min. The sample can then be maintained at 650°C for 3 hours. During this heat treatment, CO2 gas can be released. In a 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 furnace can then be cooled to room temperature.

[0492] The porous MgO template material produced by this process is designated as C1T1 in this paper.

[0493] Example Ca1T1: In another exemplary template stage procedure, precipitated CaCO3 template precursor material (Albafil) (described herein as Ca1) may be heat-treated to form a porous MgO template material.

[0494] Precipitated Ca1-type particles represent template precursor materials that can be generated in the precursor stage of a general implementation of the method.

[0495] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to scheme C, as detailed in Part III. The Ca1-type sample can be placed in a ceramic boat within the tube furnace. The furnace can be heated to 1050°C under a flowing Ar at 1102 sccm. During this heat treatment, CO2 gas can be released. In a 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 the furnace reaches 1050°C, methane (CH4) gas can be introduced into the system to begin forming a carbon coating on the template surface. While this surface replication step can be considered part of the replication phase, the template material can simultaneously continue to be roughened until the carbon coating stabilizes it. The system can be maintained at 1050°C for 15 minutes under flowing CH4 and Ar, after which the CH4 flow can be interrupted and the furnace can be cooled to room temperature under a continuous Ar flow.

[0496] The type of calcium oxide (CaO) template material produced by this process is designated Ca1T1 herein, and the PC material made using the Ca1T1 template material is designated Ca1T1P herein. 17 Observe the P after extracting the Ca1T1 template material. 17The carbon-coated material is inspiring because the framework in its native form is a replica of the template surface (and a negative replica of the template body). Furthermore, the carbon framework is partially electronically transparent, allowing visualization of the template's internal substructure.

[0497] Figure 56 P is after extracting the content Ca1T1 template material. 17 SEM micrograph of the carbon-coated material. Thermal decomposition at 1050℃ causes individual CaCO3 or CaO particles to sinter together, resulting in the formation of a template with a cluster morphology. Except for some damage, P appears to be in its original morphology. 17 The carbon-encapsulated framework preserves this cluster-like geometry.

[0498] Example Li1T1: In another exemplary template stage procedure, a spray-dried lithium carbonate template precursor material comprising hollow hierarchical equiaxed particles may be heat-treated to form a porous Li2CO3 template material.

[0499] To demonstrate this, the procedure described in Example Li1 can be used to generate Li1-type spray-dried particles. This material represents a template precursor material that can be generated in the precursor stage of a full implementation of the general method.

[0500] Next, the template precursor material can be heat-treated. This can be performed in a tube furnace according to scheme C, as detailed in Part III. The Li1-type sample can be placed in a ceramic boat within the tube furnace. The furnace can be heated to 580°C under a flowing Ar at 1271 sccm. At this point, C3H6 gas can be introduced into the system to begin forming a carbon coating on the template surface. Although this surface replication step can be considered part of the replication phase, the template material can be further roughened simultaneously until the carbon coating stabilizes it. The system can be maintained at 580°C for 870 minutes under flowing C3H6 and Ar, after which the C3H6 flow can be interrupted and the furnace can be cooled to room temperature under a continuous Ar flow.

[0501] The type of Li2CO3 template material produced by this process is designated Li1T1 in this document, and the PC material made using the Li1T1 template material is designated Li1T1P in this document. 18 Observe the P after extracting the content Li1T1 template material. 18 The carbon-coated material is inspiring because the framework in its native form is a replica of the template surface (and a negative replica of the template body). Furthermore, the carbon framework is partially electronically transparent, allowing visualization of the template's internal substructure.

[0502] Figure 57 P generated on Li1T1 template particles 18SEM micrograph of the Li1T1 template framework. The porous carbon framework largely retains its original morphology. In addition to intact unit cell subunits, extracellular pores are also identifiable, indicating that the Li1T1 template particles (like...) Figure 31 The Li1 precursor particles shown comprise a porous shell. Typical liquid-phase precipitation of crystalline Li2CO3 produces non-porous, anhydrous crystals. However, the spray-drying process promotes the formation of porous template precursors, and the template can retain these pores.

[0503] VI. Replication Phase - Examples

[0504] To demonstrate the general applicability of the replication stage to a variety of template materials, several exemplary replication stage procedures are presented below. For illustrative purposes, each exemplary procedure includes CVD growth of a carbon coating on selected template particles. However, it should be noted that other procedures and alternative compositions of coatings will be apparent to those skilled in the art.

[0505] In some exemplary replication stage procedures, template material can be formed from template precursor material in separate and distinct template stages occurring in different reactors. In other cases, both the template stage procedure and the replication stage procedure can be performed in the same reactor.

[0506] Some of the exemplary replication stage procedures presented in this section use template materials that have been previously named and described. Additionally, some exemplary template stage procedures describe new template materials, and for this reason, we describe the synthesis of these new templates in this section. Table 6 is an overview of all template materials used in the following exemplary replication stage procedures. The table includes basic parameters for manufacturing the template materials, including the template precursor material, the furnace configuration for the template stage treatment, and the temperature, time, heating rate, carrier gas, and gas flow rate associated with the template stage treatment. Some treatments include multiple stages, as shown in Table 6. There are special cases where the heating rate is described as “Max” in Table 6, indicating that the furnace is not heating at a fixed rate but rather at the furnace's maximum power setting. Typically, the heating rate in such cases is around 40°C / min. There is another special case where the heating rate is described as “Flash” in Table 6, indicating that the template precursor material is introduced into the preheating furnace, causing it to be heated extremely rapidly.

[0507] Table 7 provides an overview of the CVD parameters used in exemplary replication stage procedures. Table 7 lists templates that can be used to demonstrate various replication stage procedures. Table 7 also lists furnace configurations that can be used for each replication stage procedure as previously described in Part III. Each replication stage procedure outlined in Table 7 may consist of one or more segments. Each segment has a target temperature associated with that segment. The target temperature is represented in Table 7 by T. n This indicates that n' represents the segment number. Each segment also has a target temperature T.n The target holding time is specified in Table 7. The holding time is determined by t. n This indicates that 'n' also represents the segment number. Each segment also has a range up to T. n The target heating time. The heating time is specified in Table 7 by R. n This indicates that 'n' also represents the segment number. There is a special case where R... n This is described as 'max' in Table 7. This indicates that the furnace is not heating at a fixed rate, but rather at a fixed maximum power setting. Typically, the heating rate in this case is around 40°C / min.

[0508] In some programs, the copy phase immediately follows the template phase. In this case, R... n It is described as 'Not Applicable' in Table 7. This indicates that the heating rate is not applicable because the replication phase initiates immediately after the template phase and continues from the same temperature used in the template phase procedure.

[0509] Table 7 lists the hydrocarbon gases (“HC type”) and flow rates (“HC flow”) used in the replication stage. Table 7 also lists the carrier gas types and flow rates used in the CVD replication stage, which are represented by “CR type” and “CR flow” for each segment.

[0510] VII. Separation Stage - Example

[0511] The separation stage includes content extraction and coating separation. In some variations, this can occur in an integrated one-pot process. In other variations, the separation stage can occur in two or more separate and distinct stages. For example, content extraction may involve mixing PC material in a stored process liquid and dissolving the content material within the coating material. The coating material can then be separated from the stock solution. The stock solution can then be precipitated at atmospheric pressure. The precipitate can then be slurried into process water at a higher solids concentration. By adjusting the temperature or pressure, the solids in this concentrated mixture can then be redissolved at a higher concentration to produce a concentrated stock solution usable in the precursor stage.

[0512] Example VIIa: In an exemplary content extraction procedure, MgO contents can be extracted from a carbon-coated body by dissolving MgO in an extractant solution containing aqueous H2CO3.

[0513] First, approximately 12.5 g of C@MgO PC powder (containing approximately 94.75% MgO content and 5.25% carbon coating (grown via CVD) by weight) can be slurried in a 3 L round-bottom flask into 2.5 L of deionized water. This water represents the preserved process water obtained from the precursor stage of a full implementation of the general method. A gas line containing 0.5 μm diffuser (to reduce CO2 bubble size and improve reaction efficiency) can be fed into the bottom of the flask, and the water can be stirred with a magnetic stir plate. (4 scfh) 空气 The flow rate continuously puffs CO2 gas into the tank over 141 minutes. This CO2 represents the preserved process gas obtained in the precursor or template stage during the full implementation of the general method. The dissolution of CO2 and its reaction with process water generate an aqueous H2CO3 extractant solution. The reaction of the aqueous H2CO3 extractant solution with the MgO content leads to content extraction and the generation of a new aqueous Mg(HCO3)2 reserve solution outside the carbon-coated framework.

[0514] Carbon-coated frameworks can be separated from aqueous Mg(HCO3)2 stock solutions by filtering the mixture. The carbon-coated frameworks can be rinsed and dried, and ash content testing can be performed. The carbon-coated frameworks may contain approximately 9.49% MgO, representing a 99.5% removal efficiency of the MgO template material. Any remaining unextracted MgO can be hermetically encapsulated within certain carbon frameworks. Higher extraction efficiencies can be achieved using higher-energy agitation techniques that promote the cracking of the hermetically encapsulated walls.

[0515] In the full implementation of the general method, the separated aqueous Mg(HCO3)2 stock solution can then be preserved for use in the precursor stage.

[0516] Example VIIb: In another exemplary content extraction procedure, MgO contents can be extracted from carbon-coated bodies using a shuttle technique.

[0517] First, stir 500 mL of water magnetically at 700 RPM in a 1 L glass beaker. This water represents the preservation process water obtained during the precursor stage of the general implementation of the method. Next, add 3-5 scfh. 空气 CO2 process gas is continuously bubbled through process water via a dropper to form an aqueous H2CO3 extractant solution. This CO2 represents the preserved process gas obtained in the precursor or template stage during the full implementation of the general method. Approximately 10 g of C@MgO PC material containing elongated particles (yield 3.5%) can be gradually introduced into the extractant solution. When the C@MgO PC material is fully integrated into the solution, the mixture may be black and have a pH of 9. The beaker can be covered to maintain a CO2-rich atmosphere.

[0518] After a 24-hour reaction, the conductivity of the mixture was measured at 19.7 mS / cm at 19.6 °C, the pH was 8, and the mixture was gray. This mixture contains the coated product and a fresh aqueous Mg(HCO3)2 stock solution, which can be used in the precursor stage of a general implementation of the method. The solids can then be separated from the stock solution using conventional techniques.

[0519] The solids from this mixture can be Figure 58 Optical micrographs of A and Figure 58 B and Figure 58 As seen in the SEM micrograph of C, two distinct phases exist in the sample. The first phase comprises precipitated magnesite particles, which... Figure 58 Phase A presents as transparent, elongated crystals. The second phase includes coated products comprising a carbon-coated framework, which... Figure 58 In A, the particles appear black. Some frames appear curved, indicating their flexibility during the extraction of rigid contents. The aqueous H₂CO₃ extractant solution reacts with the MgO contents to form solvated MgO. 2+ Ions and HCO3 3- Ions, which diffuse out of the carbon-coated body. During this diffusion, some of these ions precipitate as magnesite trihydrate. The dissolution and precipitation mechanisms occur simultaneously.

[0520] exist Figure 58 In diagram B, a carbon-coated framework is shown. The framework has been deformed into a non-native morphology, demonstrating both the extraction of its flexible and rigid MgO content. Content solids are clearly present, but they are not the original MgO content. Instead, they are MgCO3·xH2O content precipitated from the residual aqueous Mg(HCO3)2 reserve solution inside the framework, which was never rinsed during the drying process of the highly porosity-coated framework. In other words, the framework was essentially devoid of content solids prior to drying. The residual reserve solution can be replaced using a liquid-liquid separation technique, in this case, such a shuttle technique would result in the removal of 10 g of MgO from the framework using only 500 mL of water. This is approximately twice the maximum concentration of MgO soluble in an aqueous H2CO3 extractant solution at atmospheric pressure.

[0521] The mechanism likely involves the preferential adsorption and nucleation of CO2 nanobubbles within a hydrophobic carbon framework, thereby increasing the internal CO2 pressure and consequently the solubility of Mg(HCO3)2 within the framework. This generates a concentration gradient that drives solvated ions into the surrounding process water, where these ions precipitate due to the lower external CO2 pressure. Therefore, shuttle operation reduces the amount of process water required for content extraction, as well as the required container size.

[0522] Example VIIc: Extraction of contents from certain metal oxides or metal carbonates can be facilitated by supercritical CO2. In an exemplary procedure, 3.007 g of MgO (Elastomag 170 calcined at 1050 °C for 1 hour) was slurried with 100.00 g of DI water, resulting in a solution conductivity of 340 μS / cm at 12.4 °C. This translates to a mixture concentration of 30 g / L MgO. The mixture was poured into a 1 L pressure vessel equipped with a magnetic stirrer and a heating mantle. Approximately 600 g of dry ice (solid CO2) was added to the reactor, and the reactor was sealed. After heating for 101 minutes, the minimum conditions for supercritical CO2 were exceeded at 31.4 °C and 1,125 psi. After a total of 144 minutes, reactor conditions reached 36.2 °C and 1200 psi. The reactor was then actively cooled with cooling coils for 74 minutes, after which its conditions reached 18.3 °C and 675 psi. The pressure in the reactor can then be slowly released, and after 6 minutes, the reactor can be equilibrated to atmospheric pressure, with a temperature probe reading of -5.0°C. Approximately 23 minutes after pressure release, the sample can be removed from the solution, which has a conductivity of 30.2 mS / cm at 4.5°C. The solution is likely clear, without any signs of particles or precipitation. This higher concentration solution can then be used for crystallization of the template precursor material.

[0523] Example VIId: In another exemplary separation stage procedure, content extraction of water-soluble content template material can be obtained by simply dissolving it in water. This can be achieved by, for example, by dissolving the content template material in water. Figure 59 The SEM micrograph of A illustrates the C@MgSO4 PC material mixed in process water. In a full implementation of the general method, this process water may include preservative process water from the precursor stage. The MgSO4 content material mass dissolves in the process water at room temperature. Content extraction can be confirmed by SEM image analysis, such as... Figure 59 B to Figure 59 As shown in C. Then, the new solvated Mg can be used in the full implementation of the general method. 2+ and SO4 2- An aqueous stock solution of ions is used to crystallize an aqueous MgSO4 template precursor material. The resulting solution can be alkaline, indicating trace decomposition of MgSO4 to MgO during the template or replication stage. The alkaline stock solution can be neutralized with a small amount of sulfuric acid (H2SO4). The coated product can then be separated by filtration or some other separation technique. In a full implementation of the general method, the stock solution can be preserved for reuse in the precursor stage.

[0524] Packet separation

[0525] Several conventional techniques can be used to separate the coated products. In one technique, liquid-liquid separation can be utilized. This can be demonstrated by taking the mixture produced by the shuttle process described above and blending it with an immiscible solvent (such as hexane). The carbon-coated framework migrates into the solvent phase, while the trihydrate magnesite remains in the aqueous phase. This results in phase separation and two different slurries, such as... Figure 60 As shown, this image is a photograph taken after hexane was blended into the mixture produced by the shuttle process described above. The black mixture contains solvent and a carbon-coated framework. The mixture below contains water and magnesite trihydrate, and appears to consist primarily of white magnesite trihydrate particles (although some carbon particles are mixed in and adhere to the sides of the shimmering vial).

[0526] Separation of carbon-coated frameworks can also be achieved simply using flotation. In some carbon-coated frameworks, bubbles can be retained trapped in the extracellular pores during liquid-phase content extraction. This allows the frameworks to float or quasi-float during content extraction. Furthermore, subjecting the mixture of these bubble-injected frameworks to partial vacuum increases their buoyancy as the internal bubbles expand and expel water from the porous framework. Gradual flotation and separation of carbon-coated frameworks under partial vacuum... Figure 61 As shown in the figure. This partial vacuum flotation is achieved without using the solvents used in bubbling or typical foam flotation processes.

[0527] Various variations and improvements to these separation techniques can be readily envisioned. Flotation can be improved by using solvents, which are typical in conventional foam flotation processes. Frames made on template materials with greater particle porosity can retain more air and provide greater buoyancy. Hollow spheres, in particular, can contain more trapped air and provide even greater buoyancy.

[0528] Concentrated stock solution

[0529] In some cases, it may be desirable to produce a concentrated stock solution after separating the coated product. Mixtures of precipitated particles (such as magnesite trihydrate precipitated in the aforementioned shuttle process) can be redissolved under conditions allowing for higher solution concentrations. For example, an aqueous mixture of precipitated MgCO3·xH2O particles can be subjected to higher CO2 pressures to prepare a concentrated stock solution, such as… Figure 14 As shown. This concentrated stock solution can be used in the precursor stage.

[0530] Example VIIe: In an exemplary procedure, MgO can be dissolved at a higher concentration under pressure. To demonstrate this, 15 g of MgO (Elastomag 170) template can be slurried together with 750 g of deionized water, which may represent the preservation process water retained from the precursor stage. The water can be cooled to 5°C. The solids concentration of the mixture can be 20 g / L MgO, or approximately twice the maximum concentration of MgO that can be dissolved in an aqueous H2CO3 extractant solution at atmospheric pressure. The mixture can have a solution pH of approximately 10.5 and a resulting solution conductivity of 146 μS / cm. The mixture can be poured into a 1 L pressure vessel equipped with a magnetic stirrer, a high-pressure gas inlet, and a purge needle valve. The reactor can be sealed and purged by opening the high-pressure gas inlet via the purge needle valve, allowing pressurized CO2 gas (representing the preservation CO2 process gas recaptured in the precursor and template stages) to flow into the vessel for 2 minutes to remove any air. The purge valve can then be closed, and the reactor pressurized to 125 psi with CO2. After 65 minutes, the conductivity measured at 16.3 °C and pH 8.5 is approximately 15.6 mS / cm. This conductivity represents a Mg(HCO3)2 solution concentration equivalent to 10 g / L of dissolved MgO, which would likely require an order of magnitude longer reaction time at atmospheric pressure. After 290 minutes, the conductivity measured at 19.5 °C and pH 7.5 is approximately 27.8 mS / cm. The conductivity and pH measurements at 290 minutes represent a Mg(HCO3)2 solubility greater than the possible approximately 10 g / L MgO at atmospheric pressure.

[0531] Increased CO2 pressure can also be used to produce concentrated stock solutions from MgCO3·xH2O solutes (such as those produced via shuttle processes). These concentrated stock solutions can be produced through a multi-step separation stage process, in which the stock solution is used to precipitate solids that have been redissolved under conditions allowing for higher solubility. Alternatively, coating extraction using an aqueous H2CO3 extractant solution can be performed at increased CO2 pressure, allowing for higher concentrations to be obtained without precipitation and redissolution under increased CO2 pressure.

[0532] VIII. Envelope Frame Implementation

[0533] In the preferred method, carbon-coated frameworks are synthesized using MgO templates obtained from MgCO3·xH2O precursors. While roughening can reduce the fine structure of these MgO templates, typical MgO templates comprise a porous substructure of coupled nanocrystals. This produces labyrinthine frameworks with both intracellular and extracellular mazes. This labyrinthine structure is not specific to the carbon frameworks formed on these templates—that is, any framework will have the same native morphology. However, carbon frameworks with thin, conformal coating walls can be used to study these structures because they are capable of producing fine, electronically translucent replicas of the template.

[0534] As an example, Figure 62 Image A is a SEM micrograph taken at high magnification, showing a labyrinthine carbon framework that retains its native morphology. The nanocellular subunits are quasi-discrete but interconnected. Like the discrete MgO subunits on which they are synthesized, these cells are monodisperse, exhibiting a consistent equiaxed morphology and size throughout the superstructure. This consistency and their filling regularity are best observed at different magnifications. Figure 62 Including 25,000 times ( Figure 62 A) 100,000 times ( Figure 62 B) and 250,000 times ( Figure 62 C) SEM micrographs of the same carbon framework at magnification. Highly regular cell morphology and compaction can be observed throughout the framework. Figure 62 The labyrinthine framework was constructed on a pre-trihydrate magnesite MgO template.

[0535] Although the subunits are uniformly isometric, the superstructures of frameworks derived from porous MgO templates exhibit diverse geometries relative to the various precursors from which the MgO templates can be obtained. For example, frameworks generated on MgO templates made from magnesite template precursors possess elongated fibrous superstructures, such as... Figure 63 A to Figure 63 The labyrinthine framework in C is shown. The framework, formed on a template made from a magnesite or spheroidal magnesite template precursor, imparts a thin superstructure ( Figure 64 A to Figure 64 B, of which Figure 64 B indicates that... Figure 64 (Enlarged view of the area indicated by the yellow square in A) or hierarchical superstructure ( Figure 64 C). Figure 64 The labyrinthine framework shown in C was generated on a graded isometric magnesite template.

[0536] In addition to these diverse architectures, the fragmentation and deformation of the framework can originate from mechanical agitation, such as... Figure 65The diagram shows a multilayer stack of thin pseudomorphs. Unlike stacks of monolayer materials (e.g., graphene), these thin, mesoporous stacks should have high specific porosity, retain most of their surface area, and be relatively easy to exfoliate due to the limited contact area between their surfaces. Small subunit clusters can also be generated by agitation. Figure 66 The image is a SEM image showing a carbon framework that has been decomposed by agitation to form smaller polycellular clusters.

[0537] If the template precursor or some decomposition product of the template precursor becomes roughened during the template stage, the resulting coated framework becomes less compact. In one experiment, an MgO template was sintered at 1,000 °C for 2 hours prior to the replication stage. The resulting MgO template was quasi-polyhedral and typically had a diameter greater than 100 nm. Figure 67 These are SEM images of the less compact frameworks formed on these roughened templates. Roughening through particle sintering and coalescence degrades the inherited superstructure, resulting in particles with irregular geometries rather than those with regular pseudocrystalline geometries.

[0538] While these less compact, less regular frames are not as ordered as more compact frames with more regular geometries, they can still be combined to form polycell clusters with attractive functional properties, as described in U.S. Patent Application 62 / 448,129. One advantage of less compact frames with flexible coated walls is their increased pseudoelasticity—that is, the ability of natively rough collapsed frames, although compacted due to their collapse, to retain the ability to expand back to their native size without covalent failure.

[0539] elasticity in Figure 68 The optical image sequence is shown. In the first sequence (1-4), elongated carbon-coated frames are shown drying on a glass slide. These frames initially shrink and deform as the surface tension of the reduced residual water inside them deforms the flexible coating walls, then expand back to their original geometry as the deformed walls locally spring back to their original shape. This elastic response ultimately restores the original superstructure geometry. In the first sequence, two frames (labeled A and B) progress from their most contracted non-original state back to their original expanded state. The outline of frame A is drawn in image 1, and this outline is applied to images 2-4 for comparison. Ultimately, both frame A and frame B recover to their straight original superstructure. In the second sequence (I-IV), hollow spherical carbon-coated frames are shown drying on a glass slide. These frames progress from their most contracted non-original state back to their original expanded state. The outline of a representative frame is drawn in image I, and this outline is applied to images II-IV for comparison.

[0540] Figure 69Includes SEM micrographs of the carbon-coated framework grown on an elongated template (N2T4) as described in Part V. The framework is flexible. Figure 69 A), but it survives relatively well under high shear agitation. The surface of porous carbon particles appears uniform and blurred due to the fine collapsed cellular substructure. Figure 69 B).

[0541] Figure 70 Includes SEM micrographs of the carbon-coated framework grown on the elongated template (N2T8) as described in Part V. Templates N2T4 and N2T8 were generated from the same sample template precursor material (N2) through different treatments during the template stage. Figure 69 Compared to the framework shown, Figure 70 The carbon framework in the cells remains flexible, but after high-shear agitation, they exhibit damage and pitting.

[0542] Figure 71 Includes SEM micrographs of carbon-coated frameworks grown on elongated templates (N2T1) as described in Part V. These frameworks are represented by N2T1P 21 Content extraction and coating separation of PC materials generate coating products. The framework is both flexible and highly wrinkled, such as... Figure 71 As shown. They are related to... Figure 72 A more compact framework synthesized on N2T4 was compared. Figure 72 A shows a more compact framework synthesized on N2T4, while Figure 72 B shows the less compact cellular substructure of the framework synthesized on N2T4. Frameworks with different compaction degrees can be obtained from a common template precursor material by changing the processing procedure of the template stage.

[0543] Figure 73 A is a PC material (Ca1T1P) obtained from a calcium oxide (CaO) template material (Ca1T1). 17 Carbon-coated framework (P) 17 The images are SEM micrographs. The replication stage is discussed in Part 5. Although some fragmentation is observed, the frames largely retain their original morphology after content extraction and separation. Figure 73 B is a SEM image of the template precursor material (Ca1) used to prepare the CaT1 template material, namely the commercial product of precipitated calcium carbonate (CaCO3) (Albafil). The average size of the precursor particles is 0.7 micrometers. These precursor particles were heated to 1050°C, thereby decomposing them into CaO and sintering them into individual particles.

[0544] Raman spectroscopy is commonly used to characterize carbon and is a key means of characterizing the lattice structure of the exemplary carbon-coated materials in this disclosure. Details of the equipment and techniques used for Raman analysis are described in Part III.

[0545] Three main spectral features are usually associated with sp 2 Bonded carbon associated with: "G band" (typically at 1585 cm⁻¹) -1 (Location or left / right), "2D band" (usually between 2500 and 2800 cm) -1 (between) and "D-band" (usually between 1200 and 1400 cm) -1 (between). G-band and sp 2 Hybridized carbon is associated. The D band is associated with polycyclic sp... 2 Radial breathing mode phonons in hybrid carbon are associated and activated by defects. Therefore, the D-band is associated with disorder, and the peak intensity ratio of the D-band to the G-band provides a measure of disorder. Another feature associated with disorder is the interband region located between the D-band and the G-band. The presence of broad peaks within this interband region increases the height of the valley between the D-band and the G-band, and thus, this height can be used as a measure of disorder, with higher valleys associated with greater disorder. For this reason, this disclosure utilizes the height of this valley to characterize disorder. The valley height is defined herein as the local minimum intensity value occurring between the wavenumber associated with the D-peak and the wavenumber associated with the G-peak. The intensity value at this wavenumber is then compared with the G-peak intensity to characterize disorder.

[0546] To avoid relying on subjective line-fit judgments, this disclosure analyzes the unfitted Raman spectra of the carbon-coated materials presented herein. Therefore, all references to peak positions and intensities are related to the unfitted peak positions and are derived without line-fitting. Furthermore, all reported peak positions and intensities were measured at 532 nm excitation. The intensities of G, 2D, D, and valleys are denoted as I in this document. G I 2D I D and I Tr .

[0547] Table 8 summarizes the Raman spectra of the carbon frameworks generated in this disclosure. Table 8 details the sample names of the template precursor, template, and PC material from which the frameworks were generated. The CVD growth temperature, hydrocarbons used, and program time during the replication stage are also detailed in Table 8. The yields obtained from TGA analysis of PC are also detailed in Table 8. The Raman laser power used for the spectroscopic measurements is also listed in Table 8. The Raman spectra presented in Table 8 include I... D / I G and I Tr / I GPeak ratios, as well as the G peak position, D peak position, and the span between the G and D peak positions. These Raman indices, when combined, convey information about the degree of order and disorder in the sample.

[0548] I of carbon coating in PC material D / I G The peak intensity ratios ranged from 0.78 to 1.27, indicating that these samples contained disordered carbon. This disorder is caused by the typically high Ig Tr / I G Peak intensity ratios confirm that the range of peak intensity ratios is between 0.17 and 0.64, as shown in Table 8. This is also evidenced by the presence of peak intensity ratios in high-resolution TEM micrographs (such as...). Figure 5 The non-planarity of the graphene lattice is confirmed in the enlarged illustration of B.

[0549] For crystals such as graphite sp 2 Hybridized carbon, with the G-band expected to be centered at ~1580 cm⁻¹ -1 It has also been shown that for carbon, the G-band can red-shift under compressive strain and blue-shift under tensile strain. For sp 2 The center of the carbon D band (if present) should be at approximately 1350 cm⁻¹. -1 Left and right (for a 532nm laser). As seen in some samples, the redshift of the D-band position indicates disordered sp. 2 sp in carbon 3 Defective state.

[0550] For the samples described in this paper, the G-band peak position ranges from 1581 to 1609 cm⁻¹. -1 The range is between 1324 and 1358 cm⁻¹. -1 The range between the peak positions in the G and D bands is shown in Table 8. The peak positions in the G and D bands can span from 239 to 279 cm⁻¹. -1 The wider the range, the greater the strain and the more disordered the sample. Some samples have already been annealed, and further annealing may be desired to reduce this disorder.

Claims

1. A method for generating a carbon-coated framework by: I. Obtain template precursor particles and aqueous mother liquor from a first aqueous reserve solution, the obtaining comprising solvent-free precipitation, wherein the first aqueous reserve solution and aqueous mother liquor each contain aqueous ionic substances, the aqueous ionic substances comprising oxygen-containing anions and metal cations; and II. Decompose the template precursor particles to evolve template particles, the template particles comprising at least one of metal carbonates and metal oxides; and III. On the template surface of each template particle, at a temperature between 350°C and 950°C: synthesize coated walls comprising at least one graphene carbon layer to form coated composite particles, wherein the coated walls are characterized by having a thickness of 1300 cm⁻¹. -1 and 1332cm -1 The 532-nm Raman spectrum of the unfitted D peak position between; and IV. Expose the coated composite particles to an aqueous extractant solution as follows: Extract template particles from the coated wall; and A second aqueous reserve solution is generated, the second aqueous reserve solution containing a portion of the aqueous mother liquor and containing aqueous ionic substances; and A carbon-coated framework is formed, each carbon-coated framework including a coating wall and an intracellular space.

2. A method for generating a carbon-coated framework, the method comprising: I. Obtaining template precursor particles and an aqueous distillate from a first aqueous stock solution, the obtaining comprising at least one of spray drying and spray pyrolysis, wherein the first aqueous stock solution comprises an aqueous ionic substance containing oxygen-containing anions and metal cations; and II. Decomposing template precursor particles to evolve template particles, the template particles comprising at least one of metal carbonates and metal oxides; and III. On the template surface of each template particle, at a temperature between 350°C and 950°C: synthesize coated walls comprising at least one graphene carbon layer to form coated composite particles, said coated walls being characterized by having a thickness of 1300 cm⁻¹. -1 and 1332cm -1 The 532-nm Raman spectrum of the unfitted D peak position between; and IV. Expose the coated composite particles to an aqueous extractant solution as follows: Extract template particles from the coated wall; and A second aqueous reserve solution is generated, the second aqueous reserve solution containing aqueous distillate and aqueous ionic substances; and A carbon-coated framework is formed, and each carbon-coated framework includes a coating wall and an intracellular space.

3. A method for generating a carbon-coated framework, the method comprising: I. Obtaining a portion of template precursor particles and process liquid from a first aqueous reserve solution containing process liquid, the obtaining comprising solvent-free precipitation, wherein the first aqueous reserve solution comprises an aqueous ionic substance comprising oxygen-containing anions and metal cations; and II. Decompose template precursor particles to evolve template particles and process gas, a portion of the process gas is preserved, and each template particle includes at least one of metal carbonate and metal oxide; and III. On the template surface of each template particle, at a temperature between 350°C and 950°C: synthesize coated walls containing at least one graphene carbon layer to form coated composite particles. and IV. Exposing the coated composite particles to an aqueous extractant solution formed from the preservation portion of the process liquid and process gas: Extract template particles from the coated wall; and A second aqueous stock solution is produced, the second aqueous stock solution containing aqueous ionic substances; and A carbon-coated framework is formed, and each carbon-coated framework includes a coating wall and an intracellular space.

4. A method for generating a carbon-coated framework, the method comprising: I. Obtaining a portion of template precursor particles and process liquid from a first aqueous reserve solution containing process liquid, the obtaining comprising solvent-free precipitation, wherein the first aqueous reserve solution comprises an aqueous ionic substance comprising oxygen-containing anions and metal cations; and II. Decomposing template precursor particles to evolve template particles, each template particle comprising at least one of a metal carbonate and a metal oxide; and III. On the template surface of each template particle, at a temperature between 350°C and 950°C: synthesize coated walls containing at least one graphene carbon layer to form coated composite particles. and IV. Expose the coated composite particles to an aqueous extractant solution formed from the preservation portion of the process liquid: Extract template particles from the coated wall; and A second aqueous reserve solution is generated, the second aqueous reserve solution containing aqueous ionic substances; and A carbon-coated framework is formed, and each carbon-coated framework includes a coating wall and an intracellular space; V. Removal of the carbon-coated framework from the second aqueous reserve solution by migrating them into an immiscible solvent.

5. The method of claim 4, wherein the coated wall is characterized by having a thickness of 1330 cm. -1 and 1332cm -1 The 532-nm Raman spectrum of the unfitted D peak position between.

6. The method of claim 1, wherein the solvent-free precipitation comprises process gases released during precipitation.

7. The method of claim 1, wherein the generation of the second aqueous reserve solution and the precipitation of the aqueous ionic substance occur simultaneously.

8. The method of claim 1, wherein the extractant solution comprises a weak acid.

9. The method of claim 1, wherein the extractant solution is formed by dissolving a stored process gas in an aqueous mother liquor.

10. The method of claim 1, wherein the first aqueous reserve solution and the second aqueous reserve solution comprise organic salts.

11. The method of claim 1, wherein the first aqueous reserve solution and the second aqueous reserve solution comprise surfactants.

12. The method of claim 1, wherein the first aqueous reserve solution and the second aqueous reserve solution comprise an aqueous solution of Mg(HCO3)2.

13. The method of claim 1, wherein the first aqueous stock solution comprises 0.62 mol / kg -1 and 1.39 mol kg -1 Water-based Mg 2+ concentration.

14. The method of claim 1, wherein obtaining the template precursor particles from the first aqueous reserve solution comprises: Precipitate is formed from the first aqueous stock solution by solvent-free precipitation; and Template precursor particles are formed from precipitates.

15. The method of claim 1, wherein the decomposition of the template precursor particles comprises at least one of decarboxylation and oxidation of the organic content in the template precursor particles.

16. The method of claim 1, wherein the synthesis of the carbonaceous coated wall comprises template-guided chemical vapor deposition.

17. The method of claim 1, wherein the synthesis of the coated wall occurs at a temperature between 350°C and 700°C.

18. The method of claim 1, further comprising: Anneal the coating wall, optionally before or after extracting the template particles.

19. The method of claim 1, further comprising: V. Removal of the carbon-coated framework from the second aqueous reserve solution by migrating them into an immiscible solvent.

20. The method of claim 1, wherein the solvent-free precipitation comprises depressurizing the first aqueous stock solution.

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