Porous carbon materials, methods of making same, and uses thereof

Abstract

Porous carbon materials, templated materials, and methods of making same. In various examples, a porous carbon material comprises a surface area of about 3500 m2 / g to about 4800 m2 / g and / or a plurality of micropores and a plurality of mesopores. In various examples, a templated material (e.g., silicon nanoparticles) comprises a carbonaceous material disposed on a templating substrate, where the carbonaceous material comprises rim-based pentagons and / or radical specie(s) and / or carbon cylinders. In various examples, a method of making a porous carbon material comprises contacting carbon precursor(s) (e.g., carbohydrate(s), which may be water soluble) and templating substrate(s) under hypergolic conditions, where a templated material is formed; removing the templating substrate(s); activating the resulting material; and carbonizing the activated material. In various examples, a porous carbon material or materials is / are used in a filtration, a catalytic, or a carbon capture and / or sequestration application or method.

Description

Attorney Docket No.: CRNL-l lO-B-WOPOROUS CARBON MATERIALS, METHODS OF MAKING SAME, AND USES THEREOFCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 557,451, filed February 23, 2024 and entitled “High Surface Area Porous Carbon, Methods of Making Same, and Uses Thereof.” The entire contents of the above-identified priority application are hereby fully incorporated herein by reference in their entirety.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under GM 151218 and GM 146107 awarded by the National Institutes of Health. The government has certain rights in the invention.BACKGROUND

[0003] Carbon-based materials from conventional activated carbons and carbon black to the more recently discovered carbon nanotubes and graphene constitute a class of materials that are important in a wide range of applications. Their versatility stems from a number of features including, for example, chemical inertness, low density, as well as mechanical and chemical robustness. Among them, high surface area porous carbons are of significant importance in several applications as sorbents to store, recover, purify and separate species in the gas or liquid phase but also as electrodes in various electrochemical energy devices. Given their broad applicability, there are many different approaches to synthesize porous carbons with high levels of precision control over pore structure and surface areas.

[0004] Porous carbons produced by activation dominate the field because of the ease of preparation and low cost. The use of activated carbons has increased worldwide as a result of their use in applications such as industrial wastewater and gas treatment and in materials recovery. The activated carbon consumption in 2022, was approximately 5.8 million metric tons worldwide and the annual growth rate of the market was projected as 6.3 % from 2019 to 2024. The market was estimated to grow from $6.79 billion in 2022 to $13.75 billion by 2030, at a compound annual growth rate (CAGR) of 9.2 % over the forecast period of 2023-2030. More recently researchers have been exploring high / ultra-high surface area nanoporous carbons, which may provide opportunities in emerging applications including adsorption media, nanoreactors and electrodes for supercapacitors and batteries.

[0005] Highly porous activated carbons, HP AC, possess ultra-high BET areas (ca. 3000 m2 / g) along with significant total pore volumes. The most common approach towards HP AC involves a combination of thermal and chemical treatment using various carbon precursors such as coal or biomass (e.g., coconut shells, coffee wastes and rice husks). As a result, HPAC contains large amounts of impurities that require extensive purification steps. In some cases, soft or hard templates are used to achieve better pore size control and tunable pore connectivity. While these strategies are ideal for the preparation of mesoporous carbons, they typically lack microporosity. The lack of microporosity necessitates further chemical or physical activation to introduce or increase the level of microporosity in the material. Hence, HPAC are usually synthesized by carbonizing appropriate precursors of natural or synthetic origin, followed by an activation process. The microporous nature of the majority of porous carbons is well-suited for many applications, including molecular sieving, adsorption, and catalytic reactions. Other potential applications include, for example, waste-water treatment, electrodes in fuel cells, and Ho storage.

[0006] A number of strategies already exist to synthesize porous carbons with ultra-high BET areas, including activation by potassium hydroxide KOH, direct carbonization of crosslinked polymers or metal-organic frameworks (MOFs). Especially KOH activation, offers higher levels of microporosity and more uniform pores, lower processing temperature, shorter treatment time, and higher yield.

[0007] Moreover, various solid sorbents have been examined for CO2 capture applications including nanoparticle hybrids, alkaline residues, zeolites, and porous activated carbons (PACs). Highly porous materials such as PACs offer certain advantages including high porosity, surface functionalities that lead to enhanced uptake, low energy penalty for regeneration, long-term stability, and cost effectiveness. Porous solids including porous organic frameworks (POFs) or activated carbon are ideal candidates for capturing CO2 via physical adsorption. The development of CO2 sorbents and technologies remains a high priority for practical CO2 capture and storage applications.

[0008] Supercapacitors, batteries and flywheels are potential candidates for various energystorage applications including electric vehicles, portable devices, and other energy storage systems. The main advantages of supercapacitors compared to other systems (e.g. batteries) include high specific power, long cycle life, and fast charge / discharge rates typically withinseconds. Among the different materials used for supercapacitor electrodes, activated porous carbons offer many advantages especially in applications limited by space. Activated carbons combine large BET areas, high electrical conductivity, chemical stability, low cost, and are easily synthesized from naturally occurring precursors. Their porous structure, including pore size and distribution, significantly affects their electrochemical performance. Furthermore, oxygen containing functional groups contribute to better electrochemical performance because of the resulting pseudocapacitance due to reversible redox reactions. However, activated carbons with high porosity typically lead to very low volumetric energy and power densities, especially compared to graphene based materials. The volumetric performance becomes even more important for applications, where space is limited such as mobile electronics, electric vehicles and other compact electronic devices.SUMMARY OF THE DISCLOSURE

[0009] The present disclosure provides, inter alia, porous carbon materials and templated materials, and methods of making porous carbon materials and templated materials. The present disclosure also provides uses of porous carbon materials and templated materials.

[0010] In various examples, the present disclosure provides porous carbon materials. In various examples, a porous carbon material comprises: (i) a surface area of about 3500 m2 / g to about 4800 m2 / g; or (ii) a plurality of micropores and a plurality of mesopores; or (iii) a plurality of micropores and a plurality of mesopores and a surface area of about 3500 m2 / g to about 4800 m2 / g. In various examples, the porous carbon material comprises carbon cylinders.

[0011] In various examples, the present disclosure provides templated materials. In various examples, a templated material comprises a carbonaceous material disposed on at least a portion or substantially all or all of a surface or surfaces of a templating substrate or templating substrates, where the carbonaceous material comprises one or more or all of the following: (i) about 3 to about 20 atomic percent (e.g., based on the total weight of the templated material) of rim-based pentagons; or (ii) comprises one or more radical specie(s) (e.g., carbon-centered radicals, oxygen-centered radicals, or any combination thereof; or (iii) carbon cylinders. In various examples, the carbonaceous material comprises one or more radical specie(s), wherein the amount of the radical specie(s) corresponds to or the number of the radical species corresponds to about 1 x 1013to 1 x 1017spins / gram of the templated material. In variousexamples, the carbonaceous material comprises a plurality of carbon structures and a majority of the carbon structures arc not hexagonal carbon structures.

[0012] In various examples, the present disclosure provides a method of making a templated material or materials and / or porous carbon material or materials. In various examples, a method of making a porous carbon material or materials and / or templated material or materials comprises contacting one or more carbon precursor(s) and one or more templating substrate(s) under hypergolic conditions, where a templated material is formed; removing substantially all or all of the templating substrate(s) from the templated material; activating the material resulting after the removing substantially all or all of the templating substrate(s) from the templated material; and carbonizing the activated material, where the porous carbon material is formed. In various examples, the one or more carbon precursor(s) and the one or more templating substrate(s) are present in a reaction mixture. In various examples, the method further comprises forming a reaction mixture comprises the one or more carbon precursor(s), the one or more templating substrate(s), and optionally, one or more solvent(s); and optionally, heat treating the mixture. In various examples, the carbon precursor(s) is / are independently chosen from carbohydrates, structural analogs thereof, and any combination thereof. In various examples, one or more or all of the carbon precursor(s) is / are a water-soluble carbon precursor or water-soluble carbon precursors. In various examples, the carbon precursors(s) is / are present at about 50 wt. % to about 70 wt.%. In various examples, the templating substrate(s) is / are chosen from silica nanoparticles and any combination thereof. In various examples, at least a portion of, substantially all, or all of the templating substrate(s) is / are porous silica nanoparticle(s). In various examples, the templating precursors(s) is / are present at about 30 wt.% to about 50 wt.%. In various examples, the carbon precursor(s) : templating precursors(s) mass ratio is about 1 : 1 to about 4 : 1. In various examples, the reaction mixture heating is carried out at about 90 °C to about 180 °C and / or for about 1 hour to about 20 hours. In various examples, the contacting the one or more carbon precursor(s) and the one or more templating substrate(s) under the hypergolic conditions comprises contacting the one or more carbon precursor(s) and the one or more templating substrate(s) with one or more first hypergolic reagent(s); and contacting the contacted one or more carbon precursor(s), the one or more templating substrate(s), and the one or more first hypergolic reagent(s) with one or more second hypergolic reagent(s). In various examples, the first hypergolic reagent(s) is / are chosen from aniline, furfuryl alcohol, structuralanalogs thereof, and any combination thereof. In various examples, the second hypergolic rcagcnt(s) is / arc chosen from fuming nitric acid, hydrogen peroxide, red fuming nitric acid, structural analogs thereof, and any combination thereof. In various examples, the volume ratio of first hypergolic reagent(s) : second hypergolic reagent(s) volume ratio is about 0.5 : 1 to about 1 : 5. In various examples, the activating comprises contacting, one or more time(s) the material after the removal of substantially all or all of the templating substrate(s) with one or more base(s); and optionally, heating the base-treated templated product.

[0013] In various examples, the present disclosure provides uses of porous carbon materials of the present disclosure. In various examples, a filtration method comprises use of one or more porous carbon material(s) of the present disclosure. In various examples, a catalytic method comprising use of one or more porous carbon materials(s) of the present disclosure. In various examples, a carbon capture and / or carbon sequestration method comprising use of one or more porous carbon material(s) of the present disclosure. In various examples, a device comprising one or more porous carbon material(s) of the present disclosure. In various examples, the device is a filtration device. In various examples, the filtration device is configured for normal flow, dead-end flow, tangential flow, or any combination thereof. In various examples, the filtration device is configured for gravity filtration, centrifugation, gas-pressurization filtration, or any combination thereof. In various examples, the device is a carbon capture device. In various examples, a device comprises one or more electrode(s), where the electrode(s) independently comprise one or more porous carbon material(s) of the present disclosure. In various examples, the device is an energy-generating device, or an energy storage device. In various examples, the device is an electrochemical device. In various examples, the device is a fuel cell, a battery, a water-electrolysis device, or an electrodialysis device.

[0014] In various examples, this disclosure provides a new approach to design and synthesis of porous carbon materials. Hypergolically synthesized carbon materials were shown to be at least twice as efficient as sorbents for CO2 capture compared to other activated carbons. Additionally, these carbon materials show desirable CO2 adsorption kinetics, achieving 99% filling capacity within 2 min as well as desirable cycling performance. Porous materials of the instant disclosure show the highest to date volumetric energy density when tested as supercapacitor electrodes for energy storage.BRIEF DESCRIPTION OF THE FIGURES

[0015] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0016] FIG. 1 shows (a) XRD of HCs (for comparison SBA-15 has been also included), (b) TEM and (c) Representative SEM image of HCs showing a tubular morphology. The scale bar in the SEM image is 200 nm.

[0017] FIG. 2 shows N2 porosimetry measurements for all carbon samples: (a) non-activated, HC, and (b) HP AC.

[0018] FIG. 3 shows HRTEM (a, b) images of HPACs. The inset in (a) presents a representative TEM image of the graphitic nanoplatelet of HPACs revealing its multi-layered texture near the edges. Deconvoluted high-resolution Cis spectra of HPACs (c) HPACM (d) and HPACL(e).

[0019] FIG. 4 shows Raman spectra of all samples: (a) before activation and (b) after activation; (c) comparison of Raman intensity (ID / IG) for the activated and non-activated samples; (d) final surface area correlated to the difference in ID / IG ratios before and after activation. Right to left HCs, HCL, HCM, HCSSOO, HC sucrose-

[0020] FIG. 5 shows (a) Deconvoluted high-resolution Cis spectra of HCs along with the proposed mechanistic pathway of the highly reactive pentagonal rings towards the creation of porosity, (b) Continuous wave ESR spectra at 77 K and (c) spin density as a function of surface area for the non-activated samples.

[0021] FIG. 6 shows (a) CO2 uptake and release of HPACs measured using a thermogravimetric analyser over 10 adsorption-desorption cycles, (b) CO2 uptake of HPACs (red line) and a conventionally KOH activated carbon (black line). The inset represents the early stages of the CO2 uptake.

[0022] FIG. 7 shows electrochemical testing of a symmetric supercapacitor cell with HPACs electrodes. (a,b) CV curves in EMIM-BF4 electrolyte at (a) different voltage windows and (b) different scan rates, (c) GCD profiles at different specific currents and (d) comparison of the AHC cell with symmetric cells made using commercial, high surface area porous carbons at 2 A g-1(right to left - Cs (F g'1); Cv (F g'1); and Ev (Wh L’1)), and (e) LED tests of the same cell.

[0023] FIG. 8 shows Quenched Solid Density Functional Theory (QSDFT) pore size distributions based on the ASiQwin N2-carbon, slit-cylinder kernel for all the activated carbonaceous materials.

[0024] FIG. 9 shows SEM images of HPACs.

[0025] FIG. 10 shows XPS survey of HPACs- The inset displays the atomic elemental composition of the corresponding sample.

[0026] FIG. 11 shows deconvoluted high-resolution Cis spectra of the hypergolically derived carbons (a, b and c) and CS300 (d).

[0027] FIG. 12 shows CO2 uptake fitted with an intraparticle diffusion model indicating the different stages of the CO2 adsorption process.DETAILED DESCRIPTION OF THE DISCLOSURE

[0028] Although subject matter of the present disclosure is described in terms of certain embodiments and examples, other embodiments and examples, including embodiments and examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. For example, various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0029] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompass variations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art accepted standard, etc. and / or with, e.g., a given confidence interval (e.g., 90%, 95%, or more confidence interval from the mean), such as, for example, variations of + / - 10% or less, + / -5% or less, + / -1% or less, and + / - 0.1% or less of and from the specified value), insofar such variations in a variable and / or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value in question is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained.In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about,” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0030] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0.1% to 5%” should be interpreted to include not only the explicitly recited values of 0.1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0031] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., has one terminus that can be (is) covalently bonded to other chemical species), divalent, or polyvalent (i.e., has two or more termini that can be (are) covalently bonded to other chemical species). The term “group” also includes radicals (e.g., monovalent radicals and multivalent radicals, such as, for example, divalent radicals, trivalent radicals, and the like). Illustrative examples of groups include:

[0032] As used herein, unless otherwise stated, the term “structural analog” refers to any reactant, reaction component, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or group if one atom or group of atoms, functional group or functional groups, or substructure or substructures is / are replaced with another atom or group of atoms, functional group or functional groups, substructure or substructures, or the like. In various examples, the term “structural analog” refers to any group that is derived from an original reactant, reaction component, or the like or a portion thereof (such as, for example, one or more group(s) thereof or the like) or the like by a chemical reaction, where the reactant, reaction component, or the like or the portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is modified or partially substituted such that at least one structural feature of the reactant, reaction component, or the like or the portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is retained.

[0033] The present disclosure describes, inter alia, porous carbon materials and templated materials and methods of making same. In various examples, the present disclosure also provides uses of the porous carbons.

[0034] In an aspect, the present disclosure provides porous carbon materials. A porous carbon material may be referred to, in the alterative, herein, as a porous carbon, a high surface area carbon or carbon material, an ultra-high porous material, or HC nanomaterial, or hypergolic carbon). In various examples, porous carbon is produced by a method of the present disclosure. In various examples, porous carbon is an HCx material or the like. Non-limiting examples of porous carbon materials are disclosed herein.

[0035] In various examples, porous carbon material comprises mesopores as defined by IUPAC) and micropores (as defined by IUPAC). In various examples, porous carbon comprises a surface area of about 3600 m2 / g or more, about 3650 m2 / g or more, about 3700 m2 / g or more, about 3750 m2 / g or more, about 3800 m2 / g or more, about 3900 m2 / g or more, about 4000 m2 / g or more, about 4100 m2 / g or more, about 4200 m2 / g or more, about 4300 m2 / g or more, about 4400 m2 / g or more, about 4500 m2 / g or more, or about 4600 m2 / g or more. In various examples, porous carbon comprises a surface area of about 3500 m2 / g to about 4900 m2 / g, including all 0.1 m2 / g values and ranges therebetween (e.g., about 3500 m2 / g to about 4800 m2 / g, about 3600 m2 / g to about 4900 n / g, about 3650 m2 / g to about 4900 m2 / g, about 3700 m2 / g to about 4900 nr / g, about 3750 m2 / g to about 4900 m2 / g, about 3800 nr / g to about 4900 m2 / g, about 3900 m2 / g toabout 4900 m2 / g, about 4000 m2 / g to about 4900 m2 / g, about 4100 m2 / g to about 4900 m2 / g, about 4200 m2 / g to about 4900 m2 / g, about 4300 m2 / g to about 4900 nr / g, about 4400 m2 / g to about 4900 m2 / g, about 4500 m2 / g to about 4900 m2 / g, about 4600 m2 / g to about 4900 m2 / g, ). In various examples, porous carbon comprises mesopores as defined by IUPAC) and micropores (as defined by IUPAC) and a surface area of about 3500 m2 / g to about 4800 m2 / g or about 4900 m2 / g, including all 0.1 m2 / g values and ranges therebetween. Micropore and / or mesopore dimensions can be determined by methods known in the art. In various examples, surface area is determined by absorption isotherm analysis (e.g., BET surface area analysis or the like), or the like.

[0036] A porous carbon material can comprise various carbon structures. In various examples, a porous carbon comprises carbon cylinders or the like.

[0037] A porous carbon material can comprise various porosity. In various examples, substantially all or all the pores are micropores and / or mesopores. In various examples, about 95% or more, about 98% or more, about 99% or more, about 99.5% or more, about 99.9%, about 99.99%, or 99.999% or more, or about 100% of the pores are micropores and / or mesopores. In various examples, a micropore comprises a linear’ dimension (such as, for example, a diameter or the like) of less than 2 nm (e.g., about 0.1 nm to less than 2 nm, including all 0.05 nm values and ranges therebetween) and / or a mesopore comprises a linear dimension (such as, for example, a diameter or the like) of 2 nm to about 50 nm, including all 0.05 nm values and ranges therebetween. In various examples, the micropores comprise an average linear dimension (such as, for example, an average diameter or the like) of less than 2 nm (e.g., about 0.1 nm to less than 2 nm, including all 0.05 nm values and ranges therebetween) and / or the mesopores comprise a an average linear dimension (such as, for example, an average diameter or the like) of 2 nm to about 50 nm, including all 0.05 nm values and ranges therebetween. Micropore and / or mesopore dimensions can be determined by methods known in the art. In various examples, micropore and / or mesopore dimensions (which may be average dimensions) are determined by transmission electron microscopy, absorption isotherm analysis (e.g., BET surface area analysis or the like), or the like.

[0038] A porous carbon material can have various forms. In various examples, a porous carbon material is a monolith, a powder, a particulate material, a membrane (such as, for example, a solid-like membrane or the like), a film, or the like.

[0039] A porous carbon material can exhibit one or more desirable propert(ies). In various examples, a porous carbon exhibits desirable CO2 capture kinetics or the like. In various examples, a porous carbon reaches about 80 % or more or about 90% or more of the total CO2 capacity within about 60 seconds and / or a CO2 capture capacity of about 1.25 mmol g-1or more (e.g., tested at about 30 °C and about 1 bar', under dynamic CO2 capture conditions, such as, for example, TGA or the like).

[0040] In an aspect, the present disclosure provides templated materials. In various examples, a templated material is produced by a method of the present disclosure. In various examples, a templated material is an intermediate in the production of a porous carbon material of the present disclosure (e.g., is used in a method of the present disclosure). In various examples, a templated material is produced by a method of the present disclosure. Non-limiting examples of templated materials are disclosed herein.

[0041] In various examples, a templated material comprises a carbonaceous material disposed on at least a portion or substantially all or all of a surface or surfaces (which may be exterior surface(s)) of a templating substrate or templating substrates (which may be referred to as a template or templates). In various examples, a templating substrate is a templating precursor. Non-limiting examples of templating substrates are described herein. In various examples, the carbonaceous comprises (i) about 3 to about 20 atomic percent (e.g., based on the total weight of the templated material) of rim-based pentagons and / or (ii) comprises one or more radical specie(s) (e.g., carbon-centered radicals, oxygen-centered radicals, or the like, or any combination thereof) and / or carbon cylinders.

[0042] A templated material can comprise various radical species and / or amounts of radical species. In various examples, a templated material (or a carbonaceous material) comprises one or more radical specie(s) chosen from carbon-centered radicals, oxygen-centered radicals, and the like, and any combination thereof. In various examples, the amount of radical specie(s) corresponds to or the number of radical species corresponds to about 1 x 1013to 1 x 1017spins / gram of templated material, including all integer spins / gram values and ranges therebetween.

[0043] In various examples, a templated material comprises a plurality of carbon structures. In various examples, a majority of the carbon structures in a templated material (or a carbonaceous material) comprising carbon structures are not hexagonal carbon structures or thelike. In various examples, about 5% or less, about 10% or less, or about 20% or less of the carbon structures in a tcmplatcd material (or a carbonaceous material) comprising carbon structures are not hexagonal carbon structures or the like. In various examples, about 95% or less, about 90% or less, or about 80% or less of the carbon structures in a templated material (or a carbonaceous material) comprising carbon structures are hexagonal carbon structures or the like.

[0044] A templated material can have various forms. In various examples, a templated material is a monolith, a powder, a particulate material, a membrane (such as, for example, a solid-like membrane or the like), a film, or the like.

[0045] In an aspect, the present disclosure provides methods of making porous carbon materials. In various examples, a method comprises subjecting one or more carbon precursor(s) and one or more templating substrate(s) to hypergolic conditions. In various examples, a method comprises subjecting one or more carbon precursor(s) and one or more templating substrate(s) to hypergolic conditions and subsequently activating the product produced by the hypergolic conditions. In various examples, a method produces a templated material of the present disclosure and / or porous carbon material of the present disclosure. Non-limiting examples of methods of making templated materials and / or porous carbon materials are disclosed herein.

[0046] In various examples, a method of making a porous carbon material or materials comprises: contacting one or more carbon precursor(s) and one or more templating substrate(s) under hypergolic conditions (e.g., where a carbonaceous material (such as, for example, a templated product (e.g., a templated material) is formed), removing substantially all or all of the templating substrate(s) from the material resulting from the contacting (e.g., the templated product (e.g., a templated material) formed under the hypergolic conditions); activating the material after removal of substantially all or all of the templating substrate(s) (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)); and carbonizing the activated material (e.g., the activated carbonaceous material), where the porous carbon (which may be referred to as a hypergolic carbon or HCx (where x corresponds to the silica template or the like)) is formed.

[0047] A method of making a porous carbon comprising: forming a mixture (e.g., an aqueous mixture) comprising: one or more carbon precursor(s), one or more templating substrate(s) (e.g., hard template(s)), and optionally, one or more solvent(s); heat treating the mixture (e.g., in air),contacting the heat-treated mixture with one or more first hypergolic reagent(s) (e.g., an organic fuel); contacting (e.g., chemically activating or the like) the heat-treated mixture and the first hypergolic reagent(s) with one or more second hypergolic reagent(s) (e.g., an oxidizer) (e.g., resulting in hypergolic conditions), where a templated product (such as, for example, a templated material) is formed; and removing substantially all of the templating substrate(s) from the templated product, where a carbonaceous material is formed; activating the carbonaceous material, where an activated carbonaceous material is formed (which may be referred to as HPACx (where x corresponds to the template, such as, for example, S for SBA-15, M for MCM- 41, and L for LUDOX HS30) and carbonizing the activated carbonaceous material, where the porous carbon product (which may be referred to as a hypergolic carbon or HCx (where x corresponds to the silica template or the like) is formed.

[0048] A method may form a porous carbon material, where all of the material is the substantially the same or the same (e.g., compositionally the same, structurally the same, or both). A method may form a plurality of porous carbon materials, where two or more or all of the materials are different (e.g., compositionally different, structurally different, or both).

[0049] Various carbon precursors can be used. In various examples, a carbon precursor forms a carbonaceous material under hypergolic conditions. Non-limiting examples of carbon precursors include carbohydrates (such as, for example, sucrose, glucose, fructose, or fructan, and the like, structural analogs thereof (such as, for example, water-soluble structural analogs thereof), and the like, structural analogs thereof (such as, for example, water-soluble structural analogs thereof), and any combination thereof. In various examples, a carbon precursor is a water-soluble carbon precursor. In various examples, at least a portion, substantially all, or all of the carbon precursor(s) is / are water-soluble precursor(s).

[0050] Various amounts of carbon precursors can be used. In various examples, the carbon precursors) s) is / are present (e.g., individually or in the aggregate) at about 50 weight percent (wt.%) to about70 wt.% (based on the total weight of the reaction mixture (e.g., hypergolic mixture or the like)), including all 0.1 wt.% values and ranges therebetween). In various examples, the carbon precursors(s) is / are present (e.g., in the aggregate) at about 1 g to about 3g, including all 0.1 g values and ranges therebetween).

[0051] Various templating precursors (which may be templating substrates or templates in a templated material) can be used. The templating substrates may be substantially the same or thesame or two or more different (e.g., compositionally and / or structurally different) templating substrates may be used. Non-limiting examples of templating precursors (or templating substrates) include silica nanoparticles (such as, for example, mesoporous silica nanoparticles, colloidal silica nanoparticles, and the like, and any combination thereof), structural analogs thereof, and the like, and any combination thereof. A silica nanoparticle can have various morphologies. In various examples, a silica nanoparticle comprises tubular structures, or the like, or any combination thereof. In various examples, a silica nanoparticle is substantially spherical or spherical, substantially cylindrical or cylindrical, cube-like, or the like. In various examples, at least a portion substantially all, or all of the templating precursors(s) (such as, for example, silica nanoparticle(s) (which may be mesoporous silica(s), such as, for example, SBA-15, MCM-41, or the like, or any combination thereof, or the like, or any combination thereof) or the like, independently comprise(s) a hierarchical structure (such as, for example, hierarchical pore structure or the like).

[0052] In various examples, one or more or all of the templating substrate(s) is / are porous nanoparticle(s). In various examples, a templating substrate is a porous silica nanoparticle (e.g., comprising a size (e.g., a linear’ dimension (or an average dimension) (such as, for example, a diameter (or average diameter or the like) of about 5 nm to about 200 nm, including all 0.1 nm values and ranges therebetween) and / or a plurality of pores comprising a comprising a pore size (e.g., a linear dimension (such as, for example, a diameter or the like) of about 1 nm to about 10 nm, including all 0.1 nm values and ranges therebetween). Non-limiting examples of templating substrates include porous silica nanoparticles, structural analogs thereof, and the like, and any combination thereof. Non-limiting examples of silica nanoparticles include mesoporous silica (such as, for example, SBA-15 (e.g., less than about 150 pm particle size and / or pore size about 4 nm, or the like), SBA-16 (e.g., less than 150 pm particle size and / or pore size about 5 nm, or the like), MCM-41 (e.g., pore size about 4 nm or the like), MCM-48 (e.g., about 15 pm particle size and / or pore size about 3 nm, or the like), SBA-16 (e.g., less than 150 pm particle size and / or pore size about 5 nm, or the like), KIT-6 (e.g., particle size about 10 pm to about 100 pm, including all 0.1 pm values and ranges therebetween)), colloidal silica nanoparticles (such as, for example, LUDOX®, 30 wt % in water, or the like) (e.g., an average diameter of about 12 nm or the like), structural analogs thereof, and the like, and any combination thereof.

[0053] Various amounts of templating precursors can be used. In various examples, the tcmplating prccursor(s) is / arc present (e.g., individually or in the aggregate) at about 30 wt.% to about 50 wt.% (based on the total weight of the reaction mixture (e.g., hypergolic mixture or the like)), including all 0.1 wt.% values and ranges therebetween). In various examples, templating precursors(s) is / are present (e.g., in the aggregate) at about 1 to about 2 g, including all 0.1 g values and ranges therebetween.

[0054] Carbon precursor(s) and templating precursor(s) can be used in various ratios. In various examples, the ratio (e.g., mass ratio (such as, for example, mass ratio in grams or the like) or the like) of carbon precursor(s) : templating precursors(s) is about 1 : 1 to about 4 : 1 mass ratios (g), including all 0.01 ratio values and ranges therebetween.

[0055] A mixture of (e.g., an aqueous mixture) comprising one or more carbon precursor(s), one or more templating substrate(s) (e.g., hard template(s)), and optionally, one or more solvent(s) may be heated (e.g., at various temperatures and / or for various times). In various examples, a mixture is heated to about 90 °C to about 180 °C, including all 0.1 °C values and ranges there between, and / or for about 1 hour to about 20 hours, including all 0.1 hour values and ranges there between.

[0056] Hypergolic conditions may include use of a first hypergolic reagent or reagents and a second hypergolic reagent or reagents. Hypergolic conditions may include use of a first hypergolic reagent or reagents and a second hypergolic reagent or reagents. In various examples, a mixture (e.g., a mixture (e.g., an aqueous mixture) comprising one or more carbon precursor(s), one or more templating substrate(s) (e.g., hard template(s)), and optionally, one or more solvent(s)) is exposed to (or reacts under) hypergolic conditions (such as, for example, hypergolic conditions resulting from combining of a first hypergolic reagent or reagents and a second hypergolic reagent or reagents. The hypergolic reagents can be combined in any order. In various examples, second hypergolic reagent(s) (e.g., an oxidizer or oxidizers) are added to first hypergolic reagent(s) (e.g., an organic fuel or fuels). In various examples, a method comprises contacting a heat-treated mixture with one or more first hypergolic reagent(s) (e.g., an organic fuel or fuels); contacting (e.g., chemically activating or the like) the heat-treated mixture and the first hypergolic reagent(s) with one or more second hypergolic reagent(s) (e.g., an oxidizer or oxidizers) (e.g., resulting in hypergolic conditions).

[0057] Various first hypergolic reagents and second hypergolic reagents can be used. In various examples, a first hypergolic reagent is an organic fuel or the like. Non-limiting examples of first hypergolic reagents include aniline, furfuryl alcohol, structural analogs thereof, and the like, and any combination thereof. In various examples, a second hypergolic reagent is an oxidizer or the like. Non-limiting examples of second hypergolic reagents include fuming nitric acid, hydrogen peroxide, red or white fuming nitric acid, structural analogs thereof, and the like, and any combination thereof.

[0058] First hypergolic reagent(s) and second hypergolic reagent(s) can be used in various ratios. In various examples, the ratio (e.g., volume ratio or the like) of first hypergolic reagent(s) : second hypergolic reagent(s) is about 0.5 : 1 to about 1 : 5, including all 0.01 volume ratios and ranges therebetween.

[0059] A method comprises activating a product after removal of the templating substrate removal (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)). In various examples, activating (e.g., chemically activating or the like) comprises: contacting, one or more time(s) (e.g., impregnating or the like) the material after removal of substantially all or all of the templating substrate(s) (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)) with an base (e.g., aqueous base or the like) (such as for example, KOH or the like (e.g., aqueous KOH (e.g., about 50% w / v) or the like); and optionally, heating (e.g., drying or the like) the base-treated (e.g., impregnated or the like) templated product (e.g., at about 90 °C to about 110 °C, including all 0.1 °C values and ranges there between and / or for about 1 hour to about 2 days, including all 0.1 hour values and ranges there between, and / or the method (or the activating) further comprises carbonizing the base-treated (e.g., impregnated or the like) and, optionally, dried material after removal of substantially all or all of the templating substrate(s) (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)) (e.g., at about 500 °C to about 900 °C, including all 0.1 °C values and ranges there between and / or for about 0.5 hour to about 6 hours, including all 0.1 hour values and ranges there between (e.g., about 1 hour to about 4 hours), in an inert atmosphere (e.g., a nitrogen atmosphere or the like)), optionally, washing the porous carbon product, where the porous carbon product is formed.

[0060] A method may comprise washing an activated product. In various examples, the activated product formed from activation of the templated product is washed (e.g., once ormultiple times) with one or more liquid(s) (e.g., solvent(s) or the like) (such as, for example, water (which may be deionized water or the like), organic solvcnt(s) (such as, for example, alcohols (e.g., ethanol and the like), ketone(s) (e.g., acetone and the like), and any combination thereof).

[0061] A method may comprise drying and / or collecting a porous carbon product or products. In various examples, a method further comprises drying (e.g., the washed porous carbon product) and / or collecting the porous carbon product (e.g., the washed porous carbon product or the washed and dried porous carbon product). In various examples, the activated product formed from activation of the templated product is heated (e.g., dried) about 80 °C to about 150 °C, including all 0.1 °C values and ranges therebetween.

[0062] A method may comprise heating the porous carbon product(s) formed from carbonization of the activated product. In various examples, the porous carbon product formed from carbonization of the activated product is heated (e.g., dried) about 400 °C to about 900 °C, including all 0.1 °C values and ranges therebetween.

[0063] A method may comprise washing the porous carbon product(s) formed from carbonization of the activated product. In various examples, the porous carbon product formed from carbonization of the activated templated product is washed (e.g., once or multiple times) with one or more liquid(s) (e.g., solvent(s) or the like) (such as, for example, water (which may be deionized water or the like), organic solvent(s) (such as, for example, alcohols (e.g., ethanol and the like), ketone(s) (e.g., acetone and the like), one or more acid(s) (e.g., HC1 or the like), and any combination thereof).

[0064] In an aspect, the present disclosure provides uses of templated materials and porous carbon materials of the present disclosure. In various examples, a templated material is used to produce porous carbon material of the present disclosure. In various examples, a device comprises one or more porous carbon material(s) of the present disclosure. Non-limiting examples of uses of templated materials and / or porous carbon materials are disclosed herein.

[0065] Templated materials and high surface area carbons have various uses. Non-limiting examples of uses include use as molecular sieve(s), adsorbant(s) (which may be gas adsorbant(s) or the like (such as, for example, a carbon dioxide adsorbant or the like)), electrode(s) or electrode materials, as gas (e.g., hydrogen gas or the like) storage material(s), or the like.

[0066] Porous carbon or carbons can be used in filtration methods. In various examples, a filtration method comprises use of one or more porous carbon matcrial(s) (such as, for example, as filtration media or the like). In various examples, a sample, such as, for example, wastewater, salt water, brackish groundwater, or the like, is filtered (e.g., to remove one or more pollutant(s), such as, for example, organic dye(s), oil(s), perfluorinated compound(s), heavy metal(s), or the like, or any combination thereof).

[0067] Porous carbon or carbons can be used in catalytic methods. In various examples, a catalytic method comprises use of one or more porous carbon(s) (such as, for example, as catalyst(s), catalyst support(s), or both, or the like. In various examples, a catalyst or catalyst material or catalyst support comprises one or more porous carbon material(s) and / or one or more templated material(s). In various examples, a porous carbon or carbons is / are used as supports for anchoring a catalyst or catalysts (such as, for example, a metal or metals with catalytic activity or the like), for the preparation of supported metal catalysts, and as catalysts in their own right (such as, in acid-base reactions, in electrocatalysis, or the like).

[0068] Porous carbon or carbons can be used in a carbon capture and / or carbon sequestration method. In various examples, carbon capture and / or carbon sequestration method comprising use of one or more porous carbon(s) (such as, for example, as adsorbant(s) or the like. In various examples, porous carbon material(s) is / are used as carbon dioxide adsorbant(s) (which may be reversible carbon dioxide adsorbant(s)). In various examples, a carbon capture and / or carbon sequestration method comprises contacting the porous carbon material(s) with carbon dioxide (such as, for example, carbon dioxide gas or the like) or the like. In various examples, the source of carbon dioxide or the like is the atmosphere, an industrial process, a power generation process, or the like, or any combination thereof. In various examples, at least a portion of the carbon dioxide or the like is adsorbed by and / or desorbed by (e.g., reversibly adsorbed) the porous carbon materials ).

[0069] A device can comprise one or more porous carbon material(s). In various examples, a device is configured to carry out a use of porous carbon material(s) (such as, for example, a use of the porous carbon material(s) described herein). Non-limiting examples of devices include carbon capture and / or sequestration devices, filtration devices, devices comprising electode(s), and the like.

[0070] A device can be a carbon capture device. In various examples, a device is (or is configured to function as) a carbon capture and / or sequestration device (such as, for example, a carbon dioxide capture and / or sequestration device or the like).

[0071] A device can be a filtration device. In various examples, a device is (or is configured function as) a filtration device or the like. In various examples, a filtration device is configured for normal flow, dead-end flow, tangential flow, or the like, or any combination thereof. In various examples, a filtration device is configured for gravity filtration, centrifugation, gaspressurization filtration, or the like, or any combination thereof.

[0072] A device can comprise one or more electrode(s). In various examples, a device comprises one or more electrode(s), where the electrode(s) independently comprise one or more porous carbon material(s). In various examples, a device is (or is configured function as) an energy-generating device, an energy storage device, or the like. In various examples, a device is (or is configured function as) an electrochemical device or the like. In various examples, a device is a fuel cell, a battery, a water-electrolysis device, an electrodialysis device, or the like.

[0073] The following Statements provide examples of methods and materials and uses thereof of the present disclosure;Statement 1. A method of making a porous carbon (e.g., a porous carbon of Statement 14) comprising: contacting one or more carbon precursor(s) and one or more templating substrate(s) under hypergolic conditions (e.g., where a carbonaceous material (such as, for example, a templated product (e.g., a templated material) is formed), removing substantially all or all of the templating substrate(s) from the material resulting from the contacting (e.g., the templated product (e.g., a templated material) formed under the hypergolic conditions); activating the material after removal of substantially all or all of the templating substrate(s) (or activating the material resulting after the removing substantially all or all of the templating substrate(s) from the carbonaceous templated material) (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)); and carbonizing the activated material (e.g., the activated carbonaceous material), where the porous carbon (which may be referred to as a hypergolic carbon or HCx,y (where x corresponds to the template and y is the size of the template (e.g., silica template or the like)) is formed; or A method of making a porous carbon (e.g., a porous carbon of Statement 14) comprising: forming a mixture (e.g., an aqueous mixture) comprising: one or more carbon precursor(s) (e.g., one or more or all of which are water-solublecarbon precursor(s)), one or more templating substrate(s) (e.g., hard template(s)), and optionally, one or more solvcnt(s); heat treating the mixture (e.g., in air or the like), contacting the heat- treated mixture with one or more first hypergolic reagent(s) (e.g., an organic fuel or fuels); contacting (e.g., chemically activating or the like) the heat-treated mixture and the first hypergolic reagent(s) with one or more second hypergolic reagent(s) (e.g., an oxidizer or oxidizers) (e.g., resulting in hypergolic conditions), where a templated product (such as, for example, a templated material) is formed; and removing substantially all of the templating substrate(s) from the templated product, where a carbonaceous material is formed; activating the carbonaceous material, where an activated carbonaceous material is formed (which may be referred to as AHCx,y (where x corresponds to the template and y is the size of the template (e.g., silica template or the like))); and carbonizing the activated carbonaceous material, where the porous carbon product (which may be referred to as a hypergolic carbon or HCx,y (where x corresponds to the template and y is the size of the template (e.g., silica template or the like)) is formed.Statement 2. A method according to Statement 1, where the carbon precursor(s) is / are independently chosen from carbohydrates (such as, for example, sucrose, glucose, fructose, or fructan, and the like, structural analogs thereof (such as, for example, water-soluble structural analogs thereof), and the like), structural analogs thereof (such as, for example, water-soluble structural analogs thereof), and any combination thereof.Statement 3. A method according to Statement 1 or 2, where the carbon precursors(s) is / are present (e.g., individually or in the aggregate) at about 50 wt.% to about70 wt.% (based on the total weight of the reaction mixture (e.g., hypergolic mixture or the like)), including all 0.1 wt.% values and ranges therebetween) or (e.g., in the aggregate) at about 1 g to about 3g, including all 0.1 g values and ranges therebetween).Statement 4. A method according to any one of the preceding Statements, where the templating substrate(s) is / are chosen from silica nanoparticles (such as, for example, MCM-41, SBA-15, SBA-16, MCM-48, KIT-6, and the like, and any combination thereof) (which maybe porous silica nanoparticles) (e.g., mesoporous and / or comprise hierarchical structure), and the like and any combination thereof.Statement 5. A method according to any one of the preceding Statements, where the templating precursors(s) is / are (e.g., individually or in the aggregate) at about 30 wt.% to about50 wt.%(based on the total weight of the reaction mixture (e.g., hypergolic mixture or the like)), including all 0.1 wt.% values and ranges therebetween or (e.g., in the aggregate) at about 1 to about 2 g, including all 0.1 g values and ranges therebetween.Statement 6. A method according to any one of the preceding Statements, where the ratio (e.g., mass ratio, which may be a gram(s) ratio, or the like) of carbon precursor(s) : templating precursors(s) is about 1 : 1 to about 4 : 1.Statement 7. A method according to any one of the preceding Statements, where the mixture (e.g., reaction mixture or the like) heating is carried out at about 90 °C to about 180 °C, including all 0.1 °C values and ranges there between and / or for about 1 hour to about 20 hours, including all 0.1 hour values and ranges there between.Statement 8. A method according to any one of the preceding Statements, where the first hypergolic reagent(s) is / are chosen from aniline, furfuryl alcohol, structural analogs thereof, and the like, and any combination thereof.Statement 9. A method according to any one of the preceding Statements, where the second hypergolic reagent(s) is / are chosen from fuming nitric acid, hydrogen peroxide, red fuming nitric acid, structural analogs thereof, and the like, and any combination thereof.Statement 10. A method according to any one of the preceding Statements, where the ratio (e.g., volume ratio or the like) of first hypergolic reagent(s) : second hypergolic reagent(s) is about 0.5 : 1 to about 1 : 5, including all 0.01 volume ratios and ranges therebetween.Statement 11. A method according to any one of the preceding Statements, where the activating (e.g., chemically activating or the like) comprises: contacting, one or more time(s) (e.g., impregnating or the like) the material after removal of substantially all or all of the templating substrate(s) (e.g., the carbonaceous material resulting from removal of substantially all or all of the templating substrate(s)) with one or more base(s) (e.g., aqueous base(s) or the like) (such as for example, KOH or the like (e.g., aqueous KOH (e.g., about 50% w / v) or the like); and optionally, heating (e.g., drying or the like) the base-treated (e.g., impregnated or the like) templated product (e.g., at about 90 °C to about 110 °C, including all 0.1 °C values and ranges there between and / or for about 1 hour to about 2 days, including all 0.1 hour values and ranges there between, and / or the method (or the activating) further comprises carbonizing the basetreated (e.g., impregnated or the like) and, optionally, dried material after removal of substantially all or all of the templating substrate(s) (e.g., the carbonaceous material resultingfrom removal of substantially all or all of the templating substrate(s)) (e.g., at about 500 °C to about 900 °C, including all 0.1 °C values and ranges there between and / or for about 0.5 hour to about 6 hours, including all 0.1 hour values and ranges there between (e.g., about 1 hour to about 4 hours), in an inert atmosphere (e.g., a nitrogen atmosphere or the like)); optionally, washing the porous carbon product, where the porous carbon product is formed; and optionally; drying (e.g., the washed porous carbon product) and / or collecting the porous carbon product (e.g., the washed porous carbon product or the washed and dried porous carbon product).Statement 12. A templated material comprising a carbonaceous material disposed on at least a portion or substantially all or all of a surface or surfaces (which may be exterior surface(s)) of a templating substrate, where the carbonaceous material comprises one or more or all of the following: (i) about 3 to about 20 atomic percent (e.g., based on the total weight of the templated material) of rim-based pentagons); or (ii) comprises one or more radical specie(s) (e.g., carboncentered radicals, oxygen-centered radicals, or the like, or any combination thereof); or (iii) carbon cylinders.Statement 13. A templated material according to Statement 12, where the carbonaceous material comprises one or more radical specie(s) (e.g., carbon-centered radicals, oxygen-centered radicals, or the like, or any combination thereof), where the amount of the radical specie(s) corresponds to or the number of the radical species corresponds to about 1 x 1013to 1 x 1017spins / gram of templated material, including all integer spins / gram values and ranges therebetween, and / or a plurality of carbon structures (e.g., a majority of the carbon structures are not hexagonal carbon structures).Statement 14. A porous carbon (such as, for example, a porous carbon comprising carbon cylinders or the like) comprising (i) a surface area of about 3500 m2 / g to about 4800 m2 / g, including all 0.1 m2 / g values and ranges therebetween; or (ii) a plurality of micropores (e.g., as defined by IUPAC) and a plurality of mesopores (e.g., as defined by IUPAC); or (iii) a plurality of micropores (e.g., as defined by IUPAC) and a plurality of mesopores (e.g., as defined by IUPAC) and a surface area of about 3500 m2 / g to about 4800 m2 / g, including all 0.1 m2 / g values and ranges therebetween, where the porous carbon may reach 80 % of the total CO2 capacity of the porous carbon within about 60 seconds, or a CO2 capture capacity of 1.25 mmol g-1(tested at 30 °C and 1 bar, under dynamic CO2 capture conditions) or both.Statement 15. A filtration method comprising use of one or more porous carbon material(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to 11)).Statement 16. A filtration method according to Statement 15, where the filtration method filters wastewater, salt water, brakish groundwater, or the like is filtered.Statement 17. A catalytic method comprising use of one or more porous carbon(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to 11)).Statement 18. A catalytic method according to Statement 17, where the porous carbon(s) is / are used as catalyst(s) and / or catalyst support(s).Statement 19. A carbon capture and / or carbon sequestration method comprising use of one or more porous carbon(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to 11)).Statement 20. A carbon capture and / or carbon sequestration method according to Statement 19, where the porous carbon(s) is / are used as carbon dioxide adsorbant(s) (which may be reversible carbon dioxide adsorbant(s)).Statement 21. A carbon capture and / or carbon sequestration method according to Statement 19 or 20, where the porous carbon(s) is / are contacted with carbon dioxide (such as, for example, carbon dioxide gas) from the atmosphere, an industrial process, a power generation process, or the like, or any combination thereof (e.g., where at least a portion of the carbon dioxide is adsorbed by and / or desorbed by (e.g., reversibly adsorbed) the porous carbon(s)).Statement 22. Use of one or more porous carbon(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to 11)) as molecular sieve(s), adsorbant(s) (which may be gas adsorbant(s) or the like (such as, for example, a carbon dioxide adsorbant or the like)), electrode(s), as gas (e.g., hydrogen gas or the like) storage material(s), or the like.Statement 23. A device comprising one or more porous carbon(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to I D).Statement 24. A device according to Statement 23, where the device is (or is configured function as) a filtration device or the like.Statement 25. A device according to Statement 24, where the filtration device is configured for normal flow, dead-end flow, tangential flow, or the like, or any combination thereof.Statement 26. A device according to Statement 24 or 25, where the filtration device is configured for gravity filtration, centrifugation, gas-pressurization filtration, or the like, or any combination thereof.Statement 27. A device according to Statement 23, where the device is (or is configured to function as) a carbon capture device (such as, for example, a carbon dioxide capture device or the like).Statement 28. A device comprising one or more electrode(s), where the electrode(s) independently comprise one or more porous carbon(s) of the present disclosure (such as, for example, porous carbon(s) of Statement 14 and / or porous carbon(s) made by a method of the present disclosure (e.g., a porous carbon made by a method of any one of Statements 1 to 11)). Statement 29. A device according to Statement 28, where the device is an energy-generating device, an energy storage device, or the like.Statement 30. A device according to Statement 28, where the device is an electrochemical device or the like.Statement 31. A device according to any one of Statements 28 to 30, where the device is a fuel cell, a battery, a water-electrolysis device, an electrodialysis device, or the like.

[0074] The steps of the methods described in the various examples disclosed herein are sufficient to produce one or more material(s) (e.g., porous carbon material(s) and / or templated material(s) or the like) or carry out a method of the present disclosure. Thus, in various examples, a method consists essentially of a combination of the steps of the methods disclosed herein. In various other examples, a method consists of such steps.

[0075] The following Example is presented to illustrate the present disclosure. The Example is not intended to be limiting in any manner.EXAMPLE

[0076] This example provides a description of materials and methods and uses thereof of the present disclosure.

[0077] Synthesis of ultra-high surface area carbon sorbents by integrating hypergolic and activation reactions of a templated substrate. A family of carbon sorbents synthesized by integrating hypergolic with activation reactions on a templated substrate was developed. The materials design leads to nanoporous carbons with BET area of 4800 nr g1with an impressive total pore volume of 2.7 cm3g’1. To the best of our knowledge, this BET area value is the highest reported in the literature. Electron spin resonance (ESR) measurements determined the number of radicals in an effort to provide a mechanistic understanding towards the formation of ultra- high surface area carbons. In combination with XPS, a proposed mechanism is based on the synergistic effect between rim-based pentagonal rings and carbon radicals. The CO2 capture capacity of the hyperporous carbon tested under dynamic CO2 capture conditions was ~ 1.25 mmol g-1versus 0.66 mmol g'1of a conventionally activated carbon under similar’ conditions. The CO2 capture kinetics were extremely fast and reached 99 % of the total capacity within 120 seconds. Lastly, supercapacitor electrodes deliver a high volumetric energy density of ~60 Wh L-1and a volumetric power density of 1 kW L-1, which is the highest reported value for activated carbon.

[0078] An approach to synthesize carbons with ultra-high surface area and exceptional carbon dioxide capacity and electrochemical performance was developed. The approach involves reacting hypergolically a mixture of sucrose and a hard template, followed by KOH activation.

[0079] Hypergolic reactions are extremely important and are used in rocket and aircraft systems including orbiting satellites, manned spacecrafts, defense aircrafts and deep space probes for propulsion and hydraulic power. Hypergolic reactions involve two chemicals, which spontaneously ignite upon contact in the absence of external stimuli. The main advantages are rapid reaction without the need of any external energy input and fast product formation. The absence of any energy input for completion is the main difference between hypergolics and existing synthetic processes which are typically energy-consuming. Such reactions can be used in chemistry demonstrations to show the extraordinary power of chemical energy and have been exploited in real life applications (e.g., for rocket propellants and fuels). The energy produced can also be harnessed in materials synthesis to produce various materials, including carbon, atambient conditions. In contrast to previous reports that led to nonporous materials, it was demonstrated that the combination of hypergolic and activation reactions can lead to the production of highly porous materials with exceptionally high surface area and pore volume. More specifically, treating a templated (SBA-15) mixture of a carbon precursor hypergolic ally followed by the removal of the template and KOH activation results in ultra-high surface area carbons. The choice of template is critical as the use of SBA-15 results in a replica cylindrical structure. Subsequent activation with KOH leads to an ultra-high BET area of more than 4750 nr / g. Note that the use of other silica-based templates including those with a cylindrical structure (MCM-41) or spherical colloidal silica results in carbons with more modest surface areas that are also accessible via more conventional approaches.

[0080] Having a mechanistic understanding of the synthesis approach vis a vis, the effect of different parameters on porosity is especially important to synthesize ultra-high surface area carbon materials. It is believed that both the chemical and physical features of the initially derived carbon structures allowed by hypergolics are critical in determining the subsequent activation and achieving ultra-high surface area. To delineate the effect of various design parameters a systematic study probing the relationship between the type of template and the reaction temperature was carried out and the results contrasted to those obtained by traditional means. The ultra-high surface area is due to the synergy between the rim-based pentagonal rings and carbon radicals present prior to activation as pail of the combination of the hypergolic treatment and the SBA-15 template.

[0081] Owing to an interest in developing materials for CO2 capture, the performance of the HP AC was evaluated by thermogravimetric methods (TGA) under ambient conditions and contrasted to a conventionally activated carbon. Additionally, their stability and regeneration properties were studied over repetitive adsorption-desorption cycles.

[0082] Moreover, their performance was evaluated as the active material for supercapacitor electrodes in an ionic liquid electrolyte. The electrodes show great rate capability and stability up to 3.5 V. Moreover, their volumetric energy density of 60 Wh L-1is about 4 times higher than the commercially available activated porous carbons and, to the best of our knowledge, the highest reported to date for activated carbons.

[0083] The synthesis approach for the ultra-high porous carbons involves using a water solution of sucrose templated with SBA-15 in a manner similar to the synthesis of mesoporouscarbons. However, instead of using conventional heat treatment the mixture is treated hypcrgolically. This is an important (c.g., critical) process enhancement to achieve ultra-high surface area materials after activation. The silica in the carbon / silica hybrid was removed subsequently by NaOH and heating at 80 °C to produce hypergolic carbon and using SBA-15 as template (HCs). Finally, activation by KOH produces HPACs, where S corresponds to the SBA- 15. In an effort to elucidate the synthesis mechanism a large experimental matrix was investigated, and a large number of samples was characterized. Specifically, samples synthesized with different templates as described above and in the absence of a template as well as samples prepared hypcrgolically and by a conventional thermal treatment were compared. Interestingly, only the hypcrgolically treated sucrose templated by SBA-15 reaches the ultra-high surface area after KOH activation. FIG. 1(a) shows the XRD pattern in the low 20 region (0.8°-5.0°) for HCs after the removal of the SBA-15 template. For reference, the XRD pattern of SBA-15 is also included. Both show a prominent peak at 20 = 1.3°, which is assigned to the (100) diffraction of the ordered hexagonal structure. Interestingly the hexagonal structure is only present in HCs while a featureless XRD pattern is obtained, when MCM-41 is used as a template. The difference is consistent with previous observations, and has been attributed to the presence of micropores connecting the main nanochannels of SBA-15. These micropores are evidently absent from MCM-41. As a result, the hexagonal structure disappears after the template removal. No ordering was noticed for the other referenced samples before activation (i.e., HCL, HCsucrose or CS300), as shown in the corresponding XRD patterns. TEM and SEM were further used to probe the morphological characteristics of the material. TEM shows the presence of a tubular carbon structure (FIG. 1(b)) while SEM shows a rod- like morphology (FIG. 1(c)) consistent with an ordered structure. The last step of the process involves activation of HCs with KOH. The resulting material, HPACs shows a broad (002) diffraction peak characteristic of amorphous carbon lacking any structural order in lower angles. Similar results were obtained for all activated samples regardless of template or process used.

[0084] Nitrogen porosimetry was used to characterize the surface area (SBET) before and after activation of all carbons synthesized hypcrgolically or by conventional means as well as using different templates (FIG. 2). For convenience the samples are divided into two categories: before activation (HC category I), and after activation (HP AC, category II). The SBET values for the samples before KOH activation decreases in the order HCs > HCM > CS300 > HCL > HCsucrose.The relatively low surface area for all templated samples which were not treated hypergolically is likely due to the failure to fill the microporcs connecting the cylindrical mcsoporcs (when SBA-15 is used as template), the absence of such micropores (for MCM-41) and the absence of both cylindrical mesopores and micropores (in the case of colloidal silica). Filling of the micropores keeps the carbon cylinders apart and leads to a porous structure with increased surface area. Note that the lack of micropores that connect the cylindrical mesopores prevents conventionally processed carbons from developing a high level of porosity, when MCM-41 is used as a template instead of SBA-15. Consistent with the above, hypergolically treated sucrose, which was templated with MCM-41 results in an even lower porosity material. To demonstrate the critical role of hypergolic versus conventional heating in attaining ultra-high surface area carbons after KOH activation, a baseline experiment was conducted using the same precursors (sucrose, SBA-15, H2SO4) and followed by pyrolysis at 300 °C for Ih (more details are provided in the experimental section). The temperature of 300 °C was chosen to simulate the temperature of hypergolic flame. After removal of the template and before KOH activation the material displayed more or less a similar surface area (33 m2 / g) with the hypergolically treated samples (HCs). The lowest surface area (no porosity) was obtained for HCL (3 m2 / g), where colloidal silica was used as the template. Interestingly, sucrose in the absence of any template (denoted as HCsucrose) also leads to basically a nonporous material.

[0085] KOH activation is a well-known strategy for generating additional micropores to carbon-based materials. In contrast to the non-activated samples, the activated carbons show as one might expect much higher BET areas. What was unexpected though was the ultra-high BET area obtained for the hypergolically treated sample templated with SBA-15. HPACs displays ahigh value of 4800 m2g-1with an impressive total pore volume of 2.72 cm3g-1. Most importantly, the pore volume pertains to pore sizes below 8 nm, as clearly depicted in the quenched-solid-density-functional-theory (QSDFT) pore size distribution (PSD), given in FIG. 8. The shape of the isotherm is similar to that of recently reported ultra-high surface area carbons derived from waste biomass and activated with KOH at 800 °C. It is noted, however, that the BET area presented here is much higher from those reported previously. In previous reports the activation at 800 °C appears optimal as activation at higher temperatures decreases the surface area due to partial collapse of the porous network. Introduction of micropores through the activation step leads to an increase in the surface area and the fraction of micropores present.Consistent with previous work, CS300 after KOH activation (sample ACS300) reaches a BET area of only 2370 m2 / g, significantly lower than that of HPACs. This BET area is in line with other conventionally pyrolyzed activated carbon samples emphasizing the criticality of the hypergolic treatment to achieve an ultra-high surface area. For completeness, the corresponding Quenched Solid Density Functional Theory (QSDFT) pore size distributions of all activated samples are presented in FIG. 8. All surface areas were calculated by the BETSI software, by respecting all the Rouruerol BET consistency criteria. Furthermore, the results for HPACs have been confirmed by using additional software (Micromeritics and Quantachrome) as well as on-line routines, namely BEaTmap (Brunauer Emmett and Teller heatmap and SESAMI). The optimal BET area values ranged from 4760 to 4825 m2 / g). It should however be emphasized that in general the BET area is not a measure of the actual specific surface area of a sample. It represents the extent of apparent gas-solid interactions, which may serve as a “fingerprint” of the material (as also noted by the IUPAC Technical Report on adsorption).

[0086] It is noted, that to the best of our knowledge, the BET area for HPACs is the highest reported to date. Although there are numerous studies reporting BET areas in the range of 3000-3800 m2 / g, very few claim BET areas above 4000 m2 / g (Table 1).

[0087] Table 1. Summary of ultra-high surface area activated carbons.Samples Surface Area Activating Temperature[m2 / g] Agent [°C]Cigarette butt- 4310 KOH 600 Previous derived carbons workActivated asphalt 4200 KOH 900 Previous workPhloroglucinol 4476 NaNHj 600 Previous based carbon workHypercrosslinked 4334 KOH 800 Previous pyrrole workPorous graphitic 4073 KOH 400 Previous carbon workHPACs 4800 KOH 800 This work[00881 The surface morphology of HPACs with the highest BET area was further characterized by SEM and TEM. After KOH activation, the material shows Swiss cheese morphology (FIG. 9). A representative TEM image shows graphitic nanoplatelets (FIG. 3(a), inset) with a multi-layered texture near the edges, a feature typical of phylomorphic or layered- like materials. The morphology change from tubular to flake- like after activation is attributed to the longitudinal unzipping of the tubes by KOH. High-resolution TEM (HRTEM) images (FIG.3 (a, b) display a “worm-like”, interconnected porous structure, with micropores randomly distributed and occasionally an ordered area with a lattice spacing of 0.33 nm, in good agreement with the XRD results. The chemical nature of HPACs was further investigated using XPS. The XPS survey of HPACs is shown in FIG. 10. The high-resolution Cis spectrum of HPACs (FIG. 3(c)) can be deconvoluted into four separate peaks at 284.6, 286, 288.3 and 291.3 eV attributed to C-C / C=C, C-O / C-N, C=O, and O-C=O bonds, respectively. Similar chemical groups were also present for all the activated samples (see, for example, samples HPACM and HPACL in FIG. 3d and e). In addition to carbon, all samples before activation also contain N and O. The nitrogen is introduced during the hypergolic reaction from the aniline and nitric acid used.

[0089] Raman spectroscopy was used to further characterize all samples and the results are shown in FIG. 4. All spectra show the two peaks characteristic of carbon-based materials: one around 1340 cm"1(D band) and another at 1580 cm-1(G band). The D band is due to the lattice structural disorder (i.e., vacancies, edges and other defects), while the G band is attributed to the in-plane stretching vibration of the sp2carbons. The intensity ratio between the D and the G peak (ID / IG) is a measure of the material disorder. All non-activated samples show ID / IG < 1, but still much higher than 0.1-0.2 for crystalline graphite. Activation with KOH consistently creates more defects and the ID / IG increases for all samples (ID / IG ~ 1) (FIG. 4(b)). Previous reports have described these defects as zigzag / armchair edges, vacancies and more active sites. There appears to be a correlation between the differences in ID / IG before and after activation and the surface area obtained (FIG. 4(c)). The sample with the highest surface area is the one that also shows the largest ID / IG difference before and after activation (FIG. 4(d)).

[0090] Interestingly, the Cis spectra of HCs (FIG. 5(a)) and HCM (FIG. 11(a)) show a peak centered at 283.6 eV attributed to carbon pentagonal rings. Such metastable, reactive species have been also observed in the formation mechanism of carbon soot in flames. It seems that the environment present during flame pyrolysis promotes the formation of these pentagonal rings.The peaks at higher binding energies (e.g. 286, 288.3 and 291 .3 eV) are attributed to C-O / C-N, C=O, and O-C=O bonds, respectively. These highly reactive species at the edges of the carbon lattice promote the formation of pores during KOH activation. Note that the reactive pentagonal rings appear only in the samples where a hexagonally structured template was used. All the Cis spectra of the hypergolically derived carrions are shown in FIG. 11.

[0091] Based on the chemistry of hydroxylated fullerenes, which also contain pentagonal rings in their structure, the following activation mechanism was proposed for the samples. First, the pentagonal rings are decorated with hydroxyl groups upon reaction with KOH. Subsequent ring opening triggered by heating creates voids and leads to porosity (FIG. 5(a), inset).

[0092] However, if this was the only effect then high BET area in HCM (the sample templated with MCM-41) would have been seen as well, which also showed a relatively high amount of these pentagonal rings present. Since this was not the case, other drivers and specifically the presence of free radicals prior to activation were considered. Thus, ESR measurements were used to quantify the type and amounts of free radicals present in the samples (FIG. 5(b)). The spectra reveal the presence of stable, free radicals characterized by a single Gaussian derivative with similar peak-to-peak linewidth values (AHPP~ 5 G). The g-factor reflecting the chemical environment is also included. Carbon-centered radicals show g-values that are slightly higher compared to the free electron g-value of 2.0023. Values in the range of 2.003-2.004 usually correspond to carbon-based radicals with a nearby oxygen heteroatom. With respect to spin density, HCs. possesses the highest amount of spins (1.7 x 1016spins / g). Interestingly, HCM contains the second highest number of spins (1.1 x 1016spins / g) and a reasonable number of highly reactive pentagonal rings but its surface area after activation is much lower compared to HPACs indicating that an additional requirement is the presence of micropores which connect the main nanochannels of SB A- 15. Note that the amount of spins increases monotonically with the BET area in the sample (FIG. 5(c)). A summary table of ESR features of HC and CS300 samples is presented in Table 4. After activation, the g values (not shown) for all the materials decreased somewhat consistent with the decrease in oxygen concentration at elevated temperatures.

[0093] Based on the above, an additional mechanism of activation based on carbon radicals that takes place in tandem and is synergistic to that shown in FIG. 5 was proposed. In the first step, the potassium ions are reduced by the carbon radicals forming a carbocation and potassiummetal (equation 1). In the second step, a hydroxide ion replaces the carbocation through nucleophilic substitution, breaking the C-C bond into carbene and an alcohol (equation 2). Then, potassium metal and alcohol react to form potassium ethoxide (equation 3). Finally, in the fourth step, potassium ethoxide thermally decomposes to K2CO3 (equation 4). The breaking of C-C bonds along with the formation of K2CO3 are essential steps in creating porosity.

[0094] Cyclic CO2 adsorption-desorption studies. The CO2 capture and desorption behaviour of the HPACs was evaluated using a thermogravimetric analyser (TGA). The solid sorbents are first degassed and pre-treated with N2 at 200 °C to ensure the removal of volatiles or trapped moisture and thermally activate the sample, then exposed to CO2 for 15 min at 30 °C. Due to their high surface area and microporosity, the HPACs exhibit extremely fast capture kinetics. As shown in FIG. 6(a), a sharp linear weight gain was observed due to rapid CO2 uptake by the sample, reaching a capacity of ~ 1.25 mmol CO2 g'1. To the best of our knowledge, this is the highest reported capacity for an activated carbon measured by TGA. The adsorption was very fast that 99 % of CO2 uptake occurred in a span of 2 min signalling an ultra-fast CO2 adsorption process. The kinetics of CO2 adsorption is contrasted amongst different samples. FIG. 6(b) presents the CO2 adsorption as a function of time for the hypergolically treated (HPACs) and conventionally activated carbon (ACS300) samples with BET areas of 4800 and 2369 m2 / g, respectively. First, HPACs shows an almost double CO2 capacity (1.25 vs 0.67 mmol CO2 g'1, respectively. Second, the HPACs sample reaches its total capacity of -1.25 mmol CO2 g'1within2 minutes whereas the lower surface area material achieves roughly 47 % of its total capacity in that time frame.

[0095] To the best of our knowledge and consistent with the results above the capacity for HPACs is higher compared to what has previously reported for KOH activated carbons under the same dynamic conditions (TGA). For example, a capacity of 1.07 mmol g"1for KOH activated carbons derived from recycled polymers under pure CO2 conditions was previously demonstrated. Similarly, KOH mediated activation resulting in a carbon with a CO2 capacity of 0.76 mmol g'1was previously reported. Conversion of fly ash to activated carbon after alkali activation resulting in a capturing capacity of ~0.6 mmol g'1was previously reported. It is noted that, although there are higher CO2 adsorption capacities reported in the literature for carbonbased sorbents, they were not measured by the same technique as in this work or in the works referenced above. For instance, a straightforward synthesis of N-doped porous carbon using NaNH2 as porogen and nitrogen source with a CO2 adsorption capacity of 6.33 mmol g-1at 100 kPa and 273 K was previously reported. In another work, a photo-responsive sorbent based on a metalloporphyrin-fullerene doped metal organic framework reached a CO2 capacity of 2.69 mmol g-1at 1 bar and 273 was previously reported.

[0096] To gain further insights into the adsorption process, the CO2 adsorption data was fit to a pseudo first-order kinetics model. The choice of this model is justified by that the CO2 adsorption is reversible as evidenced by the several adsorption-desorption cycles shown in FIG. 6(a) and commented below. The experimental data were fitted using the following equation: qt= qe(l - ekt) (5) where qtis the amount of CO2 adsorbed at time t, qeis the adsorption at equilibrium (the total adsorption capacity), and k is the first order rate constant. A good fit is obtained for HPACs using one rate constant. In contrast, there are two distinct steps for the conventionally activated (ACS300) sample prior to equilibrium, one fast followed by a slower step. The rate constants of each step are summarized in Table 2. Note that the initial step for HPACs is about three times faster compared to the lower surface area sample.

[0097] Table 2. Fitting kinetics parameters for HPACs and a conventionally KOH activated carbon.Samples ki (min-1) k2 (min-1)HPACs 2.0Conventionally 0.7 0.04KOH activated carbon (ACS300)

[0098] To determine the rate limiting steps of the adsorption mechanism the Weber-Morris model, which is based on a multistep process, was used. The model usually includes three steps: i) diffusion of the gas molecules to the sorbent surface, ii) intraparticle diffusion (i.e. diffusion into the internal pores), and iii) the final equilibrium within the pores. Implicit to the model is that diffusion from the bulk to the surface and the surface reaction are fast and not the rate limiting steps. The model is expressed by: qt= kpt0 5+ C (6) where kpis the rate constant and C is a constant related to the boundary layer thickness.

[0099] As shown in FIG. 12, the data for HPACs can be fitted into the three-stage process described above with progressively slower rate constants indicating that adsorption occurs rapidly in Stage I. Adsorption becomes slower as CO2 travels through the internal pores (Stage II) and eventually the process reaches a plateau or saturation (Stage III). The rate constants for the individual steps are summarized in Table 3. The process for the conventionally activated sample appears more complex as the data is best fit using a four-stage model. Nevertheless, the rate constants in the first two steps which are likely the steps controlling the kinetics are faster for the hypergolically derived sample. These and other subtleties including correlating the CO2 capacity as well as the adsorption kinetics to the sample morphology and chemistry are currently under investigation and will be communicated in a forthcoming publication.

[0100] Table 3. Rate constants of Weber-Morris model for HPACs and a conventionally KOH activated carbon. kpikP2 kP3 kp4Samples(mmol g1min05) (mmol g1min05) (mmol g1min05) (mmol g1min05)HPACs 24 0A5 - 5.6 x 104Conven. activated0.52 0.046 0.058 92 x IO’4carbon (ACSaoo)

[0101] Easy regeneration is another critical property that must be considered, when designing CO2 sorbents. In this respect, porous carbons are preferred over other sorbents, such as zeolites because of the ease of regeneration due to the weak interactions involved (e.g. the heat of adsorption between carbon and CO2 is ~20 kJ mol-1). The HPACs, in addition to the excellent CO2 adsorption kinetics, also show rapid desorption kinetics, with complete desorption achieved within 3 min after the gas carrier is switched from CO2 to N .

[0102] Furthermore, practical CO2 capture applications require sorbents with long-term stability and regenerability with a minimum difference in adsorption / desorption temperatures or pressures to achieve lower cost and high efficiency. To this end, a temperature swing was used to evaluate the stability and regenerability of the HPACs in a short cycling time. CO2 cycling involved adsorption at 30 °C with subsequent desorption at 200 °C. In short, the HPACs can be easily, quickly and totally regenerated over multiple cycles without any loss of adsorption uptake or any noticeable changes in the desorption kinetics. The adsorption capacity was reserved through 10 adsorption - desorption cycles displaying excellent recyclability and stability.

[0103] Electrochemical performance. Lastly, the performance of HPACs as active materials for electrodes in a symmetric supercapacitor was evaluated using a two-electrode coin cell system and l-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4). Ionic liquid based electrolytes (ILs), composed of bulky organic cations allow operation in a wider voltage and temperature range with overall improved safety compared to the more traditional organic solvent-based electrolytes. Aqueous based systems tend to be more stable but suffer from low cell voltages, requiring the device to operate below the electrochemical potential for water decomposition (1.2 V). FIG. 7(a) shows the CV patterns at 50 mV s-1and different voltage windows. Fast scan rates are preferred because they emulate the fast charge / discharge rates required during operation of the supercapacitor. Note that at higher potentials (i.e. higher than 4V) decomposition of the electrolyte leads to significant increases in current density. Based on the above and the need for the voltammogram to be rectangular an operational voltage window of 3.5 V was chosen for the rest of the experiments. The cyclic voltammetry (CV, FIG. 7(b)) atdifferent scan rates showed the typical quasi-rectangular shape with low redox peaks. The former indicates non-Faradaic capacitive behaviour, at both low and high scan rates, typical of an electric double layer behavior. Consistent with the presence of oxygen containing functional groups in the material, a minor pseudocapacitive contribution is most likely superimposed on the rectangular CV profiles, which could affect the long term stability upon cycling.

[0104] The rectangular CV profile shape even at very high scan rates indicates that the cell exhibits predominantly capacitive behaviour with fast charge transport both in the bulk and at the interfaces. These features were confirmed by galvanostatic charge / discharge measurements (FIG. 7(c)), which yielded linear and symmetric profiles with high energy efficiency. The discharge times can be translated to a specific capacitance of 136, 130 and 102 F g"1at 0.5, 1, and 10 A g"1, respectively. The gravimetric energy density is 55 W h kgr-1with a power density of -900 W kgr-1at 1 A g-1. Importantly, for the same current density the volumetric energy density reached 57 Wh L-1at a volumetric power density of 920 W L-1. Note that for the majority of reports on electrodes based on activated carbon the corresponding volumetric power densities are either much smaller (e.g. 5-20 W h L-1) or are not reported at all.

[0105] Volumetric capacity remains the Achilles heel of porous carbons for supercapacitor devices. The volumetric and gravimetric capacity of cells based on HPACs exceeds those based on commercially activated carbons. For instance, the instant cell exhibits -4 times higher volumetric energy density compared to other high surface area, activated carbons (e.g. porous carbon (PC) from ACS Material with a BET area of -2000 m2g-1and YP-80F Kuraray carbon with a BET area of -2400 m2g-1) tested under the same experimental protocol (FIG. 7(d)). It was suggested that the high volumetric energy density is due to the high electrode density of 1.27 g cm"3. In contrast, the majority of activated carbons have densities between 0.4-0.7 g cm"3which leads to low density electrodes. A real-life test was also performed by connecting an LED to the symmetric cell (FIG. 7(e)). The cell could operate the 3.2 V green LED efficiently, and it could run the yellow and the red LEDs for more than 5 mins.

[0106] All in all and to the best of our knowledge the HPACs outperform other, previously reported KOH activated carbons under the same measurement conditions. For instance, in a recent work, a biomass derived, KOH activated carbon with an ultra-high BET area of 3950 m2g1shows a capacitance of 45 F g"1and an energy density of 56.6 W h kg1at a power density of 375 W kg1using a voltage window of 3 V but the volumetric capacity was not reported. Inaddition, Li et. al. used a highly hydrophilic pomelo peel to synthesize an activated carbon with a packing density of 0.63 g cm-3, displaying a maximum specific energy of 40.5 Wh kg-1and energy density of 25.5 Wh L-1.

[0107] In summary, an unexplored synthetic approach to prepare highly porous nanocarbons by using a combination of hypergolic reaction of a templated substrate followed by KOH activation was developed. This methodology permits the formation of porous carbons with ultra- high BET area (up to 4800 m2 / g) along with large pore volume, high micropores and narrow mesopores. The initial structure after etching of the silica template consists of tubular- carbon as shown by XRD and TEM / SEM. After KOH activation the tubular morphology is converted to turbostratic carbon with an interconnected worm-like network structure. The presence of highly reactive rim-based pentagonal carbon rings along with the high content of carbon radicals after the hypergolic reaction of the SBA-15 templated sample has emerged as a distinctive combination for the development of ultra-high surface area carbons. The absence of interconnected pores in the hexagonal channels in the case of MCM-41 is not conducive for the development of high surface area although the geometry of the template is the same as in SBA- 15. The ultra-high surface carbon acts as a highly efficient CO2 sorbent showing a capacity of ~ 1.25 mmol CCh / g along with ultra-fast CO2 adsorption kinetics, achieving 99 % filling capacity within 2 min. The kinetics of the adsorption follow a pseudo-first-order model with a rate constant 3 times higher compared to a conventionally treated sample. The adsorption also follows the Weber-Morris model with progressively slower rate constants indicating that diffusion of the gas molecules to the sorbent surface is fastest. In addition to the highCO2 capture capacity, the carbon sorbent is readily regenerated at low temperature and displays good stability over 10 repetitive adsorption-desorption cycling tests. Lastly, the volumetric capacitance of cells based on HPACs reaches a maximum of ~60 Wh L-1and a volumetric power density of 1 kW L-1, which are the highest reported values for activated carbons. The high volumetric capacity and power density are attributed to the high electrode density of 1.27 g cm-3. The reported approach can provide an alternative strategy to the design and synthesis of carbonbased materials with ultra-high surface areas suitable for sorbents, catalyst supports, and active materials for supercapacitors especially those requiring less space.

[0108] METHODS AND EXPERIMENTS. Materials. SBA-15 (< 150 pm particle size, pore size 4 nm), MCM-41 (pore size 4 nm), colloidal silica nanoparticles (LUDOX HS30, 30 wt % inwater) with an average diameter of 12 nm, potassium hydroxide and sodium hydroxide pellets were all purchased from Sigma- Aldrich. Fuming nitric acid (98 %) was purchased from ThermoFisher Scientific. Aniline (99.9 %) was purchased from Fisher Scientific. Sucrose (99 %) was obtained from Alfa Aesar. Deionized water (18.2 MQ-cm at 25 °C) was produced by a Barnstead Pacific TII system and was used throughout the experiments. All chemicals were used as received without further purification.

[0109] Synthesis of carbonaceous tubes via hypergolic reactions. Safety Note. All hypergolic experiments were conducted using small amounts of reagents in a fume hood. The carbon samples prepared via hypergolic reactions and prior to activation are denoted by HCX, where HC refers to Hypergolic Carbon, while x corresponds to the template (S for SBA-15, M for MCM-41 and L for LUDOX HS30, respectively).

[0110] The carbon / silica mixture used subsequently was synthesized following the hard- templating process. In short, 1 g commercially available SBA-15, a hexagonally ordered silica template, was infiltrated twice with an aqueous sucrose solution containing minute amounts of H2SO4. The composite was heat-treated in air (6 h at 100 °C followed by another 6 h at 160 °C). A Pyrex test tube was charged simultaneously with 0.4 g of the carbon / silica mixture and 500 pL of aniline, followed by the slow addition of 1.5 mL fuming nitric acid, HNO (98 %). Aniline triggers ignition after the addition of the acid. The residue inside the test tube was collected and thoroughly washed with deionized water, ethanol and acetone prior to drying at 100 °C. The SBA-15 template was removed by adding NaOH and heating at 80 °C. The final product after this step hereafter denoted as HCs was a fine black powder.

[0111] The same synthetic protocol was followed to synthesize HCM and HCL, where MCM- 41 and LUDOX HS30, were used as templates, respectively. Furthermore, the same synthetic procedure was used in order to synthesize a control sample without the use of any template, denoted as HCSUcr.

[0112] Synthesis of Highly Porous Activated Carbons (HP AC). Activated forms (referred to as HPACx) where x corresponds to the template (S for SBA-15, M for MCM-41 and L for LUDOX HS30, respectively) were synthesized by chemical activation of HCx with KOH. Briefly, 500 mg of the carbons prepared as described above were impregnated with an aqueous solution of KOH (50 % w / v) and dried at 100 °C overnight. The material was subsequently carbonized under N2 flow at 800 °C (5 °C / min) for 2 h (h = hours) followed by severalwashings with DI water and acetone. An additional washing with a solution of 6 M HC1 was also used to remove residual carbonates formed during the activation process. A schematic showing the steps of the synthesis process is shown in Scheme 1.

[0113] Scheme 1. Schematic showing the steps of the hypergolic synthesis process.

[0114] Conventionally synthesized carbon (CS300 and ACS300). The sample synthesized via thermal treatment at 300 °C is denoted by CSX, where CS refers to conventionally synthesized carbon, while x corresponds to the pyrolysis temperature. The low temperature profile was selected to simulate the temperature conditions during hypergolic reaction.

[0115] 1 g of commercially available SBA-15 was added to a 5 ml aqueous solution containing 1.25 g of sucrose and 0.14 g of H2SO4. The mixture was placed in a drying oven at 100 °C for 6 h, and subsequently the oven temperature was increased to 160 °C and maintained there for 6 h. The silica-carbon sample, containing partially polymerized and carbonized sucrose, was treated again at 100 °C and 160 °C after an extra addition of 0.8 g of sucrose, 0.09 g ofH2SO4 and 5 mL of H2O. The carbonization was accomplished by pyrolysis at 300 °C for Ih, under N2 (hereafter denoted as CS300). The SBA-15 template was removed by NaOH and heating at 80 °C. ACS300 was produced after activation of CS300 as described previously.

[0116] Electrochemical characterization. All electrochemical tests were performed using a customized battery tester (Ncwarc, China). Cyclic voltammograms were performed on a Biologic potentiostat in a two-electrode system. For the electrodes, the active material was initially homogeneously dispersed in N-methyl-2-pyrrolidone (NMP) adding poly-vinyl fluoride (PVDF, Sigma- Aldrich) as a binder and a conductive carbon (Ketjen Black) in a ratio of 80:10:10. The mixture was sonicated and vortexed to form a homogenous paste with the whole procedure repeated three times. The resulting homogeneous slurry was pasted on a carbon-coated aluminum foil with a 100 pm doctor blade. The casted thin film was dried at 120 °C under vacuum overnight. Discs with diameter of 15.8 mm were cut and dried at 120 °C under vacuum for 1 hour to remove any trapped humidity before being transferred in the glovebox filled with Argon. Assembly involved placing two electrodes in a 2032 coin cell with a glass fiber separator soaked with 90-100 pl of l-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4, Sigma- Aldrich, >99.0 % (HPLC)). Before actual testing, the electrodes were conditioned by cycling at a voltage window of 0.01-1.5 V for 10 cycles, followed by 20 cycles up to 2.5 V. The height of each electrode was carefully measured using a micrometer (Mitutoyo, accuracy 0.00005 inch). The specific capacitance of the active material (Cs, F g-1) and volumetric capacitance (Cv, F cm’3) was calculated from GCD discharge curve:Cs = 2 x ((I ■ t) / (m ■ V)) (6)Cv = (Cs(m ■ Vel)) (7) where I is the discharge current, t is discharging time (IR-drop was excluded), m is the mass of the active material on one electrode, V is potential window, and Vel is the volume of the material on the electrode.

[0117] Gravimetric and volumetric energy density and power density were calculated as follows:Eg = (Cs x V2) / 28.8 [Wh kg-1] (8)Pg = (Eg / t)3600 [W kg-1] (9)Ev = (CV X V2) / 28.8 [Wh L-1] (10)Pv = (Ev / t)3600 [W L’1] (11)

[0118] Characterization Techniques. XRD measurements were conducted with a D8Advance diffractometer (Brukcr AXS GmbH) using CuKa radiation ( / . = 1.54 A). All samples were deposited on background-free Si wafers and scanned over a 1-80° 29 range, in steps of 0.02° (20), at a rate of 0.2 s (s = second(s)) per step. XPS measurements were obtained by a Thermo Scientific Nexsa G2 Spectrometer with operating pressure ~ IxlO'9Torr.Monochromatic Al Ka x-rays (1486.6 eV) with photoelectrons collected from a 200 um diameter analysis spot at a 90° emission angle and a source to analyzer angle of 54.7°. A hemispherical analyzer determined electron kinetic energy, using pass energy of 200 eV for wide / survey scans, and 50 eV for high resolution scans. A flood gun was used for charge neutralization of non- conductive samples. All XPS spectra were deconvoluted with CasaXPS software. SEM images were obtained using a Zeiss Gemini 500 SEM. TEM images were collected using FEI Tecani 12 BioTwin TEM. High resolution TEM images (HRTEM) images were acquired using a FEI / Thcrmo Fisher Titan Themis CryoS / TEM at 300 kV. 0.5 % w / v suspensions were prepared and drop-casted into carbon coated copper grids. All N2 adsorption-desorption isotherms were measured by a Micromeritics ASAP 2460 with the use of ultrahigh pure N2 (99.999 %), as adsorbate. The carbon materials were outgassed under vacuum (10-4mbar) at 170 °C overnight. Glass filling rods were placed inside the sample cells to reduce the dead volume of the sample cell, which was automatically evaluated before each ran using helium (purity 99.999%) gas. All porosimetry isotherms were recorded at 77 K using a liquid N2 Dewar vessel at a relative pressure (P / Po) of I05to 0.99 for the HP AC materials and from 102to 0.99 for the HC nanomaterials. For HP AC materials, N2 adsorption-desorption isotherms consisted of 52 adsorption points and 36 desorption points. The equilibration interval was 30 seconds. Raman spectra were recorded using a Renishaw InVia confocal Raman microscope with a laser excitation line at 532 nm. Continuous-wave ESR spectra were recorded on an ELEXSYS ESR spectrometer (Bruker Instruments. Billerica, MA) at X-band (~ 9.3 GHz) at room temperature. Spin counting was performed by comparison of the signal intensity to a 2,2-diphenyl-l- picrylhydrazyl (DPPH) standard. CO2 adsorption and desorption performance of HP AC was evaluated by a Thermo Gravimetric Analyzer (TGA, Discovery SDT 650, TA Instrument). In a typical dynamic CO2 adsorption TGA run, the initial degassing was carried out by heating the sample under flowing N2 at 10 °C min'1up to 200 °C, and then isothermally held at 200 °C for 12 hours to facilitate desorption. The initial desorption step leads to the release of moisture andother volatiles trapped in the pores of the material. The heated sample was then rapidly cooled to 30 °C and then held at 30 °C for 3 hours, followed by switching the gas flow to bone-dry CO2 (a de-humidifier was attached to the inlet gas stream to remove any moisture) which is supplied at 100 ml / min for 15 min. The CO2 capture capacity of the material was determined by measuring the mass uptake of the sample when exposed to pure CO2 and the capacity was expressed as mmol of CO2 / g of sorbent. Sample regeneration was conducted after each adsorption cycle by ramping the temperature to 200 °C at 10 °C min'1, and then holding at 200 °C for 1 hour. Dynamic CO2 capture and release test was carried out by repeating the adsorption and regeneration steps sequentially for 10 cycles.

[0119] Supporting Information. Quenched Solid Density Functional Theory (QSDFT) pore size distributions based on the ASiQwin N2-carbon, slit-cylinder kernel for all the activated carbonaceous materials. (FIG. 8); SEM images of HPACs. (FIG. 9); XPS survey of HPACs. The inset displays the atomic elemental composition of the corresponding sample. (FIG. 10);Deconvoluted high-resolution Cis spectra of the hypergolically derived carbons (a, b and c) and CS300 (d). (FIG. 11)); A summary table of ESR features of HC and CS300 samples. (Table 4);CO2 uptake fitted with an intraparticle diffusion model indicating the different stages of the CO2 adsorption process. (FIG. 12).

[0120] Table 4. A summary table of ESR features of HC and CS300 samples.

[0121] Although the present disclosure has been described with respect to one or more particular embodiments and / or examples, it will be understood that other embodiments and / or examples of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. A method of making a porous carbon material comprising: contacting one or more carbon precursor(s) and one or more templating substrate(s) under hypergolic conditions, wherein a templated material is formed; removing substantially all or all of the templating substrate(s) from the templated material; activating the material resulting after the removing substantially all or all of the templating substrate(s) from the templated material; and carbonizing the activated material, wherein the porous carbon material is formed.

2. The method of claim 1, wherein the one or more carbon precursor(s) and the one or more templating substrate(s) are present in a reaction mixture.

3. The method of claim 2, the method further comprising: forming a reaction mixture comprising: the one or more carbon precursor(s), the one or more templating substrate(s), and optionally, one or more solvent(s); and optionally, heat treating the mixture.

4. The method of claim 1, wherein the carbon precursor(s) is / are independently chosen from carbohydrates, structural analogs thereof, and any combination thereof.

5. The method of claim 1, wherein one or more or all of the carbon precursor(s) is / are a water- soluble carbon precursor or water-soluble carbon precursors.

6. The method of claim 1, wherein the carbon precursors(s) is / are present at about 50 wt. % to about 70 wt.%.

7. The method of claim 1 , wherein the templating substrate(s) is / are chosen from silica nanoparticlcs and any combination thereof.

8. The method of claim 7, at least a portion of, substantially all, or all of the templating substrate(s) is / are porous silica nanoparticle(s).

9. The method of claim 1, wherein the templating precursors(s) is / are present at about 30 wt.% to about 50 wt.%.

10. The method of claim 1, wherein the carbon precursor(s) : templating precursors(s) mass ratio is about 1 : 1 to about 4 : 1.

11. The method of claim 3, wherein the reaction mixture heating is carried out at about 90 °C to about 180 °C and / or for about 1 hour to about 20 hours.

12. The method of claim 1, wherein the contacting the one or more carbon precursor(s) and the one or more templating substrate(s) under the hypergolic conditions comprises contacting the one or more carbon precursor(s) and the one or more templating substrate(s) with one or more first hypergolic reagent(s); and contacting the contacted one or more carbon precursor(s), the one or more templating substrate(s), and the one or more first hypergolic reagent(s) with one or more second hypergolic reagent(s).

13. The method of claim 12, wherein the first hypergolic reagent(s) is / are chosen from aniline, furfuryl alcohol, structural analogs thereof, and any combination thereof.

14. The method of claim 12, wherein the second hypergolic reagent(s) is / are chosen from fuming nitric acid, hydrogen peroxide, red fuming nitric acid, structural analogs thereof, and any combination thereof.

15. The method of claim 12, wherein the volume ratio of first hypergolic reagent(s) : second hypergolic rcagcnt(s) volume ratio is about 0.5 : 1 to about 1 : 5.

16. The method of according claim 1, wherein the activating comprises: contacting, one or more time(s) the material after the removal of substantially all or all of the templating substrate(s) with one or more base(s); and optionally, heating the base-treated templated product.

17. A templated material comprising a carbonaceous material disposed on at least a portion or substantially all or all of a surface or surfaces of a templating substrate, wherein the carbonaceous material comprises one or more or all of the following:(i) about 3 to about 20 atomic percent of rim-based pentagons; or(ii) comprises one or more radical specie(s) (e.g., carbon-centered radicals, oxygen-centered radicals, or any combination thereof; or(iii) carbon cylinders.

18. The templated material of claim 17, wherein the carbonaceous material comprises one or more radical specie(s), wherein the amount of the radical specie(s) corresponds to or the number of the radical species corresponds to about 1 x 1013to 1 x 1017spins / gram of the templated material.

19. The templated material of claim 17, wherein the carbonaceous material comprises a plurality of carbon structures and a majority of the carbon structures are not hexagonal carbon structures.

20. A porous carbon material comprising:(i) a surface area of about 3500 m2 / g to about 4900 m2 / g; or(ii) a plurality of micropores and a plurality of mesopores; or(iii) a plurality of micropores and a plurality of mesopores and a surface area of about 3500 m2 / g to about 4900 m2 / g.21 . The porous carbon material of claim 20, wherein the porous carbon material comprises carbon cylinders.

22. A filtration method comprising use of one or more porous carbon material(s) of claim 20.

23. A catalytic method comprising use of one or more porous carbon materials(s) of claim 20.

24. A carbon capture and / or carbon sequestration method comprising use of one or more porous carbon material(s) of claim 20.

25. A device comprising one or more porous carbon material(s) of claim 20.

26. The device of claim 25, wherein the device is a filtration device.

27. The device of claim 26, wherein the filtration device is configured for normal flow, deadend flow, tangential flow, or any combination thereof.

28. The device of claim 26, wherein the filtration device is configured for gravity filtration, centrifugation, gas-pressurization filtration, or any combination thereof.

29. The device of claim 25, wherein the device is a carbon capture device.

30. A device comprising one or more electrode(s), wherein the electrode(s) independently comprise one or more porous carbon material(s) of claim 20.

31. The device of claim 30, wherein the device is an energy -generating device, or an energy storage device.

32. The device of claim 30, wherein the device is an electrochemical device.

33. The device of claim 30, wherein the device is a fuel cell, a battery, a water-electrolysis device, or an electrodialysis device.

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