EP4731336A1 - Porous carbon and method for the manufacture and uses thereof - Google Patents

Abstract

A method of forming a porous carbon includes pyrolyzing a functionalized polyphenylene ether to provide the porous carbon material. The porous carbon material has a particular distribution of pores. Porous carbon materials prepared according to the method and uses thereof are also disclosed.

Description

22SHPP0070-WO-PCT (SS290015PCT) POROUS CARBON AND METHOD FOR THE MANUFACTURE AND USES THEREOF CROSS REFERENCE TO RELATED APPLICATION This application claims priority to European Patent Application No.23180278.6, filed on June 20, 2023, the contents of which are hereby incorporated by reference in their entirety. BACKGROUND [0001] Carbonaceous materials are used for many electrochemical and adsorption applications. A combination of good electrical conductivity and low chemical reactivity make carbonaceous materials potentially more desirable candidates than metals for many electrochemical applications. Carbon materials are also highly durable and can sustain strong oxidizing and reducing environments inside energy conversion and energy storage devices, such as fuel cells, double layer capacitors or lithium-ion batteries. Carbon materials find further use in, for example, adsorption related applications, purification of industrial gases, anti-pollution devices, gas separation, liquid- phase purification processes in the food and chemical industries, liquid-phase recovery and separation, as a catalyst or catalyst support material, and analytical and medicinal applications. [0002] Carbon materials may be formed by pyrolyzing polymers at very high temperatures in a non- oxidative atmosphere. To enhance the surface area of the carbon material, it may be treated further to produce an activated carbon material. For example, polyacrylonitrile (PAN) has been used as a precursor to carbon fibers, and other precursors such as pitch, phenolic resin, and polyacetylenes, have been employed for making carbon materials. Carbons made from the aforementioned precursors often exhibit a low surface area in the absence of a subsequent activation process. Activation can distort, introduce defects, or completely destroy a formed carbon material. [0003] Accordingly, it would be particularly advantageous to provide a carbon material derived from a synthetic polymer that exhibits a desirable combination of high surface area, a particular pore size distribution, good electric conductivity, and satisfactory mechanical strength. SUMMARY [0004] An aspect of the present disclosure is a porous carbon having a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores comprising the first portion of pores, the second portion of pores, and the third portion of pores; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) 22SHPP0070-WO-PCT (SS290015PCT) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0005] Another aspect is a method of forming a porous carbon, the method comprising pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) 22SHPP0070-WO-PCT (SS290015PCT) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0006] Another aspect is a porous carbon having a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers. [0007] Another aspect is an article comprising the porous carbon or a porous carbon made by the method; preferably, wherein the article is: a catalyst support, wherein a catalyst is disposed on the porous carbon; or a gas diffusion layer; or a redox flow battery electrode. [0008] Another aspect is a catalyst support material comprising a porous carbon having a catalyst disposed thereon, wherein, the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C, or 450 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether comprises repeating units of Formula (I) 22SHPP0070-WO-PCT (SS290015PCT) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group,, provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0009] Another aspect is a gas diffusion layer comprising a porous carbon, wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers. [0010] The above described and other features are exemplified by the figures and detailed description. BRIEF DESCRIPTION OF THE FIGURES [0011] FIG.1 is a scanning electron microscope (SEM) image of a porous carbon according to Comparative Example 1. 22SHPP0070-WO-PCT (SS290015PCT) [0012] FIG.2 is a SEM image of a porous carbon according to Example 1. DETAILED DESCRIPTION [0013] Existing porous carbon materials suffer from various technical limitations including undesirable pore size distributions. The present inventors have discovered that porous carbon materials can be prepared from certain functionalized polyphenylene ethers. Careful selection of the functionalized polyphenylene ether and carbonization conditions can provide controlled, tunable pore size distributions. A significant advantage is therefore provided by the present disclosure. [0014] Accordingly, an aspect of the present disclosure is a method of forming a porous carbon. The method comprises pyrolyzing a functionalized polyphenylene ether to provide the porous carbon. The functionalized polyphenylene ether comprises repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, a carboxylic acid, a bromide, a chloride, a chloroalkyl group, a silyl group, a quaternized ammonium group,. [0015] The functionalized polyphenylene ether can comprise 5 to 55 weight percent of the repeating units according to Formula (II) or (III), based on the total weight of the functionalized polyphenylene ether. For example, the functionalized polyphenylene ether can comprise 10 to 45 weight percent, or 10 to 40 weight percent, or 15 to 40 weight percent, or 15 to 35 weight percent of the repeating units according to Formula (II) or (III), each based on the total weight of the functionalized polyphenylene ether. Conversely, the functionalized polyphenylene ether can comprise 45 to 95 weight percent of the repeating units according to Formula (I), based on the total weight of the functionalized polyphenylene ether. For example, the functionalized polyphenylene ether can comprise 55 to 90 weight percent, or 60 to 90 weight percent, or 60 to 85 weight percent, or 65 to 85 weight percent of the repeating units according to Formula (I), each based on the total weight of the functionalized polyphenylene ether. In an aspect, the functionalized polyphenylene ether is a copolymer consisting of repeating units according to Formula (I) and at least one of Formula (II) or (III). Stated another way, in an aspect, repeating units different from Formulas (I), (II), and (III) can be excluded from the functionalized polyphenylene ether. 22SHPP0070-WO-PCT (SS290015PCT) [0016] In an aspect, the functionalized polyphenylene ether can comprise a sulfonated polyphenylene ether (i.e., R in Formula (II) or (III) is a sulfonic acid group). Exemplary sulfonated polyphenylene ethers can be, for example, as in International Publication No. WO 2020/254885, the content of which is incorporated by reference in its entirety. For example, the functionalized polyphenylene ether can comprise a sulfonated polyphenylene ether comprising repeating units of . In particular, when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mole percent (mol%), preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. In an aspect, repeating units other than those according to formulas (IV)-(VII) can be excluded from the sulfonated polyphenylene ether. [0017] In an aspect, the functionalized polyphenylene ether can comprise a carboxylated polyphenylene ether (i.e., R in Formula (II) or (III) is a carboxylic acid group). Exemplary carboxylated polyphenylene ethers can include those prepared as described in Journal of Membrane Science, 67 (1992) 191-210, the content of which is incorporated by reference in its entirety. For example, the functionalized polyphenylene ether can comprise a carboxylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIB) 22SHPP0070-WO-PCT (SS290015PCT) [0018] In an aspect, the functionalized polyphenylene ether can comprise a carboxylated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (VIII), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (IX): wherein each amount is based on total moles of repeating units in the carboxylated polyphenylene ether copolymer. In an aspect, repeating units other than those according to formulas (IV), (VIII), (VI), and (IX) can be excluded from the carboxylated polyphenylene ether. [0019] In an aspect, the functionalized polyphenylene ether can comprise a chloromethylated polyphenylene ether (i.e., R in Formula (II) is a chloromethyl group or R in Formula (III) is a chloro group). Exemplary chloromethylated polyphenylene ethers can include those prepared as described in, for example, European Patent Application No. EP23169594.1, the content of which is incorporated by reference in its entirety. For example, the functionalized polyphenylene ether can comprise a chloromethylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIC) . [0020] In an aspect, the functionalized polyphenylene ether can comprise a chloromethylated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (X), 1 mol% or less 22SHPP0070-WO-PCT (SS290015PCT) of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (XI): wherein each amount is based on total moles of repeating units in the chloromethylated poly(phenylene ether) copolymer. In an aspect, repeating units other than those according to formulas (IV), (X), (VI), and (XI) can be excluded from the chloromethylated polyphenylene ether. [0021] In an aspect, the functionalized polyphenylene ether can comprise a silylated polyphenylene ether (i.e., R in Formula (II) or (III) is a silyl group of the formula -SiR’₃, wherein R’ is independently at each occurrence a C_1-6 alkyl group or a C_6-12 aryl group, preferably a methyl group or a phenyl group). Exemplary silylated polyphenylene ethers can include those prepared as described in, for example, Journal of Membrane Science 97 ( 1994) 275-282, the content of which is incorporated by reference in its entirety. For example, the functionalized phenylene ether can comprise a silylated polyphenylene ether comprising repeating units of Formula (I) and Formula wherein R’ is independently at each occurrence a C_1-6 alkyl group or a C_6-12 aryl group, preferably a methyl group or a phenyl group. [0022] In an aspect, the functionalized polyphenylene ether can comprise a silylated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (XII), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (XI): 22SHPP0070-WO-PCT (SS290015PCT) wherein R’ is independently at each occurrence a C_1-6 alkyl group or a C_6-12 aryl group, preferably a methyl group or a phenyl group, and wherein each amount is based on total moles of repeating units in the silylated poly(phenylene ether) copolymer. In an aspect, repeating units other than those according to formulas (IV), (XII), (VI), and (XIII) can be excluded from the silylated polyphenylene ether. [0023] In an aspect, the functionalized polyphenylene ether can comprise a quaternized polyphenylene ether. As used herein, the term “quaternized polyphenylene ether” can refer to a polyphenylene ether comprising repeating units comprising a quaternized ammonium group, a quaternized phosphonium group, a quaternized sulfonium group, a quaternized arsonium group, a quaternized stibonium group, a quaternized bismathonium group, or a combination thereof. In a specific aspect, the functionalized polyphenylene ether can comprise a quaternized ammonium group (i.e., R in Formula (II) or (III) is a quaternary ammonium group of the formula -NR”₃, wherein R” is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group, preferably a methyl group or a phenyl group). Exemplary quaternized polyphenylene ethers can include those prepared as described in, for example, Int. J. Mol. Sci.2019, 20, 3678, the content of which is incorporated by reference in its entirety. In an aspect, the functionalized polyphenylene ether can comprise a quaternized ammonium polyphenylene ether, wherein the ammonium group can comprise, for example, trimethylammonium, 1-methylpyrrolidinium, or 1-methylimidazolinium. For example, the functionalized polyphenylene ether can comprise a quaternized polyphenylene ether comprising repeating units of Formula (I) and Formula (IIE) wherein R” is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group, preferably a methyl group or a phenyl group. [0024] In an aspect, the functionalized polyphenylene ether can comprise a quaternized polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (XIV), 1 mol% or 22SHPP0070-WO-PCT (SS290015PCT) less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (XV): wherein R” is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group, preferably a methyl group or a phenyl group, and wherein each amount is based on total moles of repeating units in the quaternized poly(phenylene ether) copolymer. In an aspect, repeating units other than those according to formulas (IV), (XIV), (VI), and (XV) can be excluded from the quaternized polyphenylene ether. [0025] Without wishing to be bound by theory, it is believed that functionalizing the polyphenylene ether prior to pyrolysis can enable a desirable porosity distribution. For example, a silylated polyphenylene ether (e.g., comprising repeating units comprising trimethyl silyl groups) can provide higher penetrant permeability due to a higher volume fraction of micropores (e.g., greater than 7^) in the resultant porous carbon materials. In contrast, a sulfonated polyphenylene ether (e.g., comprising repeating units comprising sulfonate groups) can provide a porous carbon material with higher selectivity due to an increased volume fraction of ultra-micropores (e.g., less than 7^). [0026] The functionalized polyphenylene ether (prior to carbonization) can have an intrinsic viscosity of 0.03 to 2 deciliter per gram (dl/g). For example, the poly(phenylene ether) can have an intrinsic viscosity of 0.25 to 1.7 dl/g, specifically 0.25 to 0.7 dl/g, more specifically 0.35 to 0.55 dl/g, even more specifically 0.35 to 0.50 dl/g, measured at 25ºC in chloroform using an Ubbelohde viscometer. [0027] The functionalized polyphenylene ether is pyrolyzed to provide the porous carbon. Pyrolysis can be conducted at a temperature of 200 to 800°C, or 450 to 800°C and for a time of 1 to 150 minutes. Preferably, pyrolysis is conducted in an inert atmosphere, for example under nitrogen argon, helium, or vacuum. [0028] In an aspect, prior to pyrolysis, the functionalized polyphenylene ether can be heat treated. Without wishing to be bound by theory, it is believed that including an initial heat treatment step prior to pyrolysis can provide the desired pore structure in the final porous carbon product. Functionalized polyphenylene ether exhibits a glass transition temperature (Tg) that increases linearly with the degree of functionalization. This can enable efficient crosslinking during an initial 22SHPP0070-WO-PCT (SS290015PCT) heat treatment step, which can improve the stability of the material. Under such conditions, decomposition of the functional groups of the functionalized polyphenylene ether can induce formation of micro-voids in the precursor material, which are retained as micropores in the carbonized polymer matrix. Though molecular chains relaxations can repack some of these voids, crosslinking can reduce the relaxations, retaining the micro-voids, ultimately providing the desired porous carbon with a turbostratic (i.e., less graphitic) structure. [0029] The heat treating can comprise heating the functionalized polyphenylene ether to a temperature of 200 to 250°C for 1 to 120 minutes. Preferably, the heat treatment is conducted in the presence of an oxidant, for example air, oxygen, or an oxygen-containing gas stream. Preferably, the pyrolysis is conducted under neat conditions. For example, in an aspect, the functionalized polyphenylene ether is not dissolved or dispersed in a solvent prior to pyrolysis. [0030] In an aspect, pyrolysis of the functionalized polyphenylene ether can be in the presence of a pore former. As used herein, the term “pore former” refers to an organic compound that volatilizes or decomposes at a temperature less than the pyrolysis temperature. When an initial heat treatment of the functionalized polyphenylene ether is conducted, the pore former can preferably volatilize or decompose at a temperature greater than the heat treatment temperature. For example, a suitable pore former can volatilize or decompose at a temperature of greater than 200 to 250 °C and less than 450 to 800°C. In an aspect, a suitable pore former can volatilize or decompose at a temperature of greater than 250 to less than 450°C. The pore former can either completely decompose or volatilize in the desired temperature range or leave traces of residue after carbonization. [0031] In an aspect, the functionalized polyphenylene ether and the pore former can be combined such that at least a portion of the pore former is dissolved or dispersed in the funcationalized polyphenylene ether. The pore size and distribution created by the pore formers can be regulated by the molecular weight and amounts of the pore formers used. In an aspect, the pore former can be a thermoplastic material. Exemplary pore formers can include polystyrene or polymethyl methacrylate. [0032] Without wishing to be bound by theory, it is believed that the combination of the functionalized polyphenylene ether and the pore former can provide a porous structure, for example having a particular combination of pore sizes derived from the pore former (e.g., macropores, having a diameter of 0.01 to 100 micrometers) and from devolatilization of the functionalized polyphenylene ether (e.g., micropores, having a diameter of less than 0.01 micrometers). In some aspects, no pore former is used and the desired pore size distribution can be achieved by selection of the functionalized polyphenylene ether. [0033] Pyrolyzing the functionalized polyphenylene ether according to the method described herein can provide a porous carbon material. The porous carbon material has a plurality of pores having a 22SHPP0070-WO-PCT (SS290015PCT) diameter of 100 micrometers or less. In an aspect, the porous carbon can have a first portion of pores having a diameter of less than 0.01 micrometers, and a second portion of pores having a diameter of 0.01 to 100 micrometers. In an aspect, the porous carbon can have a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers. [0034] The porous carbon can have a porosity of 1 to 90 volume percent, based on the total volume of the porous carbon. For example, the porous carbon can have a porosity of 10 to 90 volume percent. In an aspect, the porous carbon can have a pore volume fraction of greater than 0.08 cubic centimeters per gram (cm³/g). [0035] The porous carbon can be in the form of a powder, a fiber, or a sheet. [0036] The porous carbon of the present disclosure can find use in various applications, such as adsorption related applications, purification of industrial gases, anti-pollution devices, gas separation, and as a catalyst or catalyst support material. Accordingly, an article comprising the porous carbon represents another aspect of the present disclosure. [0037] In an aspect, the porous carbon can be useful as a catalyst support material. Accordingly, a catalyst support comprising the porous carbon represents another aspect of the present disclosure. A catalyst can be disposed on at least a portion of the surface of the porous carbon. In an aspect, a catalyst can be disposed in a pore of the porous carbon. [0038] A gas diffusion layer comprising the porous carbon represents another aspect of the present disclosure. The gas diffusion layer comprising the porous carbon can be a component of a fuel cell. For example, a fuel cell can comprise an anode, a cathode, and an electrolyte membrane, wherein the anode or the cathode can comprise the gas diffusion layer comprising the porous carbon according to the present disclosure. In an aspect, a fuel cell can comprise the following layers in serial contact: a first separator or bipolar plate, a first gas diffusion layer, an anode comprising a catalyst, a solid polymer electrolyte or a proton exchange membrane, a cathode comprising a particulate catalyst, a second gas diffusion layer, and a second separator or bipolar plate. At least one of the first and second gas diffusion layers comprises the porous carbon according to the present disclosure. [0039] An electrode for a redox flow battery represents another aspect of the present disclosure. For example a redox flow battery can comprise a positive electrode cell comprising a positive electrode and a catholyte solution, a negative electrode cell comprising a negative electrode and an anolyte solution, and a membrane disposed between the positive electrode cell and the negative electrode cell. At least one of the positive electrode and the negative electrode can comprise a composite comprising the porous carbon according to the present disclosure. 22SHPP0070-WO-PCT (SS290015PCT) [0040] Additional applications include porous adsorbents for gas separation and gas storage, air purification and water filtration, . [0041] This disclosure is further illustrated by the following examples, which are non-limiting. EXAMPLES [0042] Exemplary substituted polyphenylene ethers are described in Table 1. Table 1 PPE Chemical Description Chemical Structure sPPE Sulfonated polyphenylene ether, prepared according to WO2020254885. cPPE Carboxylated polyphenylene ether, prepared according to Journal of Membrane Science, 67 (1992) 191-210. cmPPE Chloromethylated polyphenylene ether, prepared according to EP23169594.1. siPPE Silylated polyphenylene ether, prepared according to Journal of Membrane Science 97 ( 1994) 275-282, wherein in R’ is methyl or phenyl. qPPE Quaternized polyphenylene ether, prepared according to Int. J. Mol. ^^ ^^^ ^ ^^ Sci.2019, 20, 3678, wherein R’ is methyl. ^ ^ ^^ ^^ [0043] Porous carbon materials will be prepared through pyrolysis of the various substituted polyphenylene ethers described in Table 1. A range of temperatures from 450 to 800°C and time from 3 to 120 minutes will be tested, under vacuum and using a heating ramp rate of 10°C per minute in each example. Prior to the carbonization, the precursor material will be heat-treated under aerobic conditions in air at 220°C for up to 120 minutes. [0044] Depending on the conditions of carbonization, a range of integral pore volume fraction and pore dimensions are obtained. Typically, improved pore volume and pore dimensions are obtained at higher carbonization temperatures. [0045] Pore volume fractions of greater than 0.08 cm³ per gram, with pore dimensions exceeding 1 nanometer will be obtained. Advantageously, these features can provide improved support materials for catalysts. Comparative Example 1 22SHPP0070-WO-PCT (SS290015PCT) [0046] An unfunctionalized poly(phenylene ether) was carbonized by pyrolysis at a temperature of 500°C for 90 minutes, under inert atmosphere. Prior to carbonization, the unfunctionalized poly(phenylene ether) was pretreated in air at 220 °C for 90 minutes. The carbonized poly(phenylene ether) was imaged using scanning electron microscopy, shown in FIG.1. Pore sizes were also characterized using nitrogen adsorption isotherm measurements at 77 K. Example 1 [0047] A sulfonated poly(phenylene ether) was carbonized by pyrolysis at a temperature of 500°C for 90 minutes, under inert atmosphere. Prior to carbonization, the unfunctionalized poly(phenylene ether) was pretreated in air at 220 °C for 90 minutes. The carbonized sulfonated poly(phenylene ether) was imaged using scanning electron microscopy, shown in FIG.2. Pore sizes were also characterized using nitrogen adsorption isotherm measurements at 77 K. [0048] It was unexpectedly found that the sulfonated poly(phenylene ether) provided a carbonized material having a particular pore size distribution, which can be advantageous for certain application. In particular, a portion of pores having a diameter of less than 20 Angstroms were observed, which, without wishing to be bound by theory, are believed to be useful for depositing catalyst material. A portion of pores having an average diameter of 1000 to 15,000 Angstroms were also observed, which, without wishing to be bound by theory, are believed to be useful for penetrant transport through the material. The desirable pore size distribution was achieved even in the absence of a pore former. In contrast, carbonization of unfunctionalized poly(phenylene ether) does not lead to a significant population of pores that are less than 5 Angstroms in diameter. [0049] This disclosure further encompasses the following aspects. [0050] Aspect 1: A method of forming a porous carbon, the method comprising pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) 22SHPP0070-WO-PCT (SS290015PCT) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH₄ ⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0051] Aspect 2: The method of aspect 1, wherein the functionalized polyphenylene ether comprises the sulfonated polyphenylene ether copolymer. [0052] Aspect 3: The method of aspect 1, wherein the functionalized polyphenylene ether comprises a carboxylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIB) . [0053] Aspect 4: The method of aspect 1, wherein the functionalized polyphenylene ether comprises a chloromethylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIC) 22SHPP0070-WO-PCT (SS290015PCT) . [0054] Aspect 5: The method of claim 1, wherein the functionalized polyphenylene ether comprises a silylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IID) wherein R’ is independently at each occurrence a C_1-6 alkyl group or a C_6-12 aryl group. [0055] Aspect 6: The method of claim 1, wherein the functionalized polyphenylene ether comprises a quaternized polyphenylene ether comprising repeating units of Formula (I) and Formula (IIE) wherein R’ is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group. [0056] Aspect 7: The method of any of claims 1 to 6, wherein pyrolyzing the functionalized polyphenylene ether is in the presence of a pore former. [0057] Aspect 8: The method of any of claims 1 to 7, wherein the porous carbon has a pore volume fraction of greater than 0.08 cm³ per gram. [0058] Aspect 9: The method of any of aspects 1 to 8, further comprising heat treating the functionalized polyphenylene ether prior to the pyrolyzing, preferably wherein the heat treating comprises heating the functionalized polyphenylene ether to a temperature of 200 to 250°C for 1 to 120 minutes. [0059] Aspect 10: The method of claim 9, wherein the heat treating is in the presence of an oxidant, preferably air, oxygen, or oxygen-containing gases. [0060] Aspect 11: The method of any of claims 1 to 10, wherein the pyrolyzing is in an inert atmosphere, preferably wherein the inert atmosphere comprises nitrogen, argon, helium, or under vacuum. [0061] Aspect 12: A porous carbon made by the method of any of aspects 1 to 11. [0062] Aspect 13: A porous carbon having a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers. 22SHPP0070-WO-PCT (SS290015PCT) [0063] Aspect 14: An article comprising the porous carbon of claim 12 or 13 or a porous carbon made by the method of any of claims 1 to 11; preferably, wherein the article is: a catalyst support, wherein a catalyst is disposed on the porous carbon; or a gas diffusion layer; or a redox flow battery electrode. [0064] Aspect 15: A catalyst support material comprising a porous carbon having a catalyst disposed thereon, wherein, the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether comprises repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group, provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): 22SHPP0070-WO-PCT (SS290015PCT) wherein each X is independently hydrogen, sodium, potassium, or NH₄ ⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0065] Aspect 16: A gas diffusion layer comprising a porous carbon, wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers. [0066] Aspect 17: A porous carbon having a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores comprising the first portion of pores, the second portion of pores, and the third portion of pores; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit 22SHPP0070-WO-PCT (SS290015PCT) of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. [0067] Aspect 18: The porous carbon of aspect 17, wherein the functionalized polyphenylene ether comprises the sulfonated polyphenylene ether copolymer. [0068] Aspect 19: The porous carbon of aspect 17, wherein the functionalized polyphenylene ether comprises a carboxylated polyphenylene ether comprising repeating units of Formula (I) and Formula * . [0069] Aspect 20: The porous carbon of aspect 17, wherein the functionalized polyphenylene ether comprises a chloromethylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIC) . [0070] Aspect 21: The porous carbon of aspect 17, wherein the functionalized polyphenylene ether comprises a silylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IID) 22SHPP0070-WO-PCT (SS290015PCT) wherein R’ is independently at each occurrence a C_1-6 alkyl group or a C_6-12 aryl group. [0071] Aspect 22: The porous carbon of aspect 17, wherein the functionalized polyphenylene ether comprises a quaternized polyphenylene ether comprising repeating units of Formula (I) and Formula (IIE) wherein R’ is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group. [0072] Aspect 23: The porous carbon of any of aspects 17 to 22, wherein pyrolyzing the functionalized polyphenylene ether is in the presence of a pore former. [0073] Aspect 24: The porous carbon of any of aspects 17 to 23, wherein the porous carbon has a pore volume fraction of greater than 0.08 cm³ per gram. [0074] Aspect 25: The porous carbon of any of aspects 17 to 24, further comprising heat treating the functionalized polyphenylene ether prior to the pyrolyzing, preferably wherein the heat treating comprises heating the functionalized polyphenylene ether to a temperature of 200 to 250°C for 1 to 120 minutes. [0075] Aspect 26: The porous carbon of aspect 25, wherein the heat treating is in the presence of an oxidant, preferably air, oxygen, or oxygen-containing gases. [0076] Aspect 27: The porous carbon of any of aspects 17 to 26, wherein the pyrolyzing is in an inert atmosphere, preferably wherein the inert atmosphere comprises nitrogen, argon, helium, or under vacuum. [0077] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles. [0078] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or” unless clearly stated otherwise. Reference throughout the specification to “an 22SHPP0070-WO-PCT (SS290015PCT) aspect” means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term “combination thereof” as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. [0079] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears. [0080] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference. [0081] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. [0082] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon- carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH₂-) or, propylene (-(CH₂)₃-)). “Cycloalkylene” means a divalent cyclic alkylene group, -C_nH_2n-x, 22SHPP0070-WO-PCT (SS290015PCT) wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo atoms (e.g., bromo and fluoro), or only chloro atoms can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C_1-9 alkoxy, a C_1-9 haloalkoxy, a nitro (-NO₂), a cyano (-CN), a C_1-6 alkyl sulfonyl (-S(=O)₂-alkyl), a C_6-12 aryl sulfonyl (-S(=O)₂-aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH₃C₆H₄SO₂-), a C_3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile. [0083] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

22SHPP0070-WO-PCT (SS290015PCT) CLAIMS 1. A porous carbon having a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores comprising the first portion of pores, the second portion of pores, and the third portion of pores; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): 22SHPP0070-WO-PCT (SS290015PCT) wherein each X is independently hydrogen, sodium, potassium, or NH₄ ⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. 2. The porous carbon of claim 1, wherein the functionalized polyphenylene ether comprises the sulfonated polyphenylene ether copolymer. 3. The porous carbon of claim 1, wherein the functionalized polyphenylene ether comprises a carboxylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIB) . 4. The porous carbon of claim 1, wherein the functionalized polyphenylene ether comprises a chloromethylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IIC) . 5. The porous carbon of claim 1, wherein the functionalized polyphenylene ether comprises a silylated polyphenylene ether comprising repeating units of Formula (I) and Formula (IID) wherein R’ is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group. 6. The porous carbon of claim 1, wherein the functionalized polyphenylene ether comprises a quaternized polyphenylene ether comprising repeating units of Formula (I) and Formula (IIE) 22SHPP0070-WO-PCT (SS290015PCT) wherein R’ is independently at each occurrence a C1-6 alkyl group or a C6-12 aryl group. 7. The porous carbon of any of claims 1 to 6, wherein pyrolyzing the functionalized polyphenylene ether is in the presence of a pore former. 8. The porous carbon of any of claims 1 to 7, wherein the porous carbon has a pore volume fraction of greater than 0.08 cm³ per gram. 9. The porous carbon of any of claims 1 to 8, further comprising heat treating the functionalized polyphenylene ether prior to the pyrolyzing, preferably wherein the heat treating comprises heating the functionalized polyphenylene ether to a temperature of 200 to 250°C for 1 to 120 minutes. 10. The porous carbon of claim 9, wherein the heat treating is in the presence of an oxidant, preferably air, oxygen, or oxygen-containing gases. 11. The porous carbon of any of claims 1 to 10, wherein the pyrolyzing is in an inert atmosphere, preferably wherein the inert atmosphere comprises nitrogen, argon, helium, or under vacuum. 12. A method of forming a porous carbon, the method comprising pyrolyzing a functionalized polyphenylene ether at a temperature of 450 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether is a copolymer comprising repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) 22SHPP0070-WO-PCT (SS290015PCT) wherein R is a sulfonic acid group, a carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group; provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a fourth repeating unit of formula (VII): wherein each X is independently hydrogen, sodium, potassium, or NH₄ ⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. 13. An article comprising the porous carbon of any of claims 1 to 11 or made by the method of claim 12; preferably, wherein the article is: a catalyst support, wherein a catalyst is disposed on the porous carbon; or a gas diffusion layer; or a redox flow battery electrode. 14. A catalyst support material comprising a porous carbon having a catalyst disposed thereon, wherein, the porous carbon is made by a method comprising: pyrolyzing a functionalized polyphenylene ether at a temperature of 200 to 800°C to provide a porous carbon comprising a plurality of pores; wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, 22SHPP0070-WO-PCT (SS290015PCT) a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers; wherein the functionalized polyphenylene ether comprises repeating units of Formula (I) repeating units according to at least one of Formula (II) and (III) wherein R is a sulfonic acid group, carboxylic acid, a chloride, a chloroalkyl group, a silyl group, or a quaternized ammonium group, provided then when R is a sulfonic acid group, the functionalized polyphenylene ether is a sulfonated polyphenylene ether copolymer comprising 49 to 89 mol%, preferably 55 to 85 mol%, more preferably 60 to 80 mol% of a first repeating unit of formula (IV), 10 to 50 mol%, preferably 15 to 40 mol%, more preferably 20 to 28 mol% of a second repeating unit of formula (V), 1 mol% or less of a third repeating unit of formula (VI), and 1 mol% or less of a wherein each X is independently hydrogen, sodium, potassium, or NH4⁺, and wherein each amount is based on total moles of repeating units in the sulfonated poly(phenylene ether) copolymer. 15. A gas diffusion layer comprising a porous carbon, wherein the porous carbon has a first portion of pores having a diameter of less than 0.002 micrometers, a second portion of pores having a diameter of 0.002 to 0.1 micrometers; and a third portion of pores having a diameter of greater than 0.1 to 1.5 micrometers.