WO2020181633A1 - 一种纳米多孔碳材料的制备方法 - Google Patents

一种纳米多孔碳材料的制备方法 Download PDF

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WO2020181633A1
WO2020181633A1 PCT/CN2019/084734 CN2019084734W WO2020181633A1 WO 2020181633 A1 WO2020181633 A1 WO 2020181633A1 CN 2019084734 W CN2019084734 W CN 2019084734W WO 2020181633 A1 WO2020181633 A1 WO 2020181633A1
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preparing
carbon material
nanoporous carbon
material according
polypyrrole nanofibers
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刘杨
张超
殷鹏飞
陈佳礽
崔彬
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole

Definitions

  • the invention relates to a nano porous carbon material, in particular to a preparation method of the nano porous carbon material.
  • Nanoporous carbon material carbon refers to a type of porous carbon material with uniform nanometer pore size distribution, high specific surface area and high microporosity. It has a wide range of applications in adsorption, catalysis, energy storage and sewage treatment.
  • the existing preparation methods for nanoporous carbon materials mainly include precursor synthesis, precursor carbonization, and activation processes, and the preparation process is complicated and costly.
  • Existing preparation methods generally firstly need to synthesize precursors with regular nano-pore structure, such as zeolite molecular sieve MCM-41, silica molecular sieve SBA-15, colloidal crystals (colloidal crystals). crystal), organic metal frame, etc.; and then carbonize it at high temperature for several hours under the protection of inert gas.
  • the porous carbon material obtained after carbonization needs to be physically or chemically activated to increase its specific surface area and micropore volume.
  • the current methods for preparing nanoporous carbon materials have the disadvantages of complicated steps, high consumption and high cost. In order to further realize the large-scale preparation and application of nanoporous carbon materials, it is necessary to improve the preparation methods of nanoporous carbon materials.
  • the purpose of the present invention is to provide a simple, rapid, and one-step method for preparing nanoporous carbon materials.
  • a preparation method of nano-porous carbon material is to mix polypyrrole nanofibers and an activator, microwave heating reaction, and purify the obtained product to obtain nano-porous carbon material.
  • the mass ratio of polypyrrole nanofibers and activator is 1: (1 ⁇ 5.5); further preferably, the mass ratio of polypyrrole nanofibers and activator is 1: (4 ⁇ 5.5).
  • the preparation method of the polypyrrole nanofibers is: mixing the pyrrole monomer and the solvent, and the obtained pyrrole monomer solution is reacted with the vanadium pentoxide sol and the oxidizing agent to obtain the polypyrrole Nanofibers.
  • the amount of raw materials is as follows: the volume ratio of pyrrole monomer, solvent, and vanadium pentoxide sol is 1: (40 ⁇ 80): (0.5 ⁇ 5); pyrrole monomer and The dosage ratio of the oxidant is 1 mL: (0.5-5) g; further preferably, the volume ratio of the pyrrole monomer, the solvent, and the vanadium pentoxide sol is 1: (50-70): (0.8-2).
  • the solvent includes at least one of hydrochloric acid, sulfuric acid, and nitric acid; more preferably, the solvent is hydrochloric acid, and the concentration of hydrochloric acid is preferably 0.5 mol/L to 2 mol/L.
  • the vanadium pentoxide sol is prepared by reacting ammonium metavanadate with an aqueous dispersion of cation exchange resin.
  • the specific preparation method of vanadium pentoxide sol is: mixing cation exchange resin with water, then adding ammonium metavanadate, mixing uniformly, and aging to obtain vanadium pentoxide Sol.
  • the mass ratio of the cation exchange resin, water and ammonium metavanadate is 1: (10-50): (0.05-0.2); more preferably, the cation exchange resin, The mass ratio of water to ammonium metavanadate is 1: (15 ⁇ 35): (0.08 ⁇ 0.15).
  • the cation exchange resin is Dowex 50WX8 ion exchange resin.
  • the aging time is 3 to 20 days.
  • the oxidizing agent is selected from at least one of persulfate, ferric chloride, ferric nitrate, iron sulfate, and hydrogen peroxide; further preferably, the oxidizing agent is persulfate; Still further preferably, the oxidizing agent is selected from at least one of potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the reaction time is 0.5h-2h.
  • a purification step is included after the reaction, and the proposed steps include filtration, washing, and drying; further preferably, the filtration is suction filtration; the washing is performed with hydrochloric acid, deionized water, and ethanol in sequence. Wash the product and repeat at least three times; drying is at 50°C ⁇ 70°C for 10h ⁇ 20h.
  • the activator is selected from at least one of zinc chloride, alkali metal hydroxide, and phosphoric acid; further preferably, the activator is selected from zinc chloride, potassium hydroxide , At least one of phosphoric acid; still more preferably, the activator is zinc chloride.
  • the microwave heating is performed in a microwave device with a power of 800W ⁇ 1500W for 10min ⁇ 60min, and the frequency of the microwave is 2400MHz ⁇ 2500MHz; further preferably, the microwave heating is performed at a power of 1000W Heating in the microwave device for 15min ⁇ 45min, the frequency of the microwave is 2450MHz.
  • the purification method is: washing the product obtained by microwave heating with acid and water, and then drying.
  • the washing method is specifically: washing the product obtained by microwave heating with hydrochloric acid, then centrifugal separation, dispersing the obtained precipitate with water, and then centrifugal washing; further preferably, the washing method is specifically: microwave The product obtained by heating is washed with 0.5mol/L ⁇ 2mol/L hydrochloric acid, and then centrifuged at 10000r/min ⁇ 15000r/min, the supernatant is removed, and the obtained precipitate is dispersed in water, and then the temperature is 10000r/min ⁇ 15000r/min.
  • the washing method is specifically: washing the product obtained by microwave heating with 1mol/L hydrochloric acid, and then centrifuging at 12000r/min to remove the supernatant , Disperse the obtained precipitate with water, and then centrifuge and wash it at 12000r/min, so that the washing and dispersion cycle is at least three times.
  • the drying method is specifically: drying at 50°C to 70°C for 12h to 36h; further preferably, drying is drying at 60°C for 20h to 30h.
  • the method for preparing nanoporous carbon materials of the present invention has simple raw materials, convenient operation and short time-consuming, and is more suitable for the mass preparation and production of nanoporous carbon materials.
  • Figure 1 is a transmission electron micrograph of the nanoporous carbon material prepared in Example 3 of the present invention.
  • Figure 2 is a partially enlarged transmission electron microscope view of Figure 1;
  • Figure 3 is a Raman spectrum of the nanoporous carbon material prepared in Example 3 of the present invention.
  • the quartz glass tube is taken out and cooled to room temperature, and then the black product is taken out and placed in a 1 mol/L hydrochloric acid solution, stirred and washed for 24 hours.
  • the hydrochloric acid solution containing the product was placed in a 50 mL high-speed centrifuge tube, and centrifuged at a speed of 12000 r/min for 30 minutes to separate the product.
  • use deionized water to redisperse the precipitate in the centrifuge tube, and centrifuge at a speed of 12000r/min for 30 minutes.
  • the above re-dispersion-washing cycle process is repeated at least three times. After the centrifugal washing is completed, the supernatant liquid is removed, and the centrifuge tube is placed in an oven at 60° C. to dry for 24 hours to obtain the nanoporous carbon material of this example.
  • the quartz glass tube is taken out and cooled to room temperature, and then the black product is taken out and placed in a 1 mol/L hydrochloric acid solution, stirred and washed for 24 hours.
  • the hydrochloric acid solution containing the product was placed in a 50 mL high-speed centrifuge tube, and centrifuged at a speed of 12000 r/min for 30 minutes to separate the product.
  • use deionized water to redisperse the precipitate in the centrifuge tube, and centrifuge at a speed of 12000r/min for 30 minutes.
  • the above re-dispersion-washing cycle process is repeated at least three times. After the centrifugal washing is completed, the supernatant liquid is removed, and the centrifuge tube is placed in an oven at 60° C. to dry for 24 hours to obtain the nanoporous carbon material of this example.
  • the quartz glass tube is taken out and cooled to room temperature, and then the black product is taken out and placed in a 1 mol/L hydrochloric acid solution, stirred and washed for 24 hours.
  • the hydrochloric acid solution containing the product was placed in a 50 mL high-speed centrifuge tube, and centrifuged at a speed of 12000 r/min for 30 minutes to separate the product.
  • use deionized water to redisperse the precipitate in the centrifuge tube, and centrifuge at a speed of 12000r/min for 30 minutes.
  • the above re-dispersion-washing cycle process is repeated at least three times. After the centrifugal washing is completed, the supernatant liquid is removed, and the centrifuge tube is placed in an oven at 60° C. to dry for 24 hours to obtain the nanoporous carbon material of this example.
  • the quartz glass tube is taken out and cooled to room temperature, and then the black product is taken out and placed in a 1 mol/L hydrochloric acid solution, stirred and washed for 24 hours.
  • the hydrochloric acid solution containing the product was placed in a 50 mL high-speed centrifuge tube, and centrifuged at a speed of 12000 r/min for 30 minutes to separate the product.
  • use deionized water to redisperse the precipitate in the centrifuge tube, and centrifuge at a speed of 12000r/min for 30 minutes.
  • the above re-dispersion-washing cycle process is repeated at least three times. After the centrifugal washing is completed, the supernatant liquid is removed, and the centrifuge tube is placed in an oven at 60° C. to dry for 24 hours to obtain the nanoporous carbon material of this example.
  • the preparation method of polypyrrole nanofibers is: adding 1 mL of pyrrole monomer to 60 mL of a hydrochloric acid solution with a concentration of 1 mol/L, and stirring the solution at a speed of 1000 r/min for 3 minutes to uniformly disperse the pyrrole monomer. Then, 1 mL of vanadium pentoxide gel was quickly injected into the pyrrole monomer solution under stirring, and then 1.1 g of ammonium persulfate was added to the reaction solution, and the reaction was continued for 1 hour under stirring.
  • the preparation method of vanadium pentoxide gel is: 8g Dowex The 50WX8 ion exchange resin was dissolved in 180 mL of deionized water by stirring and dispersing. Then add 800mg ammonium metavanadate to Dowex After stirring the dispersion of 50WX8 ion exchange resin to be uniform, seal the container with cellulose filter paper and age the dispersion for two weeks at room temperature.
  • Figure 1 is a transmission electron microscope image of the nanoporous carbon material prepared in Example 3 of the present invention. It can be seen from Figure 1 that the prepared nanoporous carbon material has a clear nanoporous structure and a uniform pore size distribution, and the ordered distribution of circular micropores can be clearly observed on the bulk carbon substrate. The diameter of these micropores is between 2-10 nm, and they are widely distributed on the surface and inside of the carbon substrate.
  • Figure 2 is a partial enlarged view of Figure 1. It can be seen from Figure 2 that in addition to the micropores distributed on the surface, there is a connected network structure composed of micropores and ultrafine micropores inside the nanoporous carbon, thereby forming a very high micropore area and microporosity.
  • BET Brunner-Emmet-Teller
  • Figure 3 is a Raman spectrum of the nanoporous carbon material prepared in Example 3 of the present invention. It can be seen from Figure 3 that the intensity of the G peak representing crystalline graphite is significantly higher than the D peak representing the defect structure, and its peak ratio is as high as 1.19. It shows that the prepared nanoporous carbon material has a good graphite structure.

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Abstract

本发明公开了一种纳米多孔碳材料的制备方法。这种纳米多孔碳材料的制备方法是：将聚吡咯纳米纤维和活化剂混合，微波加热反应，所得的产物提纯，得到纳米多孔碳材料。相较于传统的高温碳化法，本发明制备纳米多孔碳材料的方法原料简单、操作便捷、耗时短，更加适合纳米多孔碳材料的大量制备与生产。

Description

一种纳米多孔碳材料的制备方法
技术领域
本发明涉及一种纳米多孔碳材料，特别是涉及一种纳米多孔碳材料的制备方法。
背景技术
纳米多孔碳材料（nanoporous carbon）是指一类具有均匀纳米孔径分布、高比表面积、高微孔率的多孔碳材料，其在吸附、催化、储能以及污水处理方面有着广泛的应用。
现有的针对纳米多孔碳材料的制备方法主要包括前驱体合成、前驱体碳化以及活化等流程，制备过程繁琐且成本较高。现有的制备方法一般首先需要合成出具有规整纳米孔径结构的前驱体，如沸石分子筛MCM-41、二氧化硅分子筛SBA-15、胶体晶体（colloidal crystal）、有机金属框架等；再将其在惰性气体保护的条件下经数小时高温碳化。碳化后的所得多孔碳材料还要再进行物理或化学活化，以增加其比表面积和微孔体积。
目前制备纳米多孔碳材料的方法存在步骤繁琐、消耗大、成本高的缺点，为进一步实现纳米多孔碳材料的大规模制备与应用，需要对纳米多孔碳材料的制备方法进行改善。
发明内容
为了克服现有技术存在的问题，本发明的目的在于提供一种简单、快速、一步式制备纳米多孔碳材料的方法。
为了实现上述的目的，本发明所采取的技术方案是：
一种纳米多孔碳材料的制备方法，是将聚吡咯纳米纤维和活化剂混合，微波加热反应，所得的产物提纯，得到纳米多孔碳材料。
优选的，这种纳米多孔碳材料的制备方法中，聚吡咯纳米纤维和活化剂的质量比为1：（1~5.5）；进一步优选的，聚吡咯纳米纤维和活化剂的质量比为1：（4~5.5）。
优选的，这种纳米多孔碳材料的制备方法中，聚吡咯纳米纤维的制备方法是：将吡咯单体与溶剂混合，所得吡咯单体溶液与五氧化二钒溶胶、氧化剂进行反应，得到聚吡咯纳米纤维。
优选的，聚吡咯纳米纤维的制备方法中，原料的用量比如下：吡咯单体、溶剂、五氧化二钒溶胶体积比为1：（40~80）：（0.5~5）；吡咯单体与氧化剂的用量比为1mL：（0.5~5）g；进一步优选的，吡咯单体、溶剂、五氧化二钒溶胶体积比为1：（50~70）：（0.8~2）。
优选的，聚吡咯纳米纤维的制备方法中，溶剂包括盐酸、硫酸、硝酸中的至少一种；进一步优选的，溶剂为盐酸，盐酸的浓度优选为0.5mol/L~2mol/L。
优选的，聚吡咯纳米纤维的制备方法中，五氧化二钒溶胶是将偏钒酸铵与阳离子交换树脂的水分散液进行反应制得。
优选的，这种聚吡咯纳米纤维的制备方法中，五氧化二钒溶胶具体的制备方法是：将阳离子交换树脂与水混合，然后加入偏钒酸铵混合均匀，陈化，得到五氧化二钒溶胶。
优选的，五氧化二钒溶胶具体的制备方法中，阳离子交换树脂、水、偏钒酸铵的质量比为1：（10~50）：（0.05~0.2）；进一步优选的，阳离子交换树脂、水、偏钒酸铵的质量比为1：（15~35）：（0.08~0.15）。
优选的，五氧化二钒溶胶具体的制备方法中，阳离子交换树脂为Dowex 50WX8离子交换树脂。
优选的，五氧化二钒溶胶具体的制备方法中，陈化的时间为3天~20天。
优选的，这种聚吡咯纳米纤维的制备方法中，氧化剂选自过硫酸盐、氯化铁、硝酸铁、硫酸铁、过氧化氢中的至少一种；进一步优选的，氧化剂为过硫酸盐；再进一步优选的，氧化剂选自过硫酸钾、过硫酸钠、过硫酸铵中的至少一种。
优选的，这种聚吡咯纳米纤维的制备方法中，反应的时间为0.5h~2h。
优选的，这种聚吡咯纳米纤维的制备方法中，反应后还包括提纯步骤，提出步骤包括过滤，洗涤，干燥；进一步优选的，过滤为抽滤；洗涤是依次用盐酸、去离子水、乙醇对产物进行洗涤，并至少重复三次；干燥是在50℃~70℃下干燥10h~20h。
优选的，这种纳米多孔碳材料的制备方法中，活化剂选自氯化锌、碱金属氢氧化物、磷酸中的至少一种；进一步优选的，活化剂选自氯化锌、氢氧化钾、磷酸中的至少一种；再进一步优选的，活化剂为氯化锌。
优选的，这种纳米多孔碳材料的制备方法中，微波加热是在800W~1500W功率的微波装置中加热10min~60min，微波的频率为2400MHz~2500MHz；进一步优选的，微波加热是在1000W功率的微波装置中加热15min~45min，微波的频率为2450MHz。
优选的，这种纳米多孔碳材料的制备方法中，提纯的方法是：将微波加热得到的产物用酸和水洗涤，再干燥。
优选的，提纯中，洗涤的方法具体是：将微波加热得到的产物用盐酸洗涤，然后离心分离，将所得的沉淀物加水分散，再离心洗涤；进一步优选的，洗涤的方法具体是：将微波加热得到的产物用0.5mol/L~2mol/L盐酸洗涤，然后在10000r/min~15000r/min下离心分离，去掉上清液，将所得的沉淀物加水分散，再在10000r/min~15000r/min下离心洗涤，如此洗涤、分散循环至少三次；再进一步优选的，洗涤的方法具体是：将微波加热得到的产物用1mol/L盐酸洗涤，然后在12000r/min下离心分离，去掉上清液，将所得的沉淀物加水分散，再在12000r/min下离心洗涤，如此洗涤、分散循环至少三次。
优选的，提纯中，干燥的方法具体是：在50℃~70℃下干燥12h~36h；进一步优选的，干燥是在60℃干燥20h~30h。
本发明的有益效果是：
相较于传统的高温碳化法，本发明制备纳米多孔碳材料的方法原料简单、操作便捷、耗时短，更加适合纳米多孔碳材料的大量制备与生产。
附图说明
图1是本发明实施例3制得纳米多孔碳材料的透射电镜图；
图2是图1的局部放大透射电镜图；
图3是本发明实施例3制得纳米多孔碳材料的拉曼光谱图。
具体实施方式
以下通过具体的实施例对本发明的内容作进一步详细的说明。实施例中所用的原料如无特殊说明，均可从常规商业途径得到。
实施例1
称取80mg聚吡咯纳米纤维以及400mg氯化锌，并将其置于10mL的圆底离心管中震荡混合5分钟。待聚吡咯纳米纤维与氯化锌混合均匀后，将所得的混合物铺平放置于50mL的石英玻璃管中。然后将石英玻璃管封口并固定放置于普通家用微波炉中，并以1000W功率、2450MHz频率的微波加热15分钟。其间可以观察到聚吡咯纳米纤维与氯化锌之间的剧烈放热反应，并伴有等离子体和火花生成。待微波加热结束后，将石英玻璃管取出并冷却至室温，然后将黑色产物取出并置于1mol/L盐酸溶液中搅拌洗涤24小时。待搅拌结束后，将含有产物的盐酸溶液置于50mL的高速离心管中，并以12000r/min的速度离心30分钟以将产物分离。去掉上层清液后使用去离子水将离心管内的沉淀物再分散，并以12000r/min的速度离心洗涤30分钟。上述再分散-洗涤的循环过程至少重复三次。待离心洗涤结束后，去掉上层清液，并将离心管置于60℃烘箱干燥24小时，得到本例的纳米多孔碳材料。
实施例2
称取80mg聚吡咯纳米纤维以及400mg氯化锌，并将其置于10mL的圆底离心管中震荡混合5分钟。待聚吡咯纳米纤维与氯化锌混合均匀后，将所得的混合物铺平放置于50mL的石英玻璃管中。然后将石英玻璃管封口并固定放置于普通家用微波炉中，并以1000W的功率、2450MHz频率的微波加热25分钟。其间可以观察到聚吡咯纳米纤维与氯化锌之间的剧烈放热反应，并伴有等离子体和火花生成。待微波加热结束后，将石英玻璃管取出并冷却至室温，然后将黑色产物取出并置于1mol/L盐酸溶液中搅拌洗涤24小时。待搅拌结束后，将含有产物的盐酸溶液置于50mL的高速离心管中，并以12000r/min的速度离心30分钟以将产物分离。去掉上层清液后使用去离子水将离心管内的沉淀物再分散，并以12000r/min的速度离心洗涤30分钟。上述再分散-洗涤的循环过程至少重复三次。待离心洗涤结束后，去掉上层清液，并将离心管置于60℃烘箱干燥24小时，得到本例的纳米多孔碳材料。
实施例3
称取150mg聚吡咯纳米纤维以及750mg氯化锌，并将其置于10mL的圆底离心管中震荡混合5分钟。待聚吡咯纳米纤维与氯化锌混合均匀后，将所得的混合物铺平放置于50mL的石英玻璃管中。然后将石英玻璃管封口并固定放置于普通家用微波炉中，并以1000W功率、2450MHz频率的微波加热35分钟。其间可以观察到聚吡咯纳米纤维与氯化锌之间的剧烈放热反应，并伴有等离子体和火花生成。待微波加热结束后，将石英玻璃管取出并冷却至室温，然后将黑色产物取出并置于1mol/L盐酸溶液中搅拌洗涤24小时。待搅拌结束后，将含有产物的盐酸溶液置于50mL的高速离心管中，并以12000r/min的速度离心30分钟以将产物分离。去掉上层清液后使用去离子水将离心管内的沉淀物再分散，并以12000r/min的速度离心洗涤30分钟。上述再分散-洗涤的循环过程至少重复三次。待离心洗涤结束后，去掉上层清液，并将离心管置于60℃烘箱干燥24小时，得到本例的纳米多孔碳材料。
实施例4
称取150mg聚吡咯纳米纤维以及750mg氯化锌，并将其置于10mL的圆底离心管中震荡混合5分钟。待聚吡咯纳米纤维与氯化锌混合均匀后，将所得的混合物铺平放置于50mL的石英玻璃管中。然后将石英玻璃管封口并固定放置于普通家用微波炉中，并以1000W功率、2450MHz频率的微波加热45分钟。其间可以观察到聚吡咯纳米纤维与氯化锌之间的剧烈放热反应，并伴有等离子体和火花生成。待微波加热结束后，将石英玻璃管取出并冷却至室温，然后将黑色产物取出并置于1mol/L盐酸溶液中搅拌洗涤24小时。待搅拌结束后，将含有产物的盐酸溶液置于50mL的高速离心管中，并以12000r/min的速度离心30分钟以将产物分离。去掉上层清液后使用去离子水将离心管内的沉淀物再分散，并以12000r/min的速度离心洗涤30分钟。上述再分散-洗涤的循环过程至少重复三次。待离心洗涤结束后，去掉上层清液，并将离心管置于60℃烘箱干燥24小时，得到本例的纳米多孔碳材料。
实施例1~4中，聚吡咯纳米纤维和五氧化二钒凝胶的制备方法如下：
聚吡咯纳米纤维的制备方法为：将1mL吡咯单体加入60mL浓度为1mol/L的盐酸溶液中，以1000r/min的速度对该溶液进行3分钟搅拌以将吡咯单体均匀分散。然后在搅拌状态下将1mL五氧化二钒凝胶快速注入吡咯单体溶液中，然后再将1.1g过硫酸铵加入该反应溶液中，并在搅拌状态下继续反应1小时。待1小时后停止搅拌以结束反应，并将该溶液置于布氏漏斗中真空抽滤以分离产物，其间可观察到产物在滤纸上沉积形成黑色滤饼。使用盐酸以及去离子水对滤饼进行洗涤，每次洗涤的溶剂用量至少为50mL，而且盐酸—去离子水的循环洗涤应至少重复三次。待洗涤过后，将滤饼置于60℃烘箱中干燥12小时即可得到干燥的聚吡咯纳米纤维。
五氧化二钒凝胶的制备方式为：将8g Dowex 50WX8离子交换树脂通过搅拌分散溶解于180mL去离子水中。然后将800mg偏钒酸铵加入Dowex 50WX8离子交换树脂的分散液中，待搅拌至均匀后，用纤维素滤纸将容器瓶口密封并将分散液于室温条件下陈化两周。
经检测，实施例1~4所得纳米多孔碳材料的比表面积如表1所示。
表1 实施例1~4所得纳米多孔碳材料的比表面积
实施例编号 实施例1 实施例2 实施例3 实施例4
比表面积（m2/g） 972 820 1007 873
附图1是本发明实施例3制得纳米多孔碳材料的透射电镜图。从图1可见，经所制得的纳米多孔碳材料具有清晰的纳米孔隙结构以及均匀的孔径分布，在块状的碳基材上可以清晰地观察到有序分布的圆形微孔。这些微孔的直径在2-10nm之间，且广泛分布于碳基材的表面以及内部。附图2是图1的局部放大图。从图2可见，除了表面分布的微孔以外，在纳米多孔碳内部还存在着由微孔和超细微孔所构成的连通网络结构，从而形成了极高的微孔面积以及微孔率。经由Brunner-Emmet-Teller（BET）比表面积测试，可得知此纳米多孔碳的比表面积可达1007m2/g，其中外比表面积为67m2/g，而微孔比表面积则达到了940m2/g，占比高达93%。
附图3是本发明实施例3制得纳米多孔碳材料的拉曼光谱图。从图3可见，代表结晶石墨的G峰强度要明显高于代表缺陷结构的D峰，且其峰值比高达1.19。说明制备所得的纳米多孔碳材料具有良好的石墨结构。

Claims (10)

  1. 一种纳米多孔碳材料的制备方法，其特征在于：将聚吡咯纳米纤维和活化剂混合，微波加热反应，所得的产物提纯，得到纳米多孔碳材料。
  2. 根据权利要求1所述的一种纳米多孔碳材料的制备方法，其特征在于：所述聚吡咯纳米纤维和活化剂的质量比为1：（1~5.5）。
  3. 根据权利要求2所述的一种纳米多孔碳材料的制备方法，其特征在于：所述聚吡咯纳米纤维的制备方法是：将吡咯单体与溶剂混合，所得吡咯单体溶液与五氧化二钒溶胶、氧化剂进行反应，得到聚吡咯纳米纤维。
  4. 根据权利要求3所述的一种纳米多孔碳材料的制备方法，其特征在于：所述聚吡咯纳米纤维的制备方法中，原料的用量比如下：吡咯单体、溶剂、五氧化二钒溶胶体积比为1：（40~80）：（0.5~5）；吡咯单体与氧化剂的用量比为1mL：（0.5~5）g。
  5. 根据权利要求4所述的一种纳米多孔碳材料的制备方法，其特征在于：所述聚吡咯纳米纤维的制备方法中，溶剂包括盐酸、硫酸、硝酸中的至少一种。
  6. 根据权利要求4所述的一种纳米多孔碳材料的制备方法，其特征在于：所述五氧化二钒溶胶是将偏钒酸铵与阳离子交换树脂的水分散液进行反应制得。
  7. 根据权利要求4所述的一种纳米多孔碳材料的制备方法，其特征在于：所述聚吡咯纳米纤维的制备方法中，氧化剂选自过硫酸盐、氯化铁、硝酸铁、硫酸铁、过氧化氢中的至少一种。
  8. 根据权利要求2所述的一种纳米多孔碳材料的制备方法，其特征在于：所述活化剂选自氯化锌、碱金属氢氧化物、磷酸中的至少一种。
  9. 根据权利要求1所述的一种纳米多孔碳材料的制备方法，其特征在于：所述微波加热是在800W~1500W功率的微波装置中加热10min~60min，微波的频率为2400MHz~2500MHz。
  10. 根据权利要求1所述的一种纳米多孔碳材料的制备方法，其特征在于：所述提纯的方法是：将微波加热得到的产物用酸和水洗涤，再干燥。
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