CN107522266B - Preparation method of hierarchical porous carbon material capacitive desalination electrode material - Google Patents
Preparation method of hierarchical porous carbon material capacitive desalination electrode material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
Abstract
The invention relates to a preparation method of a hierarchical porous carbon material capacitive desalination electrode material. The method selects water as a solvent to synthesize a metal organic framework, and introduces a surfactant as a template in the synthesis process to change the unique microporous structure of the metal organic framework to obtain a uniform mixed solution; washing off redundant active components at a certain temperature to obtain the hierarchical porous structure metal organic framework compound. The compound has a geometric shape similar to that of a pure metal organic framework compound crystal, and internal metal is removed through high-temperature calcination and hydrochloric acid solution reaction to obtain the hierarchical porous carbon material with high nitrogen content; and uniformly mixing the composite material, acetylene black and polytetrafluoroethylene emulsion, coating the mixture on graphite paper, and drying to obtain the capacitive desalting electrode. The method has the advantages of simple operation, easily controlled conditions and large-scale synthesis, and the obtained electrode has high nitrogen content, high specific surface, good conductivity and wettability and has potential application prospect in the aspect of capacitive desalination.
Description
Technical Field
The invention relates to a preparation method of a hierarchical porous carbon material capacitive desalination electrode material.
Background
With the development of human society, the existence and development of human beings are seriously affected by energy shortage and environmental pollution, wherein the water resource crisis is particularly prominent. The seawater and brackish water desalination technology has attracted extensive social attention as an important way to effectively solve the crisis. At present, the existing desalination and desalination technical methods mainly comprise a distillation method and a membrane method. However, the traditional desalination technologies have some inevitable problems, namely the cost of the selective semipermeable membrane used by the membrane method is high, the equipment investment is large, membrane parts are easy to block, and secondary pollution is easily caused; the distillation method has high requirements on heat energy, high operation temperature, large energy consumption and serious boiler scale damage and corrosion. Efforts have been made to reduce the cost and energy consumption of these conventional desalination techniques by using renewable resources such as solar, tidal and wind energy as the driving energy for the desalination system, but still not to achieve the low cost and low energy consumption requirements. Therefore, the development of new desalination technology with low cost, high efficiency, low energy consumption and environmental friendliness is urgent. Capacitive desalination is a brand new desalination technology based on the principle of double electric layers and capacitors. The method has low energy consumption and high desalting efficiency, and is environment-friendly. Can be applied to the desalination of seawater and brackish water, the softening of industrial and agricultural production and domestic water and the like, and has wide development space and application prospect.
Based on the principle of capacitive desalination, an electrode material with large specific surface area, developed gaps and good conductivity becomes the key for obtaining high capacitive desalination performance. The porous carbon material has the characteristics of high specific surface area, good conductivity, unique chemical stability, easily controlled pore structure, good conductivity and the like, and is always the first choice of the electrode material of the capacitive type desalting device. Metal-organic frameworks (MOFs) compounds have high specific surface area, large pore volume and tunable pore structure, and have recently been demonstrated to be useful as carbon precursors or templates for the preparation of porous carbon materials (Chaikitisil W, Hu M, Wang H, Huang H S, Fujita T, Wu K C W, Chen L C, Yamauchi Y, Ariga K, Nanopous carbon through direct carbon synthesis of a zeolitic adsorbent framework for supercritical electrolytes, M. Commun. 2012, 48(58): 7259) 7261). The porous carbon material has the characteristics of simple preparation method, excellent electrochemical performance and the like, and the material is endowed with unique properties of machinery, electronics, optics, semiconductors, energy storage and the like, so that the porous carbon material is widely applied to the fields of electrode materials of supercapacitors, adsorbents, hydrogen storage, catalysis and the like.
Zeolitic Imidazolate framework materials (ZIFs) are a branch of metal organic framework materials, which are three-dimensional tetrahedral Frameworks similar to zeolite structures formed from transition metal and imidazole ligands. The high thermal stability and chemical stability of ZIFs and the rich nitrogen source in the imidazole ligand make the ZIFs an ideal precursor for preparing nitrogen-doped porous carbon with excellent performance. However, it should be noted that the precursors of the currently prepared ZIF-based porous carbon materials are generally selected from organic solvents (e.g., N-dimethylformamide, methanol, etc.) which not only pollute the environment, but also are difficult to degrade. And the pore structure of the ZIF-based porous carbon material is mainly microporous, which is not beneficial to the diffusion and transmission of ions in the solution. Increasing the length of imidazole derivatives increases the cage diameter and pore size of ZIFs, but long organic ligands cause poor stability of the material framework structure, resulting in collapse of the mesoporous structure when fired. Therefore, the search for green and environmentally friendly synthetic methods, high porosity carbon materials remain challenging.
The surfactant is an effective structure directing agent of the mesoporous material, and can be effectively cooperatively assembled at an organic-inorganic interface to obtain the mesoporous material. The surfactant is used as a template and is successfully applied to the synthesis of mesoporous silica and metal oxide materials (Soler-Illia G J d A, Sanchez C, Lebeau B, Pataring J, chem. Rev. 2002, 102 (11), 4093-4138). However, to date, ordered mesoporous MOFs and their carbon materials have been reported less as capacitive desalination electrodes. In order to overcome the performance defect of a ZIF-based porous carbon material as a capacitive desalting electrode, the invention adopts a green solvent synthesis method, combines the template effect of a surfactant, and changes the pore structure of carbon by regulating and controlling the different ratios of the surfactant and a carbon precursor, so as to prepare a novel high-nitrogen-content hierarchical porous carbon capacitive desalting electrode material with high surface area, high conductivity and developed pores, thereby providing a new way for desalting with high performance, high efficiency and low energy consumption.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of a hierarchical porous carbon material capacitive desalination electrode material.
According to the invention, green, environment-friendly and pollution-free water is selected as a solvent to synthesize a metal organic framework, a surfactant is introduced as a template in the synthesis process to change the unique microporous structure of the metal organic framework, a mesoporous and microporous composite hierarchical pore channel structure is formed to promote the diffusion and transmission of ions in a solution, and redundant active agent components are washed away at a certain temperature to obtain the hierarchical porous structure metal organic framework composite. The composite has a geometric appearance similar to that of a pure metal organic framework compound crystal, and internal metal of the composite is removed through high-temperature calcination and hydrochloric acid solution reaction, so that the high-nitrogen-content hierarchical porous carbon capacitive desalination electrode material with high surface area, high conductivity and developed pores can be obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a hierarchical porous carbon material capacitive desalination electrode material is characterized by comprising the following specific steps:
a. dissolving 2-methylimidazole in a deionized water solution to prepare a solution with the concentration of 2-4 wt%, adjusting the pH value of the solution to 9-11, and uniformly mixing to obtain a solution A;
b. dissolving zinc nitrate hexahydrate and a surfactant in deionized water according to the mass ratio of 1: 1-1: 3 to prepare a solution with the concentration of 1-2 wt% of zinc nitrate, and uniformly mixing to obtain a solution B;
c. dropwise adding the solution B obtained in the step B into the reverse solution A obtained in the step a at a stirring speed of 350-500 rpm/min, stirring for reacting for 10-24 h, and then centrifuging, washing and drying to obtain a precursor, namely the porous metal organic framework ZIF-8; the volume ratio of the solution A to the solution B is 1: 1-1: 2;
d. c, carbonizing the porous metal organic framework ZIF-8 obtained in the step c in an inert atmosphere, adding 2 mol of hydrochloric acid solution to react to remove metal oxides, and fully washing and drying to obtain a hierarchical porous carbon material;
e. d, mixing the graded porous carbon material obtained in the step d, acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10: 10-90: 5:5, uniformly stirring and mixing, coating the mixture on conductive substrate graphite paper, and drying at 100-120 ℃; finally, the hierarchical porous carbon material capacitive type desalting electrode material is prepared.
The preparation method of the hierarchical porous carbon material capacitive desalination electrode material is characterized in that the surfactant is at least one of cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide.
The preparation method of the high-nitrogen-content hierarchical porous carbon material capacitive desalination electrode is characterized in that the composite material prepared by the method takes water as a solvent to synthesize a metal organic framework ZIF-8, takes a surfactant as a template to change a unique microporous structure of the metal organic framework ZIF-8, and the metal organic framework ZIF-8 is used as a carbon source and a nitrogen source to form a three-dimensional hierarchical porous structure through high-temperature calcination. The material has the characteristics of high surface area, high conductivity, developed gaps and the like, has high efficiency and low energy consumption when being applied to desalting, can be applied to desalting seawater and brackish water, and provides a new way for desalting with low energy consumption, low cost and high performance.
Detailed Description
Specific embodiments of the present invention will now be described.
Example 1
Dissolving 2-methylimidazole in a deionized water solution to prepare a solution with the concentration of 2 wt%, adjusting the pH value of the solution to 9, and uniformly mixing to obtain a solution A; dissolving zinc nitrate hexahydrate and a surfactant in deionized water according to the mass ratio of 1:1 to prepare a solution with the concentration of 1 wt% of zinc nitrate, and uniformly mixing to obtain a solution B; and dropwise adding the obtained solution B into the solution A at a stirring speed of 350rpm/min, stirring for reacting for 12 hours, centrifuging, washing for 2-3 times by using deionized water, and drying at 80 ℃ to obtain the porous metal organic framework ZIF-8.
And (3) placing the obtained porous metal organic framework ZIF-8 in a tubular furnace, controlling the heating rate to be 2 ℃/min under the protection of nitrogen with the gas flow rate of 90 mL/min, heating to 900 ℃, preserving the heat for 3 h at 900 ℃, adding 2M hydrochloric acid solution after cooling to room temperature, stirring overnight to remove metal oxides, fully washing and drying to obtain the high-nitrogen-content hierarchical porous carbon material. The obtained high-nitrogen-content hierarchical porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 80:10:10, then the mixture is coated on graphite paper, and then the graphite paper is dried at 100-120 ℃. Finally, the high-nitrogen-content hierarchical porous carbon material capacitive type desalting electrode is prepared.
And testing the specific capacitance of the high-nitrogen hierarchical porous carbon material capacitive type desalting electrode. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 5mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 100F/g. The electrode prepared above was tested for desalting performance, and the desalting efficiency was more than 80% in 100ppm of brine.
Example 2
Dissolving 2-methylimidazole in a deionized water solution to prepare a solution with the concentration of 3 wt%, adjusting the pH value of the solution to 10, and uniformly mixing to obtain a solution A; dissolving zinc nitrate hexahydrate and a surfactant in deionized water according to the mass ratio of 1:2 to prepare a solution with the concentration of 1.5 wt% of zinc nitrate, and uniformly mixing to obtain a solution B; and dropwise adding the obtained solution B into the solution A at a stirring speed of 400rpm/min, stirring for reacting for 16 hours, centrifuging, washing for 2-3 times by using deionized water, and drying at 80 ℃ to obtain the porous metal organic framework ZIF-8.
And (3) placing the obtained porous metal organic framework ZIF-8 in a tubular furnace, controlling the heating rate to be 3 ℃/min under the protection of nitrogen with the gas flow rate of 100 mL/min, heating to 800 ℃, preserving the heat for 4 h at 800 ℃, adding 2M hydrochloric acid solution after cooling to room temperature, stirring overnight to remove metal oxides, fully washing and drying to obtain the high-nitrogen-content hierarchical porous carbon material. The obtained high-nitrogen-content hierarchical porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 85:10:5, then the mixture is coated on graphite paper, and then the graphite paper is dried at 100-120 ℃. Finally, the high-nitrogen-content hierarchical porous carbon material capacitive type desalting electrode is prepared.
And testing the specific capacitance of the high-nitrogen hierarchical porous carbon material capacitive type desalting electrode. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 5mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 95F/g. The electrode prepared above was tested for desalting performance and had desalting efficiency of greater than 75% in 300ppm saline.
Example 3
Dissolving 2-methylimidazole in a deionized water solution to prepare a solution with the concentration of 3 wt%, adjusting the pH value of the solution to 11, and uniformly mixing to obtain a solution A; dissolving zinc nitrate hexahydrate and a surfactant in deionized water according to the mass ratio of 1:3 to prepare a solution with the concentration of zinc nitrate being 2 wt%, and uniformly mixing to obtain a solution B; and dropwise adding the obtained solution B into the solution A at a stirring speed of 450rpm/min, stirring for reacting for 20 hours, centrifuging, washing with deionized water for 2-3 times, and drying at 80 ℃ to obtain the porous metal organic framework ZIF-8.
And (3) placing the obtained porous metal organic framework ZIF-8 in a tubular furnace, controlling the heating rate to be 4 ℃/min under the protection of nitrogen with the gas flow rate of 130 mL/min, heating to 700 ℃, preserving the heat for 5 h at 700 ℃, adding 2M hydrochloric acid solution after cooling to room temperature, stirring overnight to remove metal oxides, fully washing and drying to obtain the high-nitrogen-content hierarchical porous carbon material. The obtained high-nitrogen-content hierarchical porous carbon material is uniformly mixed with acetylene black and polytetrafluoroethylene emulsion according to the mass ratio of 90:5:5, then the mixture is coated on graphite paper, and then the graphite paper is dried at 100-120 ℃. Finally, the high-nitrogen-content hierarchical porous carbon material capacitive type desalting electrode is prepared.
And testing the specific capacitance of the high-nitrogen hierarchical porous carbon material capacitive type desalting electrode. Using a CHI-660D type electrochemical workstation, wherein the electrolyte is 0.5M sodium chloride solution, the scanning speed is 5mV/s, and the voltage range is-0.5V; the specific capacitance of the electrode was measured to be greater than 100F/g. The electrode prepared above was tested for desalting performance, and the desalting efficiency was more than 70% in 50ppm of brine.
Claims (2)
1. A preparation method of a hierarchical porous carbon material capacitive desalination electrode material is characterized by comprising the following specific steps:
a. dissolving 2-methylimidazole in a deionized water solution to prepare a solution with the concentration of 2-4 wt%, adjusting the pH value of the solution to 9-11, and uniformly mixing to obtain a solution A;
b. dissolving zinc nitrate hexahydrate and a surfactant in deionized water according to the mass ratio of 1: 1-1: 3 to prepare a solution with the concentration of 1-2 wt% of zinc nitrate, and uniformly mixing to obtain a solution B;
c. dropwise adding the solution B obtained in the step B into the solution A obtained in the step a at a stirring speed of 350-500 rpm/min, stirring for reacting for 10-24 h, and then centrifuging, washing and drying to obtain a precursor, namely the porous metal organic frame ZIF-8; the volume ratio of the solution A to the solution B is 1: 1-1: 2;
d. c, carbonizing the porous metal organic framework ZIF-8 obtained in the step c in an inert atmosphere, adding 2 mol of hydrochloric acid solution to react to remove metal oxides, and fully washing and drying to obtain a hierarchical porous carbon material;
e. d, uniformly stirring and mixing the graded porous carbon material, the acetylene black and the polytetrafluoroethylene emulsion in a mass ratio of 80:10:10, 85:10:5 or 90:5:5, then coating the mixture on conductive substrate graphite paper, and drying the conductive substrate graphite paper at 100-120 ℃; finally, the hierarchical porous carbon material capacitive type desalting electrode material is prepared.
2. The method for preparing a capacitive desalination electrode material of hierarchical porous carbon material as claimed in claim 1, wherein the surfactant is at least one of cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide.
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| CN112820886B (en) * | 2020-12-29 | 2023-05-26 | 北京化工大学 | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof |
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| US8796462B2 (en) * | 2010-05-17 | 2014-08-05 | Rutgers, The State University Of New Jersey | Zeolitic imidazolate frameworks for kinetic separation of propane and propene |
| CN102897786B (en) * | 2012-10-16 | 2014-10-15 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
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