CN115011971A - TiO 2 2 TiC/C electrocatalyst and preparation method thereof - Google Patents
TiO 2 2 TiC/C electrocatalyst and preparation method thereof Download PDFInfo
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- CN115011971A CN115011971A CN202210740712.1A CN202210740712A CN115011971A CN 115011971 A CN115011971 A CN 115011971A CN 202210740712 A CN202210740712 A CN 202210740712A CN 115011971 A CN115011971 A CN 115011971A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of nanotechnology and electrocatalysis technology, and particularly provides TiO 2 A TiC/C electrocatalyst and a preparation method thereof. TiO 2 2 The TiC/C electrocatalyst is characterized in that polyacrylonitrile/polymethacrylic/TiO is prepared first 2 The composite material is oxidized, carbonized and thermally reduced to obtain a TiC/C composite matrix, and the TiC/C composite matrix and TiO prepared by an electrochemical method are combined 2 The nanotubes are roasted together to obtain the finished product. TiO prepared by the invention 2 the/TiC/C composite material has a large surface area, is a nano porous material in size, improves the wettability of electrolyte between electrode materials due to the exposure of more active sites, improves the conductivity of the material due to the introduction of TiC, and enhances the mechanical strength due to the existence of C.
Description
Technical Field
The invention belongs to the field of nanotechnology and electrocatalysis technology, and particularly provides TiO 2 A TiC/C electrocatalyst and a preparation method thereof.
Background
The traditional fossil energy consumption is increased year by year, the reserve is seriously insufficient, and meanwhile, the problems of environmental pollution, natural ecological environment damage, greenhouse effect and the like caused by the use of fossil energy seriously harm the survival of human beings. Hydrogen energy is regarded as a clean and pollution-free novel energy source as a new energy source with the most development potential, and the problem needing to be broken through firstly for utilizing the hydrogen energy is the preparation of the hydrogen. The hydrogen preparation by water electrolysis is simple and efficient. The platinum is used as a main active substance for electrolysis to produce hydrogen, but the platinum is expensive and has extremely high cost, so that the technology cannot be used on a large scale, and the development of the field is greatly limited. Therefore, the key point for realizing the industrialization of the non-noble metal high-efficiency hydrogen evolution electrocatalyst which is low in price and rich in reserves is to search.
TiO 2 The nano tube has adsorption capacity and larger specific surface area, and can also provide a channel for charge transmission, improve the conductivity of TiC by utilizing the excellent conductivity of the TiC, reduce the agglomeration effect among particles, improve the dispersity of the catalyst and expose more active sites, thereby improving the catalytic performance.
Disclosure of Invention
The object of the present invention is to provide a highly efficient and stable TiO 2 A TiC/C electrocatalyst and a preparation method thereof. Usually, the nanotube array with large specific surface area has good adsorption performance, and TiO is prepared under low current density by a growth competition mechanism based on parallel and vertical directions in the nanotubes 2 The nano tube array, TiC with nano size obtained by solvothermal and quenching treatment can be uniformly dispersed on carbon cloth, thereby overcoming the disadvantages of high cost in electrocatalytic hydrogen evolution and the agglomeration phenomenon frequently occurring in a catalyst.
TiO 2 2 The TiC/C electrocatalyst is characterized in that polyacrylonitrile/polymethacrylic/TiO is prepared first 2 The composite material is oxidized, carbonized and thermally reduced to obtain a TiC/C composite matrix, and the TiC/C composite matrix and TiO prepared by an electrochemical method are combined 2 The nanotubes are roasted together to obtain the finished product. The preparation method comprises the following specific steps:
(1) dissolving Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) in a mixed solution of N, N-Dimethylformamide (DMF)/Tetrahydrofuran (THF)/acetone, and violently dissolving the mixture at 66-77 DEG CStirring for 4-8 h to obtain a solution A; dissolving tetrabutyl titanate in a mixed solution of N, N-dimethylformamide/glacial acetic acid to obtain a solution B, slowly adding the solution B into the solution A, and magnetically stirring for 7-8 h at normal temperature; then quenching the obtained solution for 7-7 h, and repeatedly washing the quenched solution for multiple times by using an ice-water mixture, distilled water and absolute ethyl alcohol to obtain PAN/PMMA/TiO 2 A composite material;
(2) the PAN/PMMA/TiO obtained in the step (1) 2 The composite material is subjected to oxidation, low-temperature carbonization, high-temperature carbonization and thermal reduction to obtain a TiC/C composite matrix;
(3) to contain NH 4 Using ethylene glycol solution of F as electrolyte, using a titanium sheet as an anode and a platinum sheet as a cathode, carrying out constant-pressure oxidation reaction in a water bath at a certain temperature for a period of time, and then placing the obtained product in a muffle furnace for calcination; after the calcination is finished, cleaning the mixture by using distilled water and dilute hydrochloric acid, and drying the mixture by using nitrogen to obtain TiO 2 A nanotube;
(4) in N 2 Under the protection, the TiC/C composite matrix and the TiO are mixed 2 Calcining the nanotubes together to obtain TiO 2 a/TiC/C electrocatalyst.
Preferably, the mass ratio of the N, N-dimethylformamide/tetrahydrofuran/acetone mixed solution in the step (1) is 16: 3: 3, the mass ratio of the N, N-dimethylformamide to the glacial acetic acid in the mixed solution is 16: 1.
preferably, in the solution A in the step (1), the mass fraction of polyacrylonitrile is 7-16%, and the mass fraction of polymethyl methacrylate is 3-7%; in the solution B, the mass fraction of the tetrabutyl titanate is 6.7-2.7%.
Preferably, the quenching temperature in the step (1) is-46 ℃ to-7 ℃.
Preferably, the oxidation in the step (2) is to heat the mixture to 266-276 ℃ from normal temperature at a heating rate of 3-7 ℃/min in a pure air atmosphere of 3-7 mL/min, keep the temperature for 3-7 h, heat the mixture to 276-286 ℃ at a heating rate of 3-7 ℃/min, and keep the temperature for 3-7 h.
Preferably, the low-temperature carbonization in the step (2) is carried out in a pure nitrogen atmosphere of 6.7-1.7 mL/min, the temperature is raised to 666-776 ℃ at the temperature rise rate of 3-7 ℃/min, and the temperature is kept for 1-3 h.
Preferably, the high-temperature carbonization in the step (2) is carried out in a pure nitrogen atmosphere of 1.6-2.6 mL/min, the temperature is raised to 876-1166 ℃ at the heating rate of 3-6 ℃/min, and the temperature is kept for 2-7 h.
Preferably, the thermal reduction in the step (2) is carried out in an argon atmosphere of 1.6-2.6 mL/min, the temperature is raised to 1366-1766 ℃ at a heating rate of 3-6 ℃/min, and the temperature is kept for 2-7 h.
Preferably, H is as described in step (3) 4 The mass fraction of F is 6.17-6.7%, and the volume fraction of glycol is 1-17%.
Preferably, in the step (3), the anodic oxidation voltage is 26V-96V, the oxidation time is 1-16 h, and the water bath temperature is 7-16 ℃.
Preferably, the calcining temperature in the step (3) is 766-766 ℃, and the time is 2-3 h.
Preferably, the roasting temperature in the step (4) is 276-766 ℃, and the time is 2-7 h.
The TiO provided by the invention 2 the/TiC/C electrocatalyst is synthesized by a two-step method and is prepared into TiO by an electrochemical method 2 The nano array is roasted with the TiC/C composite material obtained by quenching to obtain TiO 2 a/TiC/C electrocatalyst. TiO prepared by the invention 2 the/TiC/C composite material has a large surface area, is a nano porous material in size, improves the wettability of electrolyte between electrode materials due to the exposure of more active sites, improves the conductivity of the material due to the introduction of TiC, and enhances the mechanical strength due to the existence of C.
TiO prepared by the invention 2 the/TiC/C electrocatalyst uses CHI766E electrochemical workstation to perform hydrogen evolution reaction catalytic activity test in a three-electrode system. Working electrode is loaded with TiO 2 1cm of/TiC electrocatalyst 2 The carbon cloth, the reference electrode is a saturated calomel electrode, the counter electrode is a carbon rod electrode, and the electrolyte solution is 1mol/L KOH. In electrochemical assayPrior to dosing, the sample was degassed by argon bubbling for 36min and the polarization curve was measured at room temperature from-6.6V to 6.1V at a scan rate of 7mV/s, as shown in FIG. 1. As can be seen from FIG. 1, the electrocatalytic hydrogen evolution of the present invention has good performance and low initial potential, in order to reach 16, 26 and 76mA cm -2 The electrodes only need an overpotential of 268, 262 and 443mV, respectively.
Drawings
FIG. 1 is a graph showing the polarization curve measured in the hydrogen evolution reaction catalytic activity test. Wherein the abscissa is the overpotential of the electrode and the ordinate is the current density.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
(1) 7g of PAN and 2.7g of PMMA were dissolved in a mixed solution of 47g of DMF, 13.7g of THF and 13.7g of acetone, and vigorously stirred at 76 ℃ for 6 hours to form a solution A. Adding 6.6g of tetrabutyl titanate into a mixed solution of 36g of DMF and 3g of glacial acetic acid to obtain a solution B, slowly dripping the solution B into the solution A, and magnetically stirring for 6 hours at normal temperature.
Pouring the obtained solution into a beaker, and putting the beaker into a refrigerator at the temperature of between 16 ℃ below zero and 7 ℃ below zero to quench for 6 hours. After quenching is finished, 766mL of ice-water mixture is quickly poured into a beaker, the organic reagent in the solution is extracted, distilled water is replaced and washed every 7 hours, and the process is repeated for more than 7 times. Washing with anhydrous ethanol for 3 times, and vacuum drying to obtain PAN/PMMA/TiO 2 A composite material.
(2) Taking about 6g of the obtained composite material, placing the composite material in a tube furnace, introducing pure air at the flow rate of 4mL/min, heating from the normal temperature to 276 ℃ at the speed of 4 ℃/min, preserving heat for 4h, then heating to 286 ℃ at the speed of 4 ℃/min, and preserving heat for 4 h.
In a pure nitrogen atmosphere of 1mL/min, the temperature is increased to 686 ℃ at the temperature increase rate of 7 ℃/min, and the temperature is kept for 2 h.
In a pure nitrogen atmosphere of 2mL/min, the temperature is increased to 976 ℃ at the heating rate of 7 ℃/min, and the temperature is preserved for 3 h.
And in an argon atmosphere of 1.7mL/min, heating to 1466 ℃ at the heating rate of 7 ℃/min, preserving heat for 3.7h, and obtaining the TiC/C composite matrix after finishing preserving heat.
(3) Cutting titanium sheet with thickness of 6.27mm into 1cm × 1cm pieces, cleaning in distilled water, acetone and isopropanol for 3 times, blowing with nitrogen gas, and using 6.3% H 4 F. Using a mixed aqueous solution with the volume fraction of 16% of ethylene glycol as an electrolyte, using a titanium sheet as an anode, carrying out anodic oxidation reaction for 7 hours under the condition of a constant-voltage direct-current power supply of 76V, controlling the temperature to be about 16 ℃, calcining for 2 hours at 666 ℃ in a muffle furnace after the reaction is finished, washing for 3 times by using distilled water after the calcination is finished, carrying out ultrasonic cleaning in 6.2M dilute hydrochloric acid, and using N 2 Blow-drying to obtain TiO 2 A nanotube.
(4) The obtained TiO is mixed 2 Placing the nanotube and TiC/C composite substrate in a muffle furnace, heating to 376 ℃, roasting for 4h, and cooling to obtain TiO 2 a/TiC/C electrocatalyst.
Example 2
(1) 7g of PAN and 2.7g of PMMA were dissolved in a mixed solution of 47g of DMF, 13.7g of THF and 13.7g of acetone, and vigorously stirred at 76 ℃ for 6 hours to form a solution A. Adding 6.6g of tetrabutyl titanate into a mixed solution of 36g of DMF and 3g of glacial acetic acid to obtain a solution B, slowly dripping the solution B into the solution A, and magnetically stirring for 6 hours at normal temperature.
Pouring the obtained solution into a beaker, and putting the beaker into a refrigerator at the temperature of between 16 ℃ below zero and 7 ℃ below zero to quench for 6 hours. After quenching is finished, 766mL of ice-water mixture is quickly poured into a beaker, the organic reagent in the solution is extracted, distilled water is replaced and washed every 7 hours, and the process is repeated for more than 7 times. Washing with anhydrous ethanol for 3 times, and vacuum drying to obtain PAN/PMMA/TiO 2 A composite material.
(2) Taking about 6g of the obtained composite material, placing the composite material in a tubular furnace, introducing pure air at the flow rate of 7mL/min, heating from the normal temperature to 276 ℃ at the speed of 7 ℃/min, preserving heat for 3h, then heating to 286 ℃ at the speed of 7 ℃/min, and preserving heat for 3 h.
In a pure nitrogen atmosphere of 1mL/min, the temperature is raised to 776 ℃ at the heating rate of 7 ℃/min, and the temperature is kept for 2 h.
Raising the temperature to 1666 ℃ at the heating rate of 7 ℃/min in a pure nitrogen atmosphere of 2mL/min, and preserving the temperature for 2.7 h.
And in an argon atmosphere of 1.7mL/min, heating to 1766 ℃ at the heating rate of 6 ℃/min, preserving heat for 2h, and obtaining the TiC/C composite matrix after the heat preservation is finished.
(3) Cutting a titanium sheet with the thickness of about 6.27mm into small pieces of 1cm multiplied by 1cm, respectively cleaning for 3 times under distilled water, acetone and isopropanol, drying by using nitrogen, and using H with the mass fraction of 6.3 percent 4 F. Using a mixed aqueous solution with the volume fraction of 16% of ethylene glycol as an electrolyte, using a titanium sheet as an anode, carrying out an anodic oxidation reaction for 4.7h under the condition of a 66V constant-voltage direct-current power supply, controlling the temperature to be about 16 ℃, calcining for 2h at 666 ℃ in a muffle furnace after the reaction is finished, washing for 3 times by using distilled water after the calcination is finished, carrying out ultrasonic cleaning in 6.2M dilute hydrochloric acid, and using N 2 Blow-drying to obtain TiO 2 A nanotube.
(4) The obtained TiO is mixed 2 Placing the nanotube and TiC/C composite substrate in a muffle furnace, heating to 476 ℃, roasting for 3h, and cooling to obtain TiO 2 a/TiC/C electrocatalyst.
Claims (10)
1. TiO (titanium dioxide) 2 the/TiC/C electrocatalyst is characterized in that: firstly, polyacrylonitrile/polymethacrylic acid/TiO is prepared 2 The composite material is oxidized, carbonized and thermally reduced to obtain a TiC/C composite matrix, and the TiC/C composite matrix and TiO prepared by an electrochemical method are combined 2 The nanotubes are roasted together to obtain the finished product.
2. TiO 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following preparation steps:
(1) dissolving polyacrylonitrile and polymethyl methacrylate in a mixed solution of N, N-dimethylformamide/tetrahydrofuran/acetone, and violently stirring for 4-8 hours at the temperature of 60-75 ℃ to obtain a solution A; titanic acid IVDissolving butyl ester in a mixed solution of N, N-dimethylformamide/glacial acetic acid to obtain a solution B, slowly adding the solution B into the solution A, and magnetically stirring for 5-8 h at normal temperature; then quenching the obtained solution for 5-7 h, and repeatedly washing the quenched solution for multiple times by using an ice-water mixture, distilled water and absolute ethyl alcohol to obtain polyacrylonitrile/polymethyl methacrylate/TiO 2 A composite material;
(2) the polyacrylonitrile/polymethyl methacrylate/TiO obtained in the step (1) 2 The composite material is subjected to oxidation, low-temperature carbonization, high-temperature carbonization and thermal reduction to obtain a TiC/C composite matrix;
(3) to contain NH 4 Using the ethylene glycol solution of F as electrolyte, using a titanium sheet as an anode and a platinum sheet as a cathode, carrying out constant-pressure oxidation reaction for a period of time in a water bath at a certain temperature, and then placing the obtained product in a muffle furnace for calcination; after the calcination is finished, cleaning the mixture by using distilled water and dilute hydrochloric acid, and drying the mixture by using nitrogen to obtain TiO 2 A nanotube;
(4) at N 2 Under the protection, the TiC/C composite matrix and the TiO are mixed 2 Calcining the nanotubes together to obtain TiO 2 a/TiC/C electrocatalyst.
3. A TiO compound according to claim 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: in the solution A in the step (1), the mass fraction of polyacrylonitrile is 5-10%, and the mass fraction of polymethyl methacrylate is 3-5%; in the solution B, the mass fraction of the tetrabutyl titanate is 0.5-2.5%.
4. A TiO compound according to claim 3 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: the mass ratio of the N, N-dimethylformamide/tetrahydrofuran/acetone mixed solution in the step (1) is 10: 3: 3, the mass ratio of the N, N-dimethylformamide to the glacial acetic acid in the mixed solution is 10: 1.
5. a TiO compound according to claim 2 2 TiC/C electro-catalysisThe preparation method of the reagent is characterized in that: the quenching temperature in the step (1) is-40 ℃ to-5 ℃.
6. A TiO compound according to claim 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: the oxidation in the step (2) is to heat the mixture to 200-250 ℃ from normal temperature at the heating rate of 3-5 ℃/min in the pure air atmosphere of 3-5 mL/min, keep the temperature for 3-5 h, heat the mixture to 270-280 ℃ at the heating rate of 3-5 ℃/min, and keep the temperature for 3-5 h; the low-temperature carbonization is carried out by heating to 600-750 ℃ at the heating rate of 3-5 ℃/min in the pure nitrogen atmosphere of 0.5-1.5 mL/min, and keeping the temperature for 1-3 h; the high-temperature carbonization is carried out by heating to 850-1100 ℃ at a heating rate of 3-6 ℃/min in a pure nitrogen atmosphere of 1.0-2.0 mL/min, and keeping the temperature for 2-5 h; the thermal reduction is to heat the mixture to 1300-1500 ℃ at a heating rate of 3-6 ℃/min in an argon atmosphere of 1.0-2.0 mL/min, and to preserve heat for 2-5 h.
7. A TiO compound according to claim 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: in the step (3), the anode oxidation voltage is 20V-90V, the oxidation time is 1-10 h, and the water bath temperature is 5-10 ℃.
8. A TiO compound according to claim 7 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: h described in step (3) 4 The mass fraction of F is 0.15-0.5%, and the volume fraction of glycol is 1-15%.
9. A TiO compound according to claim 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: the calcining temperature in the step (3) is 500-700 ℃, and the time is 2-3 h.
10. A TiO compound according to claim 2 2 The preparation method of the/TiC/C electrocatalyst is characterized by comprising the following steps: the roasting temperature in the step (4)The temperature is 250-500 ℃, and the time is 2-5 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6306343B1 (en) * | 1996-11-25 | 2001-10-23 | Ecodevice Laboratory Co., Ltd | Photocatalyst having visible light activity and uses thereof |
| CN106048783A (en) * | 2016-05-30 | 2016-10-26 | 天津工业大学 | Method for efficiently preparing titanium-based-carbon three-dimensional crimped nano fibers |
| CN108649189A (en) * | 2018-03-23 | 2018-10-12 | 浙江大学 | Titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material and its preparation method and application |
| CN111250102A (en) * | 2019-12-21 | 2020-06-09 | 西安交通大学 | TiO22Preparation method of NiMo alloy catalyst supported by nanotube array |
| CN113224293A (en) * | 2021-04-02 | 2021-08-06 | 湖北工程学院 | Preparation method and application of titanium carbide/carbon nano-film material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306343B1 (en) * | 1996-11-25 | 2001-10-23 | Ecodevice Laboratory Co., Ltd | Photocatalyst having visible light activity and uses thereof |
| CN106048783A (en) * | 2016-05-30 | 2016-10-26 | 天津工业大学 | Method for efficiently preparing titanium-based-carbon three-dimensional crimped nano fibers |
| CN108649189A (en) * | 2018-03-23 | 2018-10-12 | 浙江大学 | Titanium carbide/carbon core-shell nano linear array load nitrogen-doped titanic acid lithium composite material and its preparation method and application |
| CN111250102A (en) * | 2019-12-21 | 2020-06-09 | 西安交通大学 | TiO22Preparation method of NiMo alloy catalyst supported by nanotube array |
| CN113224293A (en) * | 2021-04-02 | 2021-08-06 | 湖北工程学院 | Preparation method and application of titanium carbide/carbon nano-film material |
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