CN114497574B - Self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material - Google Patents
Self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 29
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
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- 229910052751 metal Inorganic materials 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 6
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- 238000007254 oxidation reaction Methods 0.000 claims description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
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- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003929 acidic solution Substances 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- YYXOKPOCUHEGJE-JJXSEGSLSA-N methyl (1s,3s,4s,5r)-3-(4-chlorophenyl)-8-(2-fluoroethyl)-8-azabicyclo[3.2.1]octane-4-carboxylate Chemical compound C1([C@H]2C[C@@H]3CC[C@@H](N3CCF)[C@H]2C(=O)OC)=CC=C(Cl)C=C1 YYXOKPOCUHEGJE-JJXSEGSLSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- 230000010287 polarization Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 technical field of electrocatalytic hydrogen evolution, and provides a self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material. The electrocatalytic material prepared by the invention has excellent electrocatalytic hydrogen evolution performance under alkaline and acidic conditions, and the catalyst is not easy to fall off.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic hydrogen evolution, and particularly relates to a self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material.
Technical Field
The technology for producing hydrogen by electrolyzing water provides a convenient and sustainable way for high-efficiency conversion and effective storage of electric energy, and is also an important way for preparing high-purity hydrogen. Although noble metals such as Pt have excellent hydrogen evolution catalytic performance, the noble metals have rare reserves in the crust, are expensive, and are not suitable for large-scale commercial application. Therefore, the development of efficient, low-cost and widely available non-noble metal hydrogen evolution electrocatalysts is an urgent need for solution.
Among the current non-noble metal hydrogen evolution electrocatalysts, transition Metal Phosphides (TMPs) have been widely used for hydrogen evolution reactions due to their good mechanical strength, electrochemical conductivity and chemical stability. However, the hydrogen evolution electrocatalyst is usually powder, and a binder is required to be added to prepare the electrode into suspension for coating, or the electrode is grown on various conductive matrixes such as glassy carbon, foam nickel mesh, foam copper mesh, foam nickel iron mesh, titanium sheet, copper sheet, carbon cloth and the like in situ. The addition of the polymer binder will greatly increase the electrical resistance of the electrocatalyst and reduce the electrochemical performance of the catalyst. And the catalyst is loaded on the conductive matrix, so that the electrocatalyst is easy to fall off from the surface of the electrode under high current density in the hydrogen evolution reaction process, and the stability is poor. Therefore, the loading of the high-activity metal phosphide hydrogen evolution catalyst on a proper conductive matrix is a key to improving the hydrogen evolution performance.
Disclosure of Invention
Aiming at the situation, the invention aims to provide a self-supporting hydrogen evolution electro-catalytic material which can effectively solve the problems of few active sites, low catalytic efficiency and poor stability of the existing hydrogen evolution electro-catalytic material.
In order to achieve the above purpose, the invention provides a self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material, which is prepared by calcining a transition metal doped carbon film and sodium phosphite in an argon atmosphere, and comprises the following specific operations:
taking a certain amount of transition metal doped carbon film and sodium hypophosphite according to the mass ratio of 1:5-1:10, and respectively placing the carbon film and the sodium hypophosphitePutting into two porcelain boats; transferring the mixture into a tube furnace, wherein sodium hypophosphite is arranged at the upstream side, and an MCNT@C carbon film is arranged at the downstream side; calcining at 350 deg.C for 2 hr under argon atmosphere, and raising temp. rate to 2 deg.C min -1 The method comprises the steps of carrying out a first treatment on the surface of the After naturally cooling to room temperature, a transition metal phosphide-doped carbon film was obtained and represented as an mpcnt@c carbon film.
Preparing the transition metal doped carbon film, namely placing the porous CNT@PAN film containing transition metal ions into a muffle furnace at 260 ℃ for pre-oxidation for 2 hours, wherein the heating rate is 2 ℃/min; pre-oxidizing, transferring to a tube furnace filled with a mixed gas of hydrogen and argon, carbonizing at 700-900 ℃ for 1 h, and heating at a speed of 5 ℃/min; finally, a transition metal doped carbon film is obtained and is marked as MCNT@C film, and M is Co, fe or Ni.
The preparation of the porous CNT@PAN film containing transition metal ions mainly comprises the steps of dissolving 0.5g of transition metal chloride in 10ml of ethylene glycol to form a solution A containing transition metal ions; 2g of carbon nano tube and 2g of polyacrylonitrile (PAN, MW=40000, > 99%) are dissolved in an organic solvent and magnetically stirred for 12 hours at 60-80 ℃ to form a uniform black solution B; mixing the solution A and the solution B, magnetically stirring for 5 hours to obtain uniform black casting solution, pouring the cooled solution on a glass plate, and scraping the solution into a liquid film with the thickness of 200+/-10 mu m by using a film coater; then the glass plate carrying the film layer is soaked in ultrapure water rapidly, after 24 hours of stabilization, the film is taken out of the water and naturally dried in the air, and then the vacuum drying is carried out for 4 hours at 90 ℃ to obtain the glass plate.
The transition metal chloride is CoCl 2 ·6H 2 O、FeCl 3 ·6H 2 O or NiCl.6H 2 O。
The organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N, N-dimethylacetamide.
The volume ratio of the mixed gas is 1:5 of hydrogen to argon, and the flow rate is 20-40 mL/min.
The beneficial effects of the invention are as follows: uniformly mixing a transition metal precursor, a carbon nano tube and a high polymer compound, coating the mixture into a high polymer film with a certain thickness, and carbonizing and phosphating the high polymer film to prepare the self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material; the metal phosphide is uniformly distributed in the carbon film, is tightly combined with the conductive matrix, is not easy to fall off, and can form a high conductive network by adding the carbon nano tube, meanwhile, the carbon film generated by carbonizing the high polymer compound is used as a supporting matrix of the catalyst, can generate a synergistic effect with the metal phosphide, reduces hydrogen evolution overpotential, and simultaneously has better hydrogen evolution catalytic performance in acidic and alkaline media.
Drawings
FIG. 1 is an X-ray diffraction pattern of the CoPCNT@C carbon film prepared in example 1;
FIG. 2 is a detailed scan of electrocatalytic hydrogen evolution under acidic conditions for an example;
FIG. 3 is a detailed scan of electrocatalytic hydrogen evolution under alkaline conditions for an example;
FIG. 4 is a graph showing the hydrogen evolution stability under alkaline conditions of example 1.
Detailed Description
The self-supporting hydrogen evolution electrocatalytic material prepared by different transition metal precursors is shown in the examples, and the electrocatalytic hydrogen evolution capability is effectively demonstrated by analyzing the scanning curve of the examples under the acid and alkali conditions.
Example 1
Weigh 0.5g CoCl 2 ·6H 2 O is dissolved in 10ml glycol to form Co-containing solution 2+ Is a solution A of (2); weigh 2g carbon nanotubes and 2g polyacrylonitrile (PAN, mw=40000),>99%) was dissolved in 21g of N, N-dimethylformamide and magnetically stirred at 70℃for 12 hours to form a uniformly black solution B. Mixing the solution A and the solution B, magnetically stirring 5h to obtain uniform black casting solution, pouring the cooled solution on a glass plate, and scraping the solution into a liquid film with the thickness of 200+/-10 mu m by using a film coater. Then the glass plate carrying the film layer is soaked in ultrapure water rapidly, after 24h is stabilized, the film is taken out of the water and naturally dried in the air, and then the vacuum drying is carried out at 90 ℃ for 4h, thus obtaining the porous Co-containing film 2+ Cnt@pan film.
Will contain Co 2+ The CNT@PAN film is placed in a muffle furnace at 260 ℃ for pre-oxidation 2h (the heating rate is 2 ℃/min), and the pre-oxidation is carried outMoving the carbon film to a tube furnace filled with a mixed gas of hydrogen and argon with the volume ratio of 1:5 and the flow rate of 30mL/min, carbonizing the carbon film at the temperature of 800 ℃ for 1 h (the heating rate is 5 ℃/min), and finally obtaining the transition metal doped carbon film which is marked as CoCNT@C.
And (3) taking a certain amount of CoCNT@C carbon film and sodium hypophosphite according to the mass ratio of 1:10, and respectively putting the carbon film and the sodium hypophosphite into two porcelain boats. Then transferred to a tube furnace with sodium hypophosphite upstream and a cocnt@c carbon film downstream. Calcining at 350deg.C under argon atmosphere for 2h at a heating rate of 2deg.C/min -1 . After naturally cooling to room temperature, a cobalt phosphide-doped carbon film was obtained and represented as a CoPCNT@C carbon film.
The CoPCNT@C carbon film material prepared in the embodiment is directly used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a graphite carbon rod is used as a counter electrode for electrochemical test by 0.5M H 2 SO 4 Or 1M KOH aqueous solution is used as electrolyte, and a three-electrode testing system is adopted to perform performance test on an electrochemical workstation. LSV curves were tested.
FIG. 1 is an X-ray diffraction pattern of a CoPCNT@C carbon film prepared in example 1 of the present invention, showing that the sample prepared in example 1 has characteristic X-ray diffraction peaks typical of CoP; FIGS. 2 and 3 show the linear polarization curves of the CoPCNT@C carbon film prepared in example 1 of the present invention in acidic and alkaline solutions when the current density reached-20 mA cm -2 When the CoPCNT@C carbon film electrode is in an acidic solution and an alkaline solution, the overpotential of the CoPCNT@C carbon film electrode is-77 mV and-102 mV respectively; the test result shows that the CoPCNT@C carbon film electrode prepared in the embodiment 1 of the invention has outstanding electrocatalytic hydrogen evolution performance.
Example 2
Weigh 0.5g NiCl 2 ·6H 2 O is dissolved in 10ml glycol to form Ni-containing 2+ Is a solution A of (2); 2g carbon nanotubes were weighed with 2g polyacrylonitrile (PAN, mw=40000,>99%) was dissolved in 21g N, N-dimethylacetamide and magnetically stirred at 60 ℃ for 12 hours to form a homogeneous black solution B. Mixing the solution A and the solution B, magnetically stirring 5h to obtain uniform black casting solution, pouring the cooled solution on a glass plate, and scraping the solution into a liquid film with the thickness of 200+/-10 mu m by using a film coater. Then rapidly putting the glass plate with the film layerSoaking in ultrapure water, stabilizing 24. 24h, taking out the membrane from water, naturally airing in air, and vacuum drying at 90deg.C for 4. 4h to obtain porous Ni-containing material 2+ Cnt@pan film.
Will contain Ni 2+ Pre-oxidizing the CNT@PAN film in a muffle furnace at 260 ℃ for 2h, wherein the heating rate is 2 ℃/min; transferring the mixture to a tubular furnace filled with hydrogen and argon in a volume ratio of 1:5 and a flow rate of 40mL/min, carbonizing 1 h at 900 ℃ and heating at a rate of 5 ℃/min; finally, a transition metal doped carbon film is obtained and is marked as NiCNT@C.
And (3) taking a certain amount of NiCNT@C carbon film and sodium hypophosphite according to the mass ratio of 1:5, and respectively putting the NiCNT@C carbon film and the sodium hypophosphite into two porcelain boats. Then transferred to a tube furnace with sodium hypophosphite upstream and a NiCNT@C carbon film downstream. Calcining at 350deg.C under argon atmosphere for 2h at a heating rate of 2deg.C/min -1 . After naturally cooling to room temperature, a nickel phosphide-doped carbon film was obtained and represented as a NiPCNT@C carbon film.
The NiPCNT@C carbon film material prepared in the embodiment is directly used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a graphite carbon rod is used as a counter electrode for electrochemical test by 0.5M H 2 SO 4 Or 1MKOH aqueous solution is used as electrolyte, and a three-electrode testing system is adopted to perform performance test on an electrochemical workstation. LSV curves were tested.
As shown in FIG. 2 and FIG. 3, the linear polarization curve of the NiPCNT@C carbon film prepared in example 2 of the present invention in an acidic and alkaline solution was measured when the current density reached-mA.cm -2 At this time, the overpotential of the NiPCNT@C carbon film electrode in acidic and alkaline solutions was-86 mV and-116 mV, respectively.
Example 3
Weigh 0.5g FeCl 3 ·6H 2 O is dissolved in 10ml glycol to form Fe-containing 3+ Is a solution A of (2); 2g carbon nanotubes were weighed with 2g polyacrylonitrile (PAN, mw=40000,>99%) was dissolved in 21g N, N-dimethylformamide and magnetically stirred at 80 ℃ for 12 hours to form a homogeneous black solution B. Mixing the solution A and the solution B, magnetically stirring 5h to obtain uniform black casting solution, pouring the cooled solution onto a glass plate, and scraping with a film coaterThe thickness of the liquid film is 200+/-10 mu m. Then the glass plate with the film layer is soaked in ultrapure water rapidly, after 24h is stabilized, the film is taken out of the water and naturally dried in the air, and then the porous Fe-containing film is prepared after 4h of vacuum drying at 90 DEG C 3+ Cnt@pan film.
Will contain Fe 3+ The CNT@PAN film is placed in a muffle furnace at 260 ℃ for pre-oxidation 2h (the heating rate is 2 ℃/min), the pre-oxidation is transferred into a tube furnace filled with hydrogen and argon mixed gas with the volume ratio of 1:5 and the flow rate of 20 mL/min, and 1 h (the heating rate is 5 ℃/min) is carbonized at 700 ℃ to finally obtain a transition metal doped carbon film which is marked as FeCNT@C.
And taking a certain amount of FeCNT@C carbon film and sodium hypophosphite according to the mass ratio of 1:10, and respectively putting the FeCNT@C carbon film and the sodium hypophosphite into two porcelain boats. Then transferred to a tube furnace with sodium hypophosphite upstream and FeCNT@C carbon film downstream. Calcining at 350deg.C under argon atmosphere for 2h at a heating rate of 2deg.C/min -1 . After naturally cooling to room temperature, an iron phosphide-doped carbon film was obtained and represented as FePCNT@C carbon film.
The FePCNT@C carbon film material prepared in the embodiment is directly used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a graphite carbon rod is used as a counter electrode for electrochemical test by 0.5M H 2 SO 4 Or 1M KOH aqueous solution is used as electrolyte, and a three-electrode testing system is adopted to perform performance test on an electrochemical workstation. LSV curves were tested.
According to FIGS. 2 and 3, the linear polarization curves of FePCNT@C carbon films prepared in example 3 of the present invention in acidic and alkaline solutions are shown when the current density reaches-mA cm -2 The overpotential of the FePCNT@C carbon film electrode in the acidic and alkaline solutions is-99 mV and-136 mV respectively.
According to the embodiment, the metal phosphide is uniformly distributed in the carbon film, and is tightly combined with the conductive matrix and not easy to fall off by combining the embodiment with the attached drawing of the specification; the added carbon nano tube can form a high conductive network, and the carbon film generated by carbonizing the high molecular compound is used as a supporting matrix of the catalyst, can generate a synergistic effect with metal phosphide, reduces hydrogen evolution overpotential, and has good hydrogen evolution catalytic performance in acidic and alkaline media.
Claims (6)
1. A self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material is characterized in that metal phosphide is uniformly distributed in the carbon film, is tightly combined with a conductive matrix, forms a high-conductivity network by carbon nanotubes, and forms a porous carbon film hydrogen evolution electrocatalytic material by taking the carbon film generated by carbonizing a high-molecular compound as a supporting matrix of a catalyst and generating a synergistic effect with the metal phosphide;
the self-supporting transition metal phosphide doped porous carbon film hydrogen evolution electrocatalytic material is prepared by the following method, and the specific operation steps comprise:
taking a certain amount of transition metal doped carbon film and sodium hypophosphite according to the mass ratio of 1:5-1:10, and respectively putting the carbon film and the sodium hypophosphite into two porcelain boats; transferring the carbon film into a tube furnace, wherein sodium hypophosphite is arranged at the upstream side, and a transition metal doped carbon film is arranged at the downstream side; calcining at 350deg.C under argon atmosphere for 2h at a heating rate of 2deg.C/min -1 The method comprises the steps of carrying out a first treatment on the surface of the After naturally cooling to room temperature, a transition metal phosphide-doped carbon film was obtained and represented as an MPCNT@C carbon film.
2. A self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material as set forth in claim 1, wherein: preparing the transition metal doped carbon film, namely placing the porous CNT@PAN film containing transition metal ions into a muffle furnace at 260 ℃ for pre-oxidation for 2h, wherein the heating rate is 2 ℃/min; pre-oxidizing, transferring to a tube furnace filled with a mixed gas of hydrogen and argon, carbonizing at 700-900 ℃ for 1 h, and heating at a speed of 5 ℃/min; finally, a transition metal doped carbon film is obtained and is marked as MCNT@C film, and M is Co, fe or Ni.
3. A self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material as claimed in claim 2, wherein: the preparation of the porous CNT@PAN film containing transition metal ions mainly comprises the steps of dissolving 0.5g of transition metal chloride in 10ml of ethylene glycol to form a solution A containing transition metal ions; 2g of carbon nano tube and 2g of polyacrylonitrile are dissolved in an organic solvent and magnetically stirred for 12 hours at 60-80 ℃ to form a uniform black solution B; mixing the solution A and the solution B, magnetically stirring 5h to obtain uniform black casting solution, pouring the cooled solution on a glass plate, and scraping the solution into a liquid film with the thickness of 200+/-10 mu m by using a film coater; then the glass plate carrying the film layer is soaked in ultrapure water rapidly, after 24h is stabilized, the film is taken out of the water and naturally dried in the air, and then the film is dried in vacuum at 90 ℃ for 4h, thus obtaining the glass plate.
4. The self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material as set forth in claim 2, wherein the volume ratio of hydrogen to argon is 1:5 and the flow rate is 20-40 mL/min.
5. The self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material as set forth in claim 3, wherein said transition metal chloride is CoCl 2 ·6H 2 O、FeCl 3 ·6H 2 O or NiCl.6H 2 O。
6. A self-supporting transition metal phosphide-doped porous carbon film hydrogen evolution electrocatalytic material according to claim 3, wherein the organic solvent is selected from N, N-dimethylformamide, dimethyl sulfoxide or N, N-dimethylacetamide.
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