CN111545238A - Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst and preparation method thereof - Google Patents
Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- 239000001257 hydrogen Substances 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 82
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 82
- 239000002071 nanotube Substances 0.000 claims abstract description 62
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910015346 Ni2B Inorganic materials 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- WRLJWIVBUPYRTE-UHFFFAOYSA-N [B].[Ni].[Ni] Chemical compound [B].[Ni].[Ni] WRLJWIVBUPYRTE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 238000010438 heat treatment Methods 0.000 claims description 71
- 239000012153 distilled water Substances 0.000 claims description 56
- 239000012265 solid product Substances 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229920000877 Melamine resin Polymers 0.000 claims description 31
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 23
- 239000002121 nanofiber Substances 0.000 claims description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- 229910015667 MoO4 Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical group N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 3
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000007847 structural defect Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 description 14
- 229910021397 glassy carbon Inorganic materials 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 229920000557 Nafion® Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241001669696 Butis Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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Abstract
The invention relates to the technical field of electrocatalytic hydrogen production and discloses Co9S8‑MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst comprises the following formula raw materials and components: modified porous g-C3N4Nanotube, Co (NO)3)2Trimesic acid, thiourea and Ni-doped nano MoS2. Such a Co9S8‑MoS2Load g-C3N4By the electrocatalytic hydrogen production catalyst of nickel boride Ni2B in situ modification of g-C3N4On the surface of which structural defects are formed, and which can effectively exfoliate g-C3N4Form a large amount of mesoporous structures, increase g-C3N4Wettability with electrolyte, providing more electrochemically active sites, Ni2B has boron atoms in g-C3N4The interior forms a C-B-N ternary structure and a hexagonal boron nitride structure, and the g-C is reduced3N4Ni replaces part of the crystal lattice of Mo, and MoS is improved2Conductivity of, Ni-doped Nano MoS2Better adhesion to porous g-C3N4In the pores and mesoporous structure of nanotubes, Co9S8And MoS2And a heterogeneous interface is formed, so that the transmission and diffusion of electrons are accelerated, and the overpotential of the hydrogen evolution reaction is reduced.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen production, in particular to Co9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst and the preparation method thereof.
Background
Fossil fuel makes the indispensable energy in the human life production activity, but along with fossil energy reserves reduce day by day, and the environmental problem that the burning fossil energy brought is serious day by day, it becomes urgent to develop novel efficient renewable energy, hydrogen energy is the cleanest energy in the world, the combustion product of hydrogen is pollution-free water, the resource of hydrogen energy is abundant, the calorific value is high, combustion performance is excellent, be the most effective clean energy who solves the energy crisis, hydrogen energy mainly is applied to aspects such as hydrogen burning, hydrogen energy electricity generation, hydrogen power car, fuel cell.
At present, the preparation of hydrogen mainly comprises the hydrogen preparation by mineral fuel, the hydrogen preparation by methane catalytic thermal decomposition, the biological hydrogen preparation and the hydrogen preparation by water electrolysis, wherein the hydrogen preparation by water electrolysis is the hydrogen preparation method with the most development potential, the Pt-based catalyst has excellent performance of water hydrogen preparation by electrocatalytic decomposition, but the content of noble metals such as platinum is rare, the price is high, the wide commercial use of the Pt-based catalyst is limited, and the carbon-based catalyst such as graphene carbon nitride g-C3N4The electrolytic water hydrogen evolution activity is good; transition metal sulfides such as MoS2CdS and the like have hydrogen adsorption free energy similar to Pt and are hydrogen production catalysts for electrolysis of water with great potential, butIs MoS2The conductive performance is poor, the transmission of electrons in the oxidation-reduction reaction is hindered, the water electrolysis reaction is inhibited, and the hydrogen evolution efficiency is reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Co9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst and the preparation method thereof solve the problem of MoS2The conductivity is poor, and the efficiency of the catalyst for decomposing water to produce hydrogen is influenced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: co9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst comprises the following formula raw materials and components in parts by weight: 10-16 parts of modified porous g-C3N4Nanotube, 15-24 parts of Co (NO)3)27-9 parts of trimesic acid, 6-10 parts of thiourea and 41-62 parts of Ni-doped nano MoS2。
Preferably, the modified porous g-C3N4The preparation method of the nanotube comprises the following steps:
(1) adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 1-2 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 55-75 ℃, uniformly stirring for reaction for 2-4h, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the melamine nanofiber.
(2) Placing the melamine nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-8 ℃/min, the temperature is raised to 520-560 ℃, the heat preservation and calcination are carried out for 2-4h, and the calcination product is porous g-C3N4A nanotube.
(3) Adding distilled water and porous g-C into a reaction bottle3N4Nanotubes and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30-60min, and adding NaBH into the reaction bottle4Stirring at 10-20 deg.C for 2-4 hr, dissolvingVacuum drying the solution to remove the solvent, washing the solid product with distilled water, and drying thoroughly to obtain Ni2B modified porous g-C3N4A nanotube.
Preferably, the porous g-C3N4Nanotube, NiCl2And NaBH4The mass ratio is 1200-1600:1.1-1.3: 1.
Preferably, the Ni-doped nano MoS2The preparation method comprises the following steps:
(1) adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 180-230 ℃, reacting for 20-30h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2。
Preferably, the Na is2MoO4、Ni(NO3)2And the amount ratio of the thioacetamide to the thioacetamide is 0.04-0.08:1: 4-6.
Preferably, said Co9S8-MoS2Load g-C3N4The preparation method of the electrocatalytic hydrogen production catalyst comprises the following steps:
(1) adding acetone solvent and 10-16 parts of modified porous g-C into a reaction bottle3N4Nanotube, 15-24 parts of Co (NO)3)2And 7-9 parts of trimesic acid, placing a reaction bottle in an ultrasonic dispersion instrument for ultrasonic dispersion treatment for 1-2h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-70 ℃, uniformly stirring for reaction for 8-15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the Co-MOFs coated g-C3N4。
(2) Adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4And 6-10 parts of thiourea, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 130 ℃ and 150 ℃, reacting for 5-10h, and concentrating the solution under reduced pressure to remove the solutionWashing the solid product with distilled water, drying, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating to 360-380 deg.C at a heating rate of 2-4 deg.C/min, and calcining for 2-4 hr to obtain Co product9S8Coating g-C3N4。
(3) Adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4And 41-62 parts of Ni-doped nano MoS2The revolution speed of the planetary ball mill is 460 plus 620rpm, the rotation speed is 230 plus 310rpm, the materials are ball milled until the materials all pass through a screen with 1200 plus 1800 meshes, the mixed materials are decompressed and concentrated to remove the solvent and are fully dried, and the Co is prepared9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
such a Co9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst takes melamine nano-fiber as a precursor, and nano g-C is prepared by thermal cracking3N4Has rich pore structure and increased g-C3N4Wetting with electrolyte by nickel boride Ni2B in situ modification of g-C3N4On the surface of which structural defects are formed, and which can effectively exfoliate g-C3N4Form a large amount of mesoporous structures, shorten the transmission path of electrons and ions, and increase the g-C3N4Can provide more electrochemically active sites, and Ni2B has boron atoms in g-C3N4The interior forms a C-B-N ternary structure and a hexagonal boron nitride structure, and the g-C is reduced3N4Thereby increasing g-C3N4The conductivity of (2) reduces the overpotential of the hydrogen evolution reaction.
Such a Co9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst is prepared by hydrothermal synthesisObtaining Ni-doped nano MoS2Ni replaces part of Mo crystal lattice to improve MoS2While the Ni doping reduces the MoS2Modification of the free energy of hydrogen adsorption of unsaturated S atoms at the edge active sites to modify the porosity of g-C3N4Nano tube as matrix, Ni doped nano MoS2Better adhesion to porous g-C3N4In the pore and mesoporous structure of the nanotube, the nano MoS is effectively reduced2The agglomeration and aggregation of the catalyst can avoid covering the electrochemical active sites, thereby greatly enhancing the hydrogen evolution activity of the catalyst.
Such a Co9S8-MoS2Load g-C3N4The g-C is coated by a cobalt-based metal organic framework3N4Taking thiourea as a sulfur source as a precursor, and thermally cracking to obtain Co9S8Coating g-C3N4Then mixed with Ni doped nano MoS2Composite, Co9S8And MoS2A heterogeneous interface is formed, and the transmission and diffusion of electrons are accelerated, so that the overpotential of the hydrogen evolution reaction is reduced.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: co9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst comprises the following formula raw materials and components in parts by weight: 10-16 parts of modified porous g-C3N4Nanotube, 15-24 parts of Co (NO)3)27-9 parts of trimesic acid, 6-10 parts of thiourea and 41-62 parts of Ni-doped nano MoS2。
Modified porous g-C3N4The preparation method of the nanotube comprises the following steps:
(1) adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 1-2 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 55-75 ℃, uniformly stirring for reaction for 2-4h, filtering the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the melamine nanofiber.
(2) Placing the melamine nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-8 ℃/min, the temperature is raised to 520-560 ℃, the heat preservation and calcination are carried out for 2-4h, and the calcination product is porous g-C3N4A nanotube.
(3) Adding distilled water and porous g-C into a reaction bottle3N4Nanotubes and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30-60min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4The mass ratio of 1200-1600:1.1-1.3:1, stirring at a constant speed for 2-4h at 10-20 ℃, vacuum drying the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare Ni2B modified porous g-C3N4A nanotube.
Ni-doped nano MoS2The preparation method comprises the following steps:
(1) adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.04-0.08:1:4-6 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to the temperature of 180 DEG and 230 ℃, reacting for 20-30h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2。
Co9S8-MoS2Load g-C3N4The preparation method of the electrocatalytic hydrogen production catalyst comprises the following steps:
(1) adding acetone solvent and 10-16 parts of modified porous g-C into a reaction bottle3N4Nanotube, 15-24 parts of Co (NO)3)2And 7-9 parts of trimesic acid, placing a reaction bottle in an ultrasonic dispersion instrument for ultrasonic dispersion treatment for 1-2h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-70 ℃, uniformly stirring for reaction for 8-15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the Co-MOFs coated g-C3N4。
(2) Adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4And 6-10 parts of thiourea, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the solution into a reaction kettle heating box, heating to 130-plus-150 ℃, reacting for 5-10h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water, fully drying, placing the solid product into an atmosphere resistance furnace, introducing nitrogen, heating to 360-plus-380 ℃ at the rate of 2-4 ℃/min, keeping the temperature, and calcining for 2-4h to obtain a calcined product, namely Co9S8Coating g-C3N4。
(3) Adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4And 41-62 parts of Ni-doped nano MoS2The revolution speed of the planetary ball mill is 460 plus 620rpm, the rotation speed is 230 plus 310rpm, the materials are ball milled until the materials all pass through a screen with 1200 plus 1800 meshes, the mixed materials are decompressed and concentrated to remove the solvent and are fully dried, and the Co is prepared9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst.
Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on a glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode.
Example 1
(1) Preparation of melamine nanofiber component 1: adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 2 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 55 ℃, uniformly stirring for reaction for 2 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the melamine nanofiber component 1.
(2) Preparation of porous g-C3N4Nanotube component 1: placing the melamine nanofiber component 1 in an atmosphere resistance furnace, introducing nitrogen, heating at the speed of 2 ℃/min to a temperature ofCalcining at 520 ℃ for 2h in a heat preservation way to obtain a calcined product, namely porous g-C3N4Nanotube component 1.
(3) Preparation of modified porous g-C3N4Nanotube component 1: adding distilled water and porous g-C into a reaction bottle3N4Nanotube component 1 and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4Stirring at 10 deg.C for 2h at uniform speed with a mass ratio of 1200:1.1:1, vacuum drying the solution to remove solvent, washing the solid product with distilled water, and drying thoroughly to obtain Ni2B modified porous g-C3N4Nanotube component 1.
(4) Preparation of Ni-doped nano MoS2Component 1: adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.04:1:4 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 180 ℃, reacting for 20 hours, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2And (3) component 1.
(5) Preparation of Co-MOFs-coated g-C3N4Component 1: adding an acetone solvent and 10 parts of modified porous g-C into a reaction bottle3N4Nanotube component 1, 15 parts Co (NO)3)2And 7 parts of trimesic acid, placing a reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1 hour, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, uniformly stirring for reaction for 8 hours, performing reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain Co-MOFs coated g-C3N4And (3) component 1.
(6) Preparation of Co9S8Coating g-C3N4Component 1: adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4The components 1 and 6 portions of thiourea are evenly stirred and dissolvedTransferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating the reaction kettle to 130 ℃, reacting for 5 hours, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product into an atmosphere resistance furnace and introducing nitrogen, heating the solid product to 360 ℃ at the heating rate of 2 ℃/min, preserving heat and calcining for 2 hours, wherein the calcined product is Co9S8Coating g-C3N4And (3) component 1.
(7) Preparation of Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst material 1: adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4Component 1 and 62 parts of Ni-doped nano MoS2Performing ball milling on the component 1 at the revolution speed of 460rpm and the rotation speed of 230rpm of the planetary ball mill until the materials completely pass through a 1200-mesh screen, performing reduced pressure concentration on the mixed materials to remove the solvent, and fully drying to prepare the Co-containing material9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 1.
(8) Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 1 and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on a glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode 1.
Example 2
(1) Preparation of melamine nanofiber component 2: adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 2 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 75 ℃, uniformly stirring for reaction for 2 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the melamine nanofiber component 2.
(2) Preparation of porous g-C3N4Nanotube component 2: placing the melamine nanofiber component 2 in an atmosphere resistance furnace, introducing nitrogen, heating to 520 ℃ at the heating rate of 8 ℃/min, keeping the temperature, and calcining for 4 hours to obtain a calcined product which is a polymerHoles g-C3N4Nanotube component 2.
(3) Preparation of modified porous g-C3N4Nanotube component 2: adding distilled water and porous g-C into a reaction bottle3N4Nanotube component 2 and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4Stirring at 10 deg.C for 4h at uniform speed with a mass ratio of 1600:1.1:1, vacuum drying the solution to remove solvent, washing the solid product with distilled water, and drying thoroughly to obtain Ni2B modified porous g-C3N4Nanotube component 2.
(4) Preparation of Ni-doped nano MoS2And (2) component: adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.04:1:4 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 230 ℃, reacting for 20 hours, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2And (3) component 2.
(5) Preparation of Co-MOFs-coated g-C3N4And (2) component: adding an acetone solvent and 11 parts of modified porous g-C into a reaction bottle3N4Nanotube component 2, 17 parts Co (NO)3)2And 7.5 parts of trimesic acid, placing a reaction bottle in an ultrasonic dispersion instrument for ultrasonic dispersion treatment for 2 hours, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 8 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the Co-MOFs coated g-C3N4And (3) component 2.
(6) Preparation of Co9S8Coating g-C3N4And (2) component: adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4The component 2 and 7.5 portions of thiourea are evenly stirred and then transferred into a polytetrafluoroethylene reaction kettle,placing the solid product in a reaction kettle heating box, heating to 130 ℃, reacting for 10 hours, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in an atmosphere resistance furnace and introducing nitrogen, heating at the rate of 2 ℃/min to 360 ℃, preserving heat and calcining for 4 hours, wherein the calcined product is Co9S8Coating g-C3N4And (3) component 2.
(7) Preparation of Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst material 2: adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4Component 2 and 57 parts of Ni-doped nano MoS2And (2) performing ball milling on the material until the material completely passes through a 1200-mesh screen when the revolution speed of the planetary ball mill is 460rpm and the rotation speed of the planetary ball mill is 230rpm, concentrating the mixed material under reduced pressure to remove the solvent, and fully drying to prepare the Co-based material9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 2.
(8) Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 2 and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on a glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode 2.
Example 3
(1) Preparation of melamine nanofiber component 3: adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 1 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 65 ℃, uniformly stirring for reaction for 3 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to obtain the melamine nanofiber component 3.
(2) Preparation of porous g-C3N4Nanotube component 3: placing the melamine nanofiber component 3 in an atmosphere resistance furnace, introducing nitrogen, heating to 540 ℃ at the heating rate of 5 ℃/min, keeping the temperature, and calcining for 3h to obtain a calcined product, namely porous g-C3N4Nanotube and method of manufacturing the sameAnd (3) component.
(3) Preparation of modified porous g-C3N4Nanotube component 3: adding distilled water and porous g-C into a reaction bottle3N4Nanotube component 3 and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 45min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4The mass ratio is 1400:1.2:1, stirring at a constant speed for 3h at 15 ℃, vacuum-drying the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare Ni2B modified porous g-C3N4Nanotube component 3.
(4) Preparation of Ni-doped nano MoS2And (3) component: adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.06:1:5 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 200 ℃, reacting for 25 hours, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2And (3) component.
(5) Preparation of Co-MOFs-coated g-C3N4And (3) component: adding an acetone solvent and 12 parts of modified porous g-C into a reaction bottle3N4Nanotube component 3, 20 parts Co (NO)3)2And 8 parts of trimesic acid, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 1.5h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for reaction for 12h, performing reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain Co-MOFs coated g-C3N4And (3) component.
(6) Preparation of Co9S8Coating g-C3N4And (3) component: adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N43 parts of thiourea and 8 parts of the component are stirred uniformly, then the solution is transferred into a polytetrafluoroethylene reaction kettle and placed in a heating box of the reaction kettle, and the solution is heated until the solution is heatedReacting for 7 hours at 140 ℃, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 3 ℃/min, heating to 370 ℃, preserving heat and calcining for 3 hours, and the calcined product is Co9S8Coating g-C3N4And (3) component.
(7) Preparation of Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst material 3: adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4Component 3 and 52 parts of Ni-doped nano MoS2And (3) performing ball milling on the material until the material completely passes through a 1500-mesh screen, performing reduced pressure concentration on the mixed material to remove the solvent, and fully drying to prepare the Co-containing material, wherein the revolution speed of the planetary ball mill is 540rpm, and the rotation speed of the planetary ball mill is 270rpm9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 3.
(8) Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 3 and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on a glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode 3.
Example 4
(1) Preparation of melamine nanofiber component 4: adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 2 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 55 ℃, uniformly stirring for reaction for 4 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the melamine nanofiber component 4.
(2) Preparation of porous g-C3N4Nanotube component 4: placing the melamine nanofiber component 4 in an atmosphere resistance furnace, introducing nitrogen, heating to 560 ℃ at the heating rate of 2 ℃/min, keeping the temperature, and calcining for 4h to obtain a calcined product, namely the porous g-C3N4Nanotube component 4.
(3) Preparation of modified porous g-C3N4Nanotube component 4: adding distilled water and porous g-C into a reaction bottle3N4Nanotube component 4 and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 30min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4Stirring at 20 ℃ for 4h at a constant speed with a mass ratio of 1600:1.1:1, vacuum drying the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare Ni2B modified porous g-C3N4Nanotube component 4.
(4) Preparation of Ni-doped nano MoS2And (4) component: adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.08:1:4 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 200 ℃, reacting for 30 hours, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2And (4) component.
(5) Preparation of Co-MOFs-coated g-C3N4And (4) component: adding acetone solvent and 14.5 parts of modified porous g-C into a reaction bottle3N4Nanotube component 4, 22 parts Co (NO)3)2And 8.5 parts of trimesic acid, placing a reaction bottle in an ultrasonic dispersion instrument for ultrasonic dispersion treatment for 1h, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, uniformly stirring for reaction for 15h, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the Co-MOFs coated g-C3N4And (4) component.
(6) Preparation of Co9S8Coating g-C3N4And (4) component: adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4Uniformly stirring the components 4 and 9 parts of thiourea, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 150 ℃, reacting for 5 hours, and concentrating the solution under reduced pressureRemoving the solvent, washing the solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating to 380 ℃ at the heating rate of 4 ℃/min, keeping the temperature, and calcining for 2 hours to obtain the calcined product Co9S8Coating g-C3N4And (4) component.
(7) Preparation of Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst material 4: adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4Component 4 and 46 parts of Ni-doped nano MoS2And (4) performing ball milling on the material until the material completely passes through a 1800-mesh screen when the revolution speed of the planetary ball mill is 460rpm and the rotation speed of the planetary ball mill is 230rpm, concentrating the mixed material under reduced pressure to remove the solvent, and fully drying to prepare the Co-based material9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 4.
(8) Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 4 and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on the glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode 4.
Example 5
(1) Preparation of melamine nanofiber component 5: adding an ethylene glycol solvent and melamine into a reaction bottle, adding nitric acid to adjust the pH value of the solution to 1 after uniformly stirring, placing the reaction bottle in a constant-temperature water bath, heating to 75 ℃, uniformly stirring for reaction for 4 hours, filtering the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the melamine nanofiber component 5.
(2) Preparation of porous g-C3N4Nanotube component 5: placing the melamine nanofiber component 5 in an atmosphere resistance furnace, introducing nitrogen, heating to 560 ℃ at the heating rate of 8 ℃/min, keeping the temperature, and calcining for 4h to obtain a calcined product, namely the porous g-C3N4Nanotube component 5.
(3) Preparation of modified porous g-C3N4Nanotube component 5: adding distilled water and porous g-C into a reaction bottle3N4Nanotube component 5 and NiCl2Placing the reaction bottle in an ultrasonic disperser, performing ultrasonic dispersion treatment for 45min, and adding NaBH into the reaction bottle4Wherein the pores g-C3N4Nanotube, NiCl2And NaBH4Stirring at 20 ℃ for 4h at a constant speed with a mass ratio of 1600:1.3:1, vacuum drying the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare Ni2B modified porous g-C3N4Nanotube component 5.
(4) Preparation of Ni-doped nano MoS2And (5) component: adding distilled water and Na into a reaction bottle2MoO4And Ni (NO)3)2Adding thioacetamide with the mass ratio of 0.08:1:6 after uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating box, heating to 230 ℃, reacting for 30 hours, filtering the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare the Ni-doped nano MoS2And (5) component.
(5) Preparation of Co-MOFs-coated g-C3N4And (5) component: adding acetone solvent and 16 parts of modified porous g-C into a reaction bottle3N4Nanotube component 5, 24 parts Co (NO)3)2And 9 parts of trimesic acid, placing the reaction bottle in an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment for 2 hours, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 15 hours, performing reduced pressure concentration on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain Co-MOFs coated g-C3N4And (5) component.
(6) Preparation of Co9S8Coating g-C3N4And (5) component: adding ethanol solvent and Co-MOFs to coat g-C into a reaction bottle3N4Uniformly stirring the component 3 and 10 parts of thiourea, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating box of the reaction kettle, heating to 150 ℃, reacting for 10 hours, concentrating the solution under reduced pressure to remove the solvent, and washing the solid by using distilled waterFully drying the product, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating to 380 ℃ at the heating rate of 4 ℃/min, keeping the temperature, and calcining for 4h to obtain the calcined product Co9S8Coating g-C3N4And (5) component.
(7) Preparation of Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst material 5: adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4Component 5 and 41 parts of Ni-doped nano MoS2And (3) performing ball milling on the material until the material completely passes through a 1800-mesh screen mesh when the revolution speed of the planetary ball mill is 620rpm and the rotation speed of the planetary ball mill is 310rpm, concentrating the mixed material under reduced pressure to remove the solvent, and fully drying to prepare the Co-based material9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 5.
(8) Adding Co into the mixed solvent of oriented ethanol and distilled water9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst material 5 and the Nafion solution are uniformly stirred to form slurry, the slurry is uniformly coated on a glassy carbon electrode, and the glassy carbon electrode is fully dried to prepare the electrocatalytic working electrode 5.
A platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, an electrolyte is a 1mol/L potassium hydroxide solution, and the hydrogen evolution potential of the electrocatalytic working electrode in the embodiment 1-5 is tested by using a CHI660D electrochemical workstation, wherein the test standard is GB/T20042.4-2009.
In summary, the one Co9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst takes melamine nano-fiber as a precursor, and nano g-C is prepared by thermal cracking3N4Has the advantages ofRich pore structure, increased g-C3N4Wetting with electrolyte by nickel boride Ni2B in situ modification of g-C3N4On the surface of which structural defects are formed, and which can effectively exfoliate g-C3N4Form a large amount of mesoporous structures, shorten the transmission path of electrons and ions, and increase the g-C3N4Can provide more electrochemically active sites, and Ni2B has boron atoms in g-C3N4The interior forms a C-B-N ternary structure and a hexagonal boron nitride structure, and the g-C is reduced3N4Thereby increasing g-C3N4The conductivity of (2) reduces the overpotential of the hydrogen evolution reaction.
Ni-doped nano MoS prepared by hydrothermal synthesis method2Ni replaces part of Mo crystal lattice to improve MoS2While the Ni doping reduces the MoS2Modification of the free energy of hydrogen adsorption of unsaturated S atoms at the edge active sites to modify the porosity of g-C3N4Nano tube as matrix, Ni doped nano MoS2Better adhesion to porous g-C3N4In the pore and mesoporous structure of the nanotube, the nano MoS is effectively reduced2The agglomeration and aggregation of the catalyst can avoid covering the electrochemical active sites, thereby greatly enhancing the hydrogen evolution activity of the catalyst.
Coating of g-C with a cobalt-based metal-organic framework3N4Taking thiourea as a sulfur source as a precursor, and thermally cracking to obtain Co9S8Coating g-C3N4Then mixed with Ni doped nano MoS2Composite, Co9S8And MoS2A heterogeneous interface is formed, and the transmission and diffusion of electrons are accelerated, so that the overpotential of the hydrogen evolution reaction is reduced.
Claims (6)
1. Co9S8-MoS2Load g-C3N4The electrocatalytic hydrogen production catalyst comprises the following formula raw materials and components in parts by weight, and is characterized in that: 10-16 parts of modified porous g-C3N4Nanotube, 15-24 parts of Co (NO)3)27-9 parts of trimesic acid, 6-10 parts of thiourea and 41-62 parts of Ni-doped nano MoS2。
2. Co according to claim 19S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst is characterized in that: the modified porous g-C3N4The preparation method of the nanotube comprises the following steps:
(1) adding melamine into an ethylene glycol solvent, adding nitric acid after uniformly stirring to adjust the pH value of the solution to 1-2, heating the solution to 55-75 ℃, uniformly stirring for reacting for 2-4h, removing the solvent from the solution, washing a solid product, and drying to prepare the melamine nanofiber;
(2) placing the melamine nano-fiber in an atmosphere resistance furnace and introducing nitrogen, wherein the heating rate is 2-8 ℃/min, the temperature is raised to 520-560 ℃, the heat preservation and calcination are carried out for 2-4h, and the calcination product is porous g-C3N4A nanotube;
(3) adding porous g-C to distilled water solvent3N4Nanotubes and NiCl2Ultrasonic dispersing the solution for 30-60min, and adding NaBH4Stirring at 10-20 deg.C for 2-4 hr, removing solvent from the solution, washing the solid product, and drying to obtain Ni2B modified porous g-C3N4A nanotube.
3. Co according to claim 29S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst is characterized in that: the porous g-C3N4Nanotube, NiCl2And NaBH4The mass ratio is 1200-1600:1.1-1.3: 1.
4. Co according to claim 19S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst is characterized in that: the Ni-doped nano MoS2The preparation method comprises the following steps:
(1) is turned to the reverse directionAdding distilled water solvent and Na into the reactor2MoO4、Ni(NO3)2And thioacetamide, heating to 230 ℃ for reaction for 20-30h, removing the solvent from the solution, washing the solid product and drying to prepare the Ni-doped nano MoS2。
5. Co according to claim 49S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst is characterized in that: the Na is2MoO4、Ni(NO3)2And the amount ratio of the thioacetamide to the thioacetamide is 0.04-0.08:1: 4-6.
6. Co according to claim 19S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst is characterized in that: the Co9S8-MoS2Load g-C3N4The preparation method of the electrocatalytic hydrogen production catalyst comprises the following steps:
(1) adding 10-16 parts of modified porous g-C into acetone solvent3N4Nanotube, 15-24 parts of Co (NO)3)2And 7-9 parts of trimesic acid, performing ultrasonic dispersion treatment on the solution for 1-2h, heating to 50-70 ℃, reacting for 8-15h, removing the solvent from the solution, washing a solid product, and drying to obtain Co-MOFs coated g-C3N4；
(2) Adding ethanol solvent and Co-MOFs to coat g-C in a polytetrafluoroethylene reaction kettle3N4And 6-10 parts of thiourea, heating to 130-150 ℃, reacting for 5-10h, removing the solvent from the solution, washing and drying the solid product, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating to 360-380 ℃ at the heating rate of 2-4 ℃/min, and carrying out heat preservation and calcination for 2-4h to obtain a Co-doped product9S8Coating g-C3N4；
(3) Adding ethanol solvent and Co into a planetary ball mill9S8Coating g-C3N4And 41-62 parts of Ni-doped nano MoS2Revolution and revolution of planetary ball millThe speed is 460 plus 620rpm, the rotation speed is 230 plus 310rpm, the materials are ball milled until the materials all pass through a screen with 1200 plus 1800 meshes, the solvent of the mixed materials is removed and the mixed materials are dried, and the Co is prepared9S8-MoS2Load g-C3N4The electro-catalysis hydrogen production catalyst.
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