CN116334689A - PVP modified NiMoS electrocatalyst and preparation method thereof - Google Patents
PVP modified NiMoS electrocatalyst and preparation method thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 28
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 34
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 34
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/095—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 at least one of the compounds being organic
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses a PVP modified NiMoS electrocatalyst and a preparation method thereof, wherein the electrocatalyst is in the shape of a nano flower-shaped NiMoS material with the surface uniformly coated with PVP film, and the particle size is 100-300 nm; the preparation method comprises the following steps: respectively dissolving ammonium heptamolybdate tetrahydrate and nickel nitrate in deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, fully stirring, drying residues, and grinding the residues to be powder to obtain a precursor; dissolving a precursor, PVP and thiourea in deionized water, uniformly stirring, performing hydrothermal reaction to obtain a reaction product, and washing and drying the reaction product after the reaction is finished to obtain an electrocatalyst; the electrocatalyst provided by the invention has the advantages of stable structure, simple and convenient preparation, low price, environmental protection, high electrocatalytic activity and high stability, and is beneficial to realizing large-scale industrial production.
Description
Technical Field
The invention relates to the field of electrocatalyst preparation, in particular to a PVP modified NiMoS electrocatalyst and a preparation method thereof.
Background
With the enhancement of environmental awareness of all human beings, it has been a great trend to push more efficient and green energy sources to replace the traditional fossil energy sources. The combustion product of the hydrogen is water, so that the real zero emission and no pollution can be realized, and the hydrogen is regarded as one of clean energy sources with the application prospect. Meanwhile, the hydrogen is the highest in heat value (142 kJ/g) in common fuel, is about 3 times of petroleum and 5 times of coal, consumes hydrogen, petroleum and coal with the same mass, and has the maximum energy provided by the hydrogen, and the characteristic effectively meets the development requirements in the light-weight fields of automobiles, aerospace and the like. Hydrogen gas is or will become one of the ultimate forms of future energy use.
The electrocatalytic decomposition of water to produce hydrogen is widely focused as a high-efficiency, simple and safe hydrogen production mode, but the efficiency of decomposing water to produce hydrogen in the actual production process is still to be improved, because the actual production process is a water-splitting hydrogen production process in an alkaline environment, the development of a composite material capable of remarkably improving the hydrogen production of the water in the alkaline environment is urgently needed.
Transition metal sulfides (molybdenum sulfide, nickel sulfide, etc.) have been demonstrated in published studies to exhibit excellent electrocatalytic activity in acidic conditions, whereas slow Hydrogen Evolution Reaction (HER) kinetics on the cathode under alkaline conditions lead to ultra-high overpotential, which greatly reduces energy efficiency and hinders alkaline species electrolysis. Noble metals (e.g., platinum, ruthenium, iridium) are widely used by researchers for HER electrocatalysts due to their high catalytic activity; however, the inherent disadvantages of noble metals, such as high price, rare earth stock and low durability, greatly limit the prospect of the noble metals in industry. In summary, how to design an electrolyzed water hydrogen evolution catalytic material with high catalytic activity, good stability and low cost is a current urgent problem to be solved.
Chinese patent document CN112023950A provides a Ni-doped MoS 2 The nanometer flower-porous graphene hydrogen evolution electrocatalyst and the preparation method thereof comprise the following formula raw materials and components: three-dimensional porous graphene, nickel acetate, polyvinylpyrrolidone, molybdic acid and thiourea. Ni doped MoS 2 The nano flower has unique petal shape, can expose a large number of electrocatalytic active sites, and is beneficial to Ni dopingReducing MoS 2 The free energy of hydrogen adsorption at the edge position can regulate MoS 2 The three-dimensional porous graphene has rich pore structure and superhigh specific surface area, and can be used as Ni doped MoS 2 Nanometer flower carrier, which is favorable for reducing Ni doping MoS 2 The aggregation of the nanoflower, the excellent conductivity and the rich pore structure of the three-dimensional porous graphene are beneficial to promoting the transfer of electrons and the transfer process of substances in the hydrogen evolution reaction, and the excellent electrocatalytic hydrogen evolution activity is shown; however, the preparation process is complex and is not suitable for industrial mass production.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide the PVP modified NiMoS electrocatalyst and the preparation method thereof, and the electrocatalyst provided by the invention is a transition metal sulfide electrocatalyst which has the advantages of stable structure, simple and convenient preparation, low price, environmental friendliness, electrocatalytic activity and high stability; solves the problems of high overpotential, poor stability, high price and the like of the conventional electrocatalytic decomposition water hydrogen production catalyst under alkaline conditions, and is beneficial to realizing large-scale industrial production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the PVP modified NiMoS electrocatalyst is nanometer flower-shaped NiMoS material with PVP film homogeneously coated on the surface and grain size of 100-300 nm.
The invention also claims a preparation method of the PVP modified NiMoS electrocatalyst, which comprises the following steps:
(1) Preparing a precursor: respectively dissolving ammonium heptamolybdate tetrahydrate and nickel nitrate in deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, fully stirring, drying residues, and grinding the residues to be powder to obtain a precursor;
(2) Preparing a catalyst: and (3) dissolving the precursor, PVP and thiourea in deionized water, uniformly stirring, performing hydrothermal reaction, and washing and drying a reaction product after the reaction is finished to obtain the PVP modified NiMoS electrocatalyst.
Preferably, in the step (1), the stirring temperature is 70 to 90 ℃.
Preferably, in step (1), the stirring temperature is 80 ℃.
Preferably, in the step (1), the mass ratio of the ammonium heptamolybdate tetrahydrate to the nickel nitrate is 1:4.5 to 6, and the concentration of the nickel nitrate solution is 2 to 10 weight percent.
Preferably, in the step (1), the mass ratio of the ammonium heptamolybdate tetrahydrate to the nickel nitrate is 1:4.84, the concentration of the nickel nitrate solution is 2-10wt%.
Preferably, in the step (1), the drying condition is that the drying is carried out at 50-70 ℃ for 12-24 hours.
Preferably, in step (1), the drying conditions are 60℃for 18 hours.
Preferably, in the step (2), the mass ratio of the precursor, thiourea and PVP is 1:1 to 1.5:0.05 to 0.2 percent, and the concentration of thiourea in the solution is 1 to 5 weight percent.
Preferably, in the step (2), the mass ratio of the precursor, thiourea and PVP is 1:1.2:0.15, the concentration of thiourea in the solution is 1-5 wt%.
Preferably, in the step (2), the hydrothermal reaction condition is 180-220 ℃ for 18-30 h.
Preferably, in the step (2), the hydrothermal reaction condition is that the reaction is carried out for 24 hours at 200 ℃.
Preferably, in the step (2), the washing condition is that water and ethanol are used for centrifugal washing for 3-5 times respectively.
Preferably, in the step (2), the drying condition is that the drying is carried out for 12-24 hours at 50-70 ℃.
Preferably, in step (2), the drying conditions are 60℃for 18 hours.
Compared with the prior art, the invention has the following beneficial effects:
1) The PVP modified NiMoS electrocatalyst provided by the invention is a transition metal sulfide electrocatalyst, and has the advantages of stable structure, simple and convenient preparation, low price, environmental friendliness, electrocatalytic activity and high stability; solves the problems of high overpotential, poor stability, high price and the like of the conventional electrocatalytic decomposition water hydrogen production catalyst under the alkaline condition, and is beneficial to realizing large-scale industrial production.
2) The PVP modified NiMoS electrocatalyst provided by the invention takes ammonium heptamolybdate tetrahydrate, nickel nitrate and polyvinylpyrrolidone as raw materials, and the catalyst is prepared in a relatively simple and low-temperature mode, and the preparation method is simple and convenient, environment-friendly, low in energy consumption and easy for industrial production and preparation.
3) The PVP modified NiMoS electrocatalyst provided by the invention is prepared by firstly preparing the precursor, and then preparing the catalyst by taking the precursor which is completely ground into powder as a raw material, so that the catalyst structure is more stable on the molecular level, and nickel atoms are more uniformly distributed in the catalyst.
4) The PVP modified NiMoS electrocatalyst provided by the invention has the advantages that the catalyst is more uniformly dispersed through the design of a process flow, and the exposure of active sites is more facilitated to improve the catalytic performance.
5) The PVP modified NiMoS electrocatalyst provided by the invention adopts non-noble metal elements, reduces the cost of electro-catalytic decomposition of water to produce hydrogen, and is beneficial to commercialization of pushing electro-catalytic decomposition of water to produce hydrogen.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1, a linear voltammetry scan;
FIG. 2, taffy slope schematic;
FIG. 3, a schematic representation of electrochemically active areas;
FIG. 4 is a schematic diagram of an impedance test;
FIG. 5, X-ray diffraction characterization;
FIG. 6, scanning electron microscope images of the catalysts prepared in comparative example 1 and example 3.
In FIG. 6, (a), (b) and (c) are the scanning electron microscope images of the catalyst prepared in comparative example 1, and (d), (e) and (f) are the scanning electron microscope images of the catalyst prepared in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
The invention will be further illustrated by the following examples.
Example 1
A preparation method of PVP modified NiMoS electrocatalyst comprises the following steps:
(1) Preparing a precursor: respectively dissolving 1.2g of ammonium heptamolybdate tetrahydrate and 5.8g of nickel nitrate in 100mL of deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, stirring at 80 ℃ until water in a system is basically volatilized, drying the residue at 60 ℃ for 12-24 h, and grinding to powder to obtain a precursor;
(2) Preparing a catalyst: 1.3g of precursor, 0.065g of PVP and 1.57g of thiourea are dissolved in 80mL of deionized water, the mixture is stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction products are respectively centrifugally washed for 3 times by water and ethanol, and the mixture is dried for 12 to 24 hours at 60 ℃ to obtain the PVP modified NiMoS electrocatalyst.
Example 2
A preparation method of PVP modified NiMoS electrocatalyst comprises the following steps:
(1) Preparing a precursor: respectively dissolving 1.2g of ammonium heptamolybdate tetrahydrate and 5.8g of nickel nitrate in 100mL of deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, stirring at 80 ℃ until water in a system is basically volatilized, drying the residue at 60 ℃ for 12-24 h, and grinding to powder to obtain a precursor;
(2) Preparing a catalyst: 1.3g of precursor, 0.13g of PVP and 1.57g of thiourea are dissolved in 80mL of deionized water, the mixture is stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction products are respectively centrifugally washed for 3 times by water and ethanol, and the mixture is dried for 12 to 24 hours at 60 ℃ to obtain the PVP modified NiMoS electrocatalyst.
Example 3
A preparation method of PVP modified NiMoS electrocatalyst comprises the following steps:
(1) Preparing a precursor: respectively dissolving 1.2g of ammonium heptamolybdate tetrahydrate and 5.8g of nickel nitrate in 100mL of deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, stirring at 80 ℃ until water in a system is basically volatilized, drying the residue at 60 ℃ for 12-24 h, and grinding to powder to obtain a precursor;
(2) Preparing a catalyst: 1.3g of precursor, 0.195g of PVP and 1.57g of thiourea are dissolved in 80mL of deionized water, the mixture is stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction products are respectively centrifugally washed for 3 times by water and ethanol, and the mixture is dried for 12 to 24 hours at 60 ℃ to obtain the PVP modified NiMoS electrocatalyst.
Example 4
A preparation method of PVP modified NiMoS electrocatalyst comprises the following steps:
(1) Preparing a precursor: respectively dissolving 1.2g of ammonium heptamolybdate tetrahydrate and 5.8g of nickel nitrate in 100mL of deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, stirring at 80 ℃ until water in a system is basically volatilized, drying the residue at 60 ℃ for 12-24 h, and grinding to powder to obtain a precursor;
(2) Preparing a catalyst: 1.3g of precursor, 0.26g of PVP and 1.57g of thiourea are dissolved in 80mL of deionized water, the mixture is stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction products are respectively centrifugally washed for 3 times by water and ethanol, and the mixture is dried for 12 to 24 hours at 60 ℃ to obtain the PVP modified NiMoS electrocatalyst.
Comparative example 1
A method for preparing an electrocatalyst comprising the steps of:
(1) Preparing a precursor: respectively dissolving 1.2g of ammonium heptamolybdate tetrahydrate and 5.8g of nickel nitrate in 100mL of deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, stirring at 80 ℃ until water in a system is basically volatilized, drying the residue at 60 ℃ for 12-24 h, and grinding to powder to obtain a precursor;
(2) Preparing a catalyst: 1.3g of precursor and 1.57g of thiourea are dissolved in 80mL of deionized water, stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction products are respectively centrifugally washed for 3 times by water and ethanol, and dried for 12-24 hours at 60 ℃ to obtain the electrocatalyst.
Comparative example 2
A method for preparing an electrocatalyst comprising the steps of:
1.2g of ammonium heptamolybdate tetrahydrate, 5.8g of nickel nitrate, 0.195g of PVP and 1.57g of thiourea are dissolved in 80mL of deionized water, the solution is stirred uniformly and then put into a reaction kettle to react for 24 hours at 200 ℃, after the hydrothermal reaction is finished, the reaction product is respectively centrifugally washed for 3 times by water and ethanol, and the solution is dried for 12 to 24 hours at 60 ℃ to obtain the electrocatalyst.
0.5g of the electrocatalyst prepared in examples 1 to 4 and comparative examples 1 to 2 is respectively placed in 480 mu L of ethanol, 480 mu L of deionized water and 40 mu L of Nafion solution, and is dropped into 0.5cm after ultrasonic treatment for 60min 2 Carbon paper surface. And (3) performing linear voltammetry, cyclic voltammetry and EIS electrochemical impedance spectroscopy analysis and test by taking the treated carbon paper as a cathode, a carbon rod as an anode and a 1mol/L potassium hydroxide solution as electrolyte. In the figure, 0-NiMoS (PVP) 1:0.5, 0-NiMoS (PVP) 1:1. 0-NiMoS (PVP) 1:1.5, 0-NiMoS (PVP) 1:2 correspond to examples 1 to 4,0-NiMoS to example 1, and the control group to example 2.
(1) Linear voltammetry
The electrocatalysts prepared in examples 1 to 4 and comparative examples 1 to 2 were tested by linear voltammetry on an electrochemical workstation of Shanghai Chenhua CHI600E, the test results are shown in FIG. 1, and the Taffy slope calculation results are shown in FIG. 2.
From FIGS. 1 and 2, it can be seen that the overpotential and the Taphenanthrene gradient of the catalyst prepared in example 3 are optimal, which is significantly better than those of the catalyst (Pt/C) for the commercial electrocatalytic decomposition of water to produce hydrogen and the catalysts prepared in example 1, example 2, example 4, comparative example 1 and comparative example 2.
(2) Cyclic voltammetry
The electrocatalysts prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to cyclic voltammetry test on an electrochemical workstation of Shanghai Chenhua CHI600E, the test results are shown in FIG. 3, and the calculation results of the electrochemical activity areas are shown in FIG. 4.
It can be seen from fig. 4 that the catalyst prepared in example 3 has an optimal electrochemical active area, which is significantly better than the catalysts prepared in example 1, example 2, example 4, and comparative example 1.
(3) EIS electrochemical impedance spectroscopy
EIS electrochemical impedance spectroscopy tests are carried out on the electrocatalysts prepared in examples 1-4 and comparative examples 1-2 on an electrochemical workstation of Shanghai Chenhua CHI600E, and the test results are shown in FIG. 4.
It can be seen from fig. 5 that the electrochemical impedance of the catalyst prepared in example 3 is most significantly better than that of the catalysts prepared in example 1, example 2, example 4 and comparative example 1.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The PVP modified NiMoS electrocatalyst is characterized in that the morphology is nano flower-shaped NiMoS material with the PVP film uniformly coated on the surface, and the particle size is 100-300 nm.
2. A method of preparing the PVP modified NiMoS electrocatalyst according to claim 1, comprising the steps of:
(1) Preparing a precursor: respectively dissolving ammonium heptamolybdate tetrahydrate and nickel nitrate in deionized water, mixing the ammonium heptamolybdate solution and the nickel nitrate solution, fully stirring, drying residues, and grinding the residues to be powder to obtain a precursor;
(2) Preparing a catalyst: and (3) dissolving the precursor, PVP and thiourea in deionized water, uniformly stirring, performing hydrothermal reaction to obtain a reaction product, and washing and drying the reaction product after the reaction is finished to obtain the electrocatalyst.
3. The process according to claim 2, wherein in the step (1), the stirring temperature is 70 to 90 ℃.
4. The method according to claim 2, wherein in the step (1), the mass ratio of ammonium heptamolybdate tetrahydrate to nickel nitrate is 1:4.5 to 6, and the concentration of the nickel nitrate solution is 2 to 10 weight percent.
5. The method according to claim 2, wherein in the step (1), the drying condition is 50 to 70 ℃ for 12 to 24 hours.
6. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the precursor, thiourea and PVP is 1:1 to 1.5:0.05 to 0.2 percent, and the concentration of thiourea in the solution is 1 to 5 weight percent.
7. The process according to claim 2, wherein in the step (2), the hydrothermal reaction is carried out at 180 to 220℃for 18 to 30 hours.
8. The method according to claim 2, wherein in the step (2), the washing conditions are centrifugal washing with water and ethanol for 3 to 5 times, respectively.
9. The method according to claim 2, wherein in the step (2), the drying condition is 50 to 70 ℃ for 12 to 24 hours.
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