CN113926479A - Potassium molybdenum sulfur/nickel nitride composite material and preparation method and application thereof - Google Patents
Potassium molybdenum sulfur/nickel nitride composite material and preparation method and application thereof Download PDFInfo
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- CN113926479A CN113926479A CN202010669431.2A CN202010669431A CN113926479A CN 113926479 A CN113926479 A CN 113926479A CN 202010669431 A CN202010669431 A CN 202010669431A CN 113926479 A CN113926479 A CN 113926479A
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- -1 Potassium molybdenum sulfur Chemical compound 0.000 title claims abstract description 299
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 161
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 7
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003218 Ni3N Inorganic materials 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 80
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention relates to a potassium-molybdenum-sulfur/nickel nitride composite material, a preparation method and application thereof, wherein the potassium-molybdenum-sulfur/nickel nitride composite material comprises potassium-molybdenum-sulfur KMoS2And nickel nitride Ni3N, and a part of potassium, molybdenum and sulfur and nickel nitride have sulfur-nickel chemical bonds between the potassium, molybdenum and sulfur.
Description
Technical Field
The invention relates to a catalyst material for oxygen evolution reaction and hydrogen evolution reaction, in particular to a potassium-molybdenum-sulfur/nickel nitride composite material and a preparation method and application thereof, belonging to the field of materials science.
Background
Since the 21 st century, with the development of global economy, the consumption of energy is increasing, the shortage of fossil fuel and environmental pollution are becoming more serious, and the research on new energy materials is becoming more concerned. Therefore, researchers are urged to urgently need to find a renewable energy source which is rich, durable, zero-emission and eco-friendly as an alternative energy source, so that the dependence on fossil fuels is greatly reduced. The full water splitting is a conversion technology of environment-friendly energy, and is widely concerned due to high energy conversion efficiency, small environmental pollution and wide application prospect. The total decomposition water is divided into two half-reactions, one is the Hydrogen Evolution Reaction (HER) and one is the Oxygen Evolution Reaction (OER), the main purpose of which is to produce pure hydrogen (H)2) And oxygen (O)2) In practice, full hydrolysis requires an effective catalyst to promote both reactions. Currently, platinum (Pt) -based catalysts are the most effective catalysts for HER, while iridium (Ir) and ruthenium (Ru) -based catalysts are highly effective catalysts for OER. However, noble metals such as Pt, Ir and Ru are expensive, scarce in reserves and poor in durability, which hinders further applications. In recent years, researchers have prepared a number of low cost HER electrocatalysts that are highly effective in accelerating the HER reaction. However, OER is a very demanding step involving a four-electron reaction and the formation of an oxygen-oxygen bond, and therefore the reaction kinetics of OER is inherently slower than HER. Therefore, efficient non-noble metal electrocatalysts are needed to be researched to reduce the OER over-potential (eta) so as to improve the energy conversion efficiency of the fully hydrolyzed water. Currently conventional catalyst RuO2And IrO2Commonly used for OER electrocatalysis, but its high price hinders its further applications due to poor stability and its presence of the noble metals Ru and Ir. Therefore, non-noble metal materials are better substitutes.
Potassium molybdenum sulfide (KMoS)2) Has higher electron transfer rate and arouses great interest. However, KMoS2The low catalytic activity hinders the popularization of the catalyst in practical application. In recent years, nickel nitride (Ni) has been a representative transition metal nitride3N) not only has a stable structure,and has good bonding strength with hydroxyl free radicals (OH) on the surface, and is a potential catalyst for oxygen evolution reaction and hydrogen evolution reaction. Therefore, a single material has the disadvantages of low electron transfer rate, insufficient active sites, unstable material or insufficient hydroxyl groups, and the like, and the catalytic performance of the material is limited.
Disclosure of Invention
The invention provides a potassium-molybdenum-sulfur/nickel nitride composite material and a preparation method and application thereof, aiming at solving the technical problems of low catalytic activity and high price of catalysts for oxygen evolution reaction and hydrogen evolution reaction in the prior art.
In one aspect, the present invention provides a potassium molybdenum sulfur/nickel nitride composite comprising a potassium molybdenum sulfur KMoS2And nickel nitride Ni3N, and a sulfur-nickel chemical bond is formed between part of the potassium-molybdenum-sulfur and the nickel nitride.
In the disclosure, the potassium-molybdenum-sulfur/nickel nitride composite material combines the high conductivity of potassium-molybdenum-sulfur and the stability of nickel nitride, and sulfur-nickel chemical bonds are formed between S in part of potassium-molybdenum-sulfur and Ni in nickel nitride, so as to form a potassium-molybdenum-sulfur/nickel nitride heterojunction, which can further regulate and control an electronic structure, improve the stability of the electronic structure, and further improve the performance of an electrocatalyst.
Preferably, the potassium molybdenum sulfur/nickel nitride composite material has a laminated structure, wherein nickel nitride is compounded in laminated potassium molybdenum sulfur KMoS2In addition, the method is favorable for forming sulfur-nickel chemical bonds, accelerates the electron transfer rate and improves the oxygen evolution reaction and hydrogen evolution reaction performances.
Preferably, the mass ratio of the potassium, molybdenum and sulfur to the nickel nitride material is 1:0.5 to 2.5.
On the other hand, the invention also provides a preparation method of the potassium-molybdenum-sulfur/nickel nitride composite material, which comprises the steps of dispersing potassium-molybdenum-sulfur and nickel nitride in a reaction kettle filled with deionized water or alkaline solution, and carrying out hydrothermal reaction at 60-170 ℃ to obtain the potassium-molybdenum-sulfur/nickel nitride composite material.
In the invention, potassium-molybdenum-sulfur and nickel nitride are placed in a hydrothermal kettle (or called reaction kettle) filled with deionized water or alkaline solution, S exposed in the potassium-molybdenum-sulfur and Ni exposed in the nickel nitride form bonds at high temperature/high pressure of the reaction kettle in the hydrothermal reaction process at 60-170 ℃, and finally the potassium-molybdenum-sulfur/nickel nitride composite material with sulfur-nickel bonds is obtained. Preferably, the mode of dispersion is ultrasonic treatment; more preferably, the power of ultrasonic treatment is 100-150W, and the time is 10-30 minutes. More preferably, the filling ratio of the reaction kettle can be 50-70 vol%.
Preferably, the particle size of the potassium, molybdenum and sulfur is 500 nm-5 μm; the particle size of the nickel nitride is 50 nm-0.5 mu m.
Preferably, the mass ratio of the potassium, molybdenum and sulfur to the nickel nitride is 1: 0.5-2.5, and the optimal ratio is 1: 2.
Preferably, the alkaline solution is at least one selected from a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and preferably has a pH of 8-12.
Preferably, the hydrothermal reaction time is 12-24 hours.
In another aspect, the invention also provides an application of the potassium-molybdenum-sulfur/nickel nitride composite material in oxygen evolution reaction and hydrogen evolution reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a hydrothermal method under alkaline conditions for the first time, so that the potassium-molybdenum-sulfur material and the nickel nitride material are subjected to heat treatment at 60-170 ℃ to form the potassium-molybdenum-sulfur/nickel nitride composite material, and the potassium-molybdenum-sulfur/nickel nitride composite material has good electrocatalytic activity in alkaline oxygen evolution reaction. The invention effectively improves the electrochemical activity and stability of the catalyst in the alkaline oxygen evolution reaction, has simple and clear preparation process, is suitable for large-scale production and has certain use value.
Drawings
FIG. 1 shows X-ray diffraction patterns (XRD) of a synthetic K-Mo-S material, a nickel nitride material and a synthetic K-Mo-S/Ni nitride composite material synthesized by hydrothermal method in example 1;
FIG. 2 shows X-ray photoelectron spectroscopy (XPS) of a potassium-molybdenum-sulfur material, a nickel nitride material synthesized according to the present invention, and a potassium-molybdenum-sulfur/nickel nitride composite synthesized according to example 1 by a hydrothermal method;
FIG. 3 shows the S2 p peaks of X-ray photoelectron spectroscopy (XPS) of the synthesized K-Mo-S material of the present invention and the synthesized K-Mo-S/Ni nitride composite of example 1 by hydrothermal method;
FIG. 4 shows a Scanning Electron Micrograph (SEM) of a potassium molybdenum sulfide/nickel nitride composite synthesized by hydrothermal method in example 1;
FIG. 5 shows a Transmission Electron Micrograph (TEM) of a potassium molybdenum sulfide/nickel nitride composite synthesized by a hydrothermal method according to example 1;
FIG. 6 shows an energy dispersive x-ray spectroscopy mapping (EDS-mapping) of a potassium molybdenum sulfur/nickel nitride composite synthesized in example 1 using a hydrothermal method;
FIG. 7 shows the LSV and overpotential plots for OER testing in 1M KOH for the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method in examples 1-5;
FIG. 8 shows the LSV and overpotential plots for HER tests in 1M KOH for the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method in examples 1-5;
FIG. 9 shows Tafel slope plots of the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method in examples 1-5 in 1M KOH;
FIG. 10 shows EIS impedance plots of the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method in examples 1-5 in 1M KOH;
FIG. 11 shows the LSV and overpotential plots for OER testing in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1, 2, respectively;
FIG. 12 shows the LSV and overpotential plots for the HER test in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1, 2, respectively;
FIG. 13 shows Tafel slope plots of the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1, 2, respectively, in 1M KOH;
FIG. 14 shows EIS impedance plots of potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1, 2, respectively, in 1M KOH;
FIG. 15 shows the LSV and overpotential plots for OER testing in 1M KOH for the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal methods at different temperatures for examples 1, 8, and 9;
FIG. 16 shows the LSV and overpotential plots for HER tests in 1M KOH for potassium molybdenum sulfide/nickel nitride composites synthesized by different temperature hydrothermal methods for examples 1, 8 and 9;
FIG. 17 shows Tafel slope plots of the potassium molybdenum sulfide/nickel nitride composites of examples 1, 8, 9 synthesized using different temperature hydrothermal methods in 1M KOH;
FIG. 18 shows EIS impedance plots of potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method at different temperatures in examples 1, 8 and 9 in 1M KOH.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In this disclosure, the potassium molybdenum sulfur/nickel nitride composite is: the catalyst is prepared by taking potassium molybdenum sulfide and nickel nitride as raw materials, placing the raw materials in deionized water or an alkaline strip solution, and adopting a hydrothermal method.
The potassium molybdenum sulfur/nickel nitride composite material provided by the present invention is exemplarily illustrated below.
The preparation of the potassium molybdenum sulfide comprises but is not limited to synthesis through high-temperature solid-phase reaction. Mixing the potassium source, the molybdenum source and the sulfur source material according to the molar ratio of 1:1:1, and fully grinding in an agate mortar for 0.5-2 h. Then pressing the mixed powder into small balls, sealing the small balls in a quartz tube in vacuum, annealing the small balls in a muffle furnace for 12 to 36 hours at the heating rate of 5 to 10 ℃ per minute-1. And then, after the sample is naturally cooled to room temperature and taken out, dispersing the sample in deionized water, and performing vacuum drying at room temperature to obtain the potassium-molybdenum-sulfur. Wherein the potassium source, the molybdenum source and the sulfur source are respectively K2S2Powder, Mo powder, MoS2And (3) powder. The potassium-molybdenum-sulfur material is obtained based on solid-phase high-temperature calcination, and the annealing temperature is 600-1000 ℃. The grain size of the obtained potassium, molybdenum and sulfur can be 500 nm-5 mu m.
The preparation of the nickel nitride comprises, but is not limited to, the preparation by first hydrothermal and then calcining in a tube furnace. Adding a nickel source and a nitrogen source into deionized water, and then carrying out hydrothermal heating in a hydrothermal kettle for 4-12 h. And after the sample is naturally cooled to room temperature, taking out, carrying out suction filtration, and carrying out vacuum drying at 60 ℃. Then the sample is put into a muffle furnace and is in air atmosphereCalcining for 2-6 h. Then taking out the sample after the sample is naturally cooled to room temperature, and putting the sample in a tube furnace NH3Calcining for 1h in the atmosphere, with the heating rate of 5-10 ℃ min-1. And finally, naturally cooling the product to room temperature and collecting the product to obtain the nickel nitride. Wherein, the nitrogen source and the nickel source material can be nickel chloride hexahydrate and ammonium fluoride or/and urea respectively. Preparing nickel nitride, namely preparing a precursor on the basis of first hydrothermal preparation, wherein the hydrothermal temperature can be 80-160 ℃. And calcining the obtained nickel nitride precursor in a muffle furnace under the air atmosphere, wherein the calcining temperature is 200-300 ℃. Or putting the nickel nitride precursor into a tube furnace NH3Calcining at the temperature of 250-450 ℃ in the atmosphere. The particle size of the obtained nickel nitride is 50 nm-0.5 μm.
The potassium molybdenum sulfur material and the nickel nitride material are prepared by a hydrothermal method under the deionized water or alkaline condition, and then are washed, filtered, collected and dried to obtain the potassium molybdenum sulfur/nickel nitride composite material. The raw materials are mixed and dispersed by ultrasonic treatment (the power can be 100-150W, and the time can be 10-30 minutes). Mixed into a mixed solution and then placed in a reaction kettle, and the filling ratio of the reaction kettle is preferably controlled to be 50-70 vol%. Wherein the mass ratio of the potassium molybdenum sulfide material to the nickel nitride material can be 1: 0.5-2.5. For example, the potassium-molybdenum-sulfur/nickel nitride composite material is obtained by respectively centrifugally washing with ethanol and deionized water for 2-6 times, carrying out suction filtration and collection, and drying the product. The alkaline condition is sodium hydroxide, potassium hydroxide or ammonia water solution. The preferred hydrothermal temperature is 60-170 deg.C, preferably 80-160 deg.C, more preferably 100-140 deg.C, and most preferably 120 deg.C. If the hydrothermal reaction temperature is too high, a large amount of potassium molybdenum sulfur/nickel nitride composite material is agglomerated, so that the impedance is increased, and the catalytic performance is reduced. If the hydrothermal reaction temperature is too low, the potassium molybdenum sulfur material and the nickel nitride material do not react or react incompletely, no or only a small amount of sulfur-nickel bonds are formed, and the reduction of impedance cannot be realized, so that the catalytic activity is caused. If the addition amount of potassium, molybdenum and sulfur is too much, the active sites are insufficient, the bonding strength of the active sites and the coded hydroxyl radicals is weak, and the catalytic performance is reduced; if the amount of nickel nitride added is too large, the electron transfer rate is reduced, resulting in a decrease in catalytic performance. The hydrothermal treatment time may be 12 to 24 hours. For example, the drying may be one of a freeze drying method, a vacuum drying method, and an air drying method.
In the invention, sulfur-nickel bonds are formed between part of potassium-molybdenum-sulfur and nickel nitride in the potassium-molybdenum-sulfur/nickel nitride composite material to form a heterojunction, so that the oxygen evolution reaction and the hydrogen evolution reaction can be improved.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Examples of the preparation of potassium molybdenum sulfide and nickel nitride
(1) Preparation of potassium molybdenum sulfide: will K2S2Powder, Mo powder, MoS2The powders are mixed according to the molar ratio of 1:1:1 and fully ground in an agate mortar for 0.5 to 2 hours. Then pressing the mixed powder into small balls, sealing the small balls in a quartz tube in vacuum, annealing the small balls in a muffle furnace at the temperature of 600 ℃ and 1000 ℃ for 12 to 36 hours at the heating rate of 5 to 10 ℃ for min-1. And then, after the sample is naturally cooled to room temperature and taken out, dispersing the sample in deionized water, and performing vacuum drying at room temperature to obtain the potassium-molybdenum-sulfur.
Preparation of nickel nitride: 1.118g of nickel chloride hexahydrate, 0.37g of ammonium fluoride and 1.5g of urea are added into 60mL of deionized water, and then are heated in a hydrothermal kettle at 80-160 ℃ for 4-12h in a hydrothermal mode. And after the sample is naturally cooled to room temperature, taking out, carrying out suction filtration, and carrying out vacuum drying at 60 ℃. And then the sample is put into a muffle furnace to be calcined for 2-6h at the temperature of 200-300 ℃ under the air atmosphere. Then taking out the sample after the sample is naturally cooled to room temperature, and putting the sample in a tube furnace NH3Calcining for 1h at the temperature of 250-450 ℃ under the atmosphere, and the heating rate is 5-10 ℃ min-1. And finally, naturally cooling the product to room temperature and collecting the product to obtain the nickel nitride.
Example 1
(1) To a solution of 50mL of ammonia at pH 11(± 0.5), 50mg of potassium molybdenum sulfide and 100mg of nickel nitride were added;
(2) adding the mixed solution of potassium, molybdenum, sulfur and nickel nitride into a lining (the filling ratio is 60%) of a reaction kettle, and ultrasonically stirring for 30min at 120W until the mixed solution is uniformly dispersed;
(3) after ultrasonic stirring, carrying out hydrothermal heating on the uniformly mixed potassium-molybdenum-sulfur and nickel nitride solution at 120 ℃ for 16 hours by a hydrothermal method, taking out the solution, and collecting the solution after the sample is naturally cooled to room temperature;
(4) and carrying out suction filtration and washing on the collected solution. In the washing process, the black sample is washed with ethanol for three times, then washed with deionized water for three times, and then placed in an oven at 60 ℃ for vacuum drying for 12 hours. And finally, collecting the potassium-molybdenum-sulfur/nickel nitride composite material.
Example 2
(1) To 50mL of an aqueous ammonia solution at pH 11(± 0.5), 50mg of potassium molybdenum sulfide and 50mg of nickel nitride were added;
(2) adding the mixed solution of potassium, molybdenum, sulfur and nickel nitride into a lining (the filling ratio is 60%) of a reaction kettle, and ultrasonically stirring for 30min at 120W until the mixed solution is uniformly dispersed;
(3) after ultrasonic stirring, carrying out hydrothermal heating on the uniformly mixed potassium-molybdenum-sulfur and nickel nitride solution at 120 ℃ for 16 hours by a hydrothermal method, taking out the solution, and collecting the solution after the sample is naturally cooled to room temperature;
(4) and carrying out suction filtration and washing on the collected solution. In the washing process, the black sample is washed with ethanol for three times, then washed with deionized water for three times, and then placed in an oven at 60 ℃ for vacuum drying for 12 hours. And finally, collecting the potassium-molybdenum-sulfur/nickel nitride composite material.
Example 3
(1) To a solution of 50mL of ammonia at pH 11(± 0.5) was added 100mg of potassium molybdenum sulfide and 50mg of nickel nitride;
(2) adding the mixed solution of potassium, molybdenum, sulfur and nickel nitride into a lining (the filling ratio is 60%) of a reaction kettle, and ultrasonically stirring for 30min at 120W until the mixed solution is uniformly dispersed;
(3) after ultrasonic stirring, carrying out hydrothermal heating on the uniformly mixed potassium-molybdenum-sulfur and nickel nitride solution at 120 ℃ for 16 hours by a hydrothermal method, taking out the solution, and collecting the solution after the sample is naturally cooled to room temperature;
(4) and carrying out suction filtration and washing on the collected solution. In the washing process, the black sample is washed with ethanol for three times, then washed with deionized water for three times, and then placed in an oven at 60 ℃ for vacuum drying for 12 hours. And finally, collecting the potassium-molybdenum-sulfur/nickel nitride composite material.
Example 4
(1) To a solution of 50mL of ammonia at pH 11(± 0.5) was added 50mg of potassium molybdenum sulfide and 75mg of nickel nitride;
(2) adding the mixed solution of potassium, molybdenum, sulfur and nickel nitride into a lining (the filling ratio is 60%) of a reaction kettle, and ultrasonically stirring for 30min at 120W until the mixed solution is uniformly dispersed;
(3) after ultrasonic stirring, carrying out hydrothermal heating on the uniformly mixed potassium-molybdenum-sulfur and nickel nitride solution at 120 ℃ for 16 hours by a hydrothermal method, taking out the solution, and collecting the solution after the sample is naturally cooled to room temperature;
(4) and carrying out suction filtration and washing on the collected solution. In the washing process, the black sample is washed with ethanol for three times, then washed with deionized water for three times, and then placed in an oven at 60 ℃ for vacuum drying for 12 hours. And finally, collecting the potassium-molybdenum-sulfur/nickel nitride composite material.
Example 5
(1) To a solution of 50mL of ammonia at pH 11(± 0.5), 50mg of potassium molybdenum sulfide and 125mg of nickel nitride were added;
(2) adding the mixed solution of potassium, molybdenum, sulfur and nickel nitride into a lining (the filling ratio is 60%) of a reaction kettle, and ultrasonically stirring for 30min at 120W until the mixed solution is uniformly dispersed;
(3) after ultrasonic stirring, carrying out hydrothermal heating on the uniformly mixed potassium-molybdenum-sulfur and nickel nitride solution at 120 ℃ for 16 hours by a hydrothermal method, taking out the solution, and collecting the solution after the sample is naturally cooled to room temperature;
(4) and carrying out suction filtration and washing on the collected solution. In the washing process, the black sample is washed with ethanol for three times, then washed with deionized water for three times, and then placed in an oven at 60 ℃ for vacuum drying for 12 hours. And finally, collecting the potassium-molybdenum-sulfur/nickel nitride composite material.
Example 6
See example 1 for the preparation of the potassium molybdenum sulfide/nickel nitride composite material in this example 6, except that: the alkaline solution was replaced with deionized water.
Example 7
See example 1 for the preparation of the potassium molybdenum sulfide/nickel nitride composite material in this example 7, except that: the pH of the alkaline solution was 9.
Example 8
See example 1 for the preparation of the potassium molybdenum sulfide/nickel nitride composite material in this example 8, except that: the hydrothermal temperature is 160 ℃ and the time is 12 h.
Example 9
See example 1 for the preparation of the potassium molybdenum sulfide/nickel nitride composite material of this example 11, except that: the hydrothermal temperature is 80 ℃ and the hydrothermal time is 12 h.
The examples are given solely for the purpose of further illustrating the invention and are not to be construed as limiting thereof. For example, the alkaline solution can be at least one of sodium hydroxide, potassium hydroxide or ammonia water solution, the temperature of the hydrothermal treatment is distributed between 80 ℃ and 160 ℃, and the time of the hydrothermal treatment can be adjusted between 8 hours and 24 hours, so that the potassium-molybdenum-sulfur/nickel nitride composite material can be prepared.
Comparative example 1
For the preparation of the potassium molybdenum sulfur/nickel nitride composite of this comparative example 1, see example 1, except that: standing at room temperature 25 deg.C for 12 h.
Comparative example 2
For the preparation of the potassium molybdenum sulfur/nickel nitride composite of this comparative example 2, see example 1, except that: the mixture is heated at 180 ℃ for 12 h.
FIG. 1 shows X-ray diffraction spectra (XRD) of a potassium-molybdenum-sulfur material, a nickel nitride material and a potassium-molybdenum-sulfur/nickel nitride composite material synthesized by a hydrothermal method in example 1. from FIG. 1, it can be observed that characteristic peaks of the potassium-molybdenum-sulfur material are consistent with XRD standard cards JCPDS No.18-1064 of potassium-molybdenum-sulfur, and characteristic peaks of the nickel nitride material are consistent with XRD standard cards JCPDS No.10-0280 of nickel nitride, which confirms that the potassium-molybdenum-sulfur and nickel nitride materials are successfully prepared;
FIG. 2 shows X-ray photoelectron spectroscopy (XPS) of the synthesized K-Mo-S material, Ni-N material and the synthesized K-Mo-S/Ni-N composite material of example 1 by hydrothermal method, and it can be seen from FIG. 2 that characteristic peaks of O, K, Mo, S, Ni and N elements all exist, thus proving successful synthesis of the K-Mo-S/Ni-N composite material;
FIG. 3 shows the S2 p peaks of X-ray photoelectron spectroscopy (XPS) of the potassium-molybdenum-sulfur material synthesized by the present invention and the potassium-molybdenum-sulfur/nickel nitride composite synthesized by hydrothermal method of example 1. from FIG. 3, it can be seen that sulfur-nickel chemical bonds exist in the potassium-molybdenum-sulfur/nickel nitride composite, thus demonstrating that sulfur-nickel chemical bonds are formed between part of potassium-molybdenum-sulfur and nickel nitride;
FIG. 4 shows a Scanning Electron Microscope (SEM) of the potassium molybdenum sulfide/nickel nitride composite material synthesized by hydrothermal method in example 1, and it can be seen from FIG. 4 that the morphology of the potassium molybdenum sulfide/nickel nitride composite material is mainly a layered material;
FIG. 5 shows a Transmission Electron Micrograph (TEM) of a potassium molybdenum sulfur/nickel nitride composite synthesized in example 1 by a hydrothermal method, from a typical TEM image in FIG. 5a, a potassium molybdenum sulfur/nickel nitride composite is seen, which is composed of layered potassium molybdenum sulfur and nickel nitride having a smooth surface, and an HRTEM image (FIG. 5b) clearly shows lattice fringes with a interplanar spacing of 0.203nm and Ni3The N (111) planes correspond;
FIG. 6 shows the energy dispersive x-ray spectroscopy mapping (EDS-mapping) of the potassium molybdenum sulfur/nickel nitride composite synthesized in example 1 by a hydrothermal method, from which it can be seen that Mo, S, Ni and N elements are uniformly distributed in the potassium molybdenum sulfur/nickel nitride composite;
FIG. 7 shows the LSV and overpotential curves of the OER test in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method in examples 1-5. As can be seen from the LSV and overpotential curves, the overpotential of the catalyst is the lowest for the example 1 sample and the overpotential curve is 10cm at the anode current density in the case of the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method in examples 1-5-2The overpotential of this catalyst is 233mV, while those of the catalysts of examples 2-5 are 264 and 2, respectively93. 262 and 251mV, thus demonstrating the higher catalytic performance of the K-Mo-S/Ni-nitride composite catalyst of example 1 for OER;
FIG. 8 shows the LSV and overpotential curves for HER tests in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method in examples 1-5. As can be seen from the LSV and overpotential curves for the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method in examples 1-5, the overpotential of the catalyst is the lowest for the sample in example 1, and the current density at the anode is-10 cm-2The overpotentials were 89mV versus 148, 208, 158, and 119mV for the catalysts of the samples of examples 2-5, respectively, demonstrating the higher catalytic performance of the potassium molybdenum sulfur/nickel nitride composite catalyst of example 1 for HER;
FIG. 9 shows the Tafel slope plots of the potassium molybdenum sulfide/nickel nitride composites synthesized by hydrothermal method in examples 1-5 in 1M KOH, and it can be seen that the Tafel slope of the catalyst in example 1 is 66mV dec-1Whereas the overpotentials of the catalysts of the samples of examples 2-5 were 95, 84, 83 and 88mV dec, respectively-1Thus, the electrocatalytic activity of the potassium molybdenum sulfur/nickel nitride composite catalyst in example 1 was again demonstrated to be higher than that of the other samples;
FIG. 10 shows EIS impedance plots of the potassium molybdenum sulfur/nickel nitride composite materials synthesized by hydrothermal method in examples 1-5 in 1M KOH, and it can be seen from the EIS impedance of the catalyst sample in example 1 is 7.925 Ω, while the EIS impedance of the catalyst samples in examples 2-5 are 47.15, 53.51, 19.36 and 18.99 Ω, respectively, thus proving that the potassium molybdenum sulfur/nickel nitride composite material catalyst in example 1 is more beneficial to electron transmission and improving OER catalytic activity.
FIG. 11 shows the LSV and overpotential graphs for OER test in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1-2, respectively, from which it can be seen that, in the samples of the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1-2, respectively, the overpotential of the catalyst of the sample of example 1 is the lowest and the current density at the anode is 10cm-2The overpotential thereof was 233mV, whereas the overpotentials of the catalysts of examples 6, 7 and comparative examples 1-2 were 288, 281, 336 and 308mV, respectively,thus, the potassium molybdenum sulfur/nickel nitride composite catalyst in example 1 is proved to have higher catalytic performance on OER;
FIG. 12 shows the LSV and overpotential graphs for HER tests in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1-2, respectively, from which it can be seen that, in the samples of the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1-21-2, respectively, the overpotential of the catalyst of the sample of example 1 is the lowest and the current density at the anode is-10 cm-2The overpotentials of the sample catalysts of examples 6, 7 and comparative examples 1 to 21 to 2 were 89mV, while the overpotentials of the sample catalysts of examples 6, 7 and comparative examples 1 to 21 to 2 were 176, 163, 231 and 210mV, respectively, thereby demonstrating the higher catalytic performance of the potassium molybdenum sulfur/nickel nitride composite catalyst of example 1 for HER;
FIG. 13 shows the Tafel slopes of the potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1-2, respectively, in 1M KOH, from which it can be seen that the Tafel slope of the catalyst of example 1 is 66mV dec as a minimum-1Whereas the overpotentials of the catalysts of the samples of examples 6, 7 and comparative examples 1-2 were 84, 79, 100 and 119mV dec, respectively-1Thus, the electrocatalytic activity of the potassium molybdenum sulfur/nickel nitride composite catalyst in example 1 was again demonstrated to be higher than that of the other samples;
fig. 14 shows EIS impedance plots of potassium molybdenum sulfur/nickel nitride composites synthesized in examples 1, 6, 7 and comparative examples 1 to 2, respectively, in 1M KOH, and it can be seen from the graphs that the EIS impedance of the sample catalyst of example 1 is 7.925 Ω, and the impedances of the sample catalysts of examples 6, 7 and comparative examples 1 to 2 are 45.74, 31.36, 76.93 and 59.05 Ω, respectively, thus proving that the potassium molybdenum sulfur/nickel nitride composite catalyst of example 1 is more advantageous for electron transport and for improving the OER catalytic activity.
FIG. 15 shows the LSV and overpotential curves of OER test in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method at different temperatures in examples 1, 8 and 9. it can be seen from these plots that, in the samples of the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method in examples 1, 8 and 9, the overpotential of the catalyst in the sample of example 1 is the lowest, and the current density at the anode is 10cm-2The overpotential is 233mV, andthe overpotentials of the catalysts of the samples in examples 8 and 9 are 306 mV and 266mV respectively, so that the potassium-molybdenum-sulfur/nickel nitride composite material catalyst in example 1 has higher catalytic performance on OER;
FIG. 16 shows the LSV and overpotential curves of HER tests in 1M KOH for the potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal methods at different temperatures in examples 1, 8 and 9. it can be seen from the LSV and overpotential curves that the catalyst of example 1 has the lowest overpotential and the anode current density of-10 cm in the samples of hydrothermal methods for synthesizing potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal methods in examples 1, 8 and 9-2The overpotentials of the catalysts of examples 8 and 9 were 187 and 181mV, respectively, thereby demonstrating that the potassium molybdenum sulfur/nickel nitride composite catalyst of example 1 has higher catalytic performance for HER;
FIG. 17 shows the Tafel slopes of the K-Mo-S/Ni-nitride composites synthesized by hydrothermal method at different temperatures in examples 1, 8 and 9 in 1M KOH, and it can be seen from the graphs that the Tafel slope of the catalyst sample in example 1 is 66mV dec-1Whereas the overpotentials of the catalysts of the samples of examples 8 and 9 were 147 mV dec and 149mV dec, respectively-1Thus, the electrocatalytic activity of the potassium molybdenum sulfur/nickel nitride composite catalyst in example 1 was again demonstrated to be higher than that of the other samples;
FIG. 18 shows EIS impedance plots of potassium molybdenum sulfur/nickel nitride composites synthesized by hydrothermal method at different temperatures in examples 1, 8 and 9 in 1M KOH, and it can be seen from the EIS impedance of the catalyst sample in example 1 is 7.925 Ω, while the impedance of the catalyst samples in examples 8 and 9 is 47.3 Ω and 43.1 Ω, respectively, thereby proving that the catalyst potassium molybdenum sulfur/nickel nitride composite in example 1 is more beneficial to electron transmission and improving OER catalytic activity.
Table 1 shows the preparation process and performance parameters of the potassium molybdenum sulfide/nickel nitride composite material prepared according to the present invention:
industrial applicability
The potassium molybdenum sulfur/nickel nitride composite material prepared by the method greatly reduces the overpotentials of HER and OER, and both the Tafel slope and EIS impedance are obviously reduced, thereby being beneficial to the electrocatalysis of HER and OER. Therefore, the potassium molybdenum sulfur/nickel nitride composite catalyst effectively improves the electrochemical activity of HER and OER, and the preparation of the material has low requirement on equipment, short preparation period and easy operation of the preparation process, and is suitable for large-scale production.
Claims (10)
1. The potassium-molybdenum-sulfur/nickel nitride composite material is characterized by comprising potassium-molybdenum-sulfur KMoS2And nickel nitride Ni3N, and a part of potassium, molybdenum and sulfur and nickel nitride have sulfur-nickel chemical bonds between the potassium, molybdenum and sulfur.
2. The potassium molybdenum sulfur/nickel nitride composite of claim 1, wherein the potassium molybdenum sulfur/nickel nitride composite has a layered structure in which nickel nitride is composited in a layered potassium molybdenum sulfur KMoS2The above.
3. The potassium molybdenum sulfur/nickel nitride composite material according to claim 1 or 2, wherein the mass ratio of the potassium molybdenum sulfur to the nickel nitride material is 1:0.5 to 2.5.
4. The preparation method of the potassium molybdenum sulfur/nickel nitride composite material as claimed in any one of claims 1 to 3, wherein the potassium molybdenum sulfur/nickel nitride composite material is prepared by dispersing potassium molybdenum sulfur and nickel nitride in a reaction kettle filled with deionized water or an alkaline solution and performing hydrothermal reaction at 60-170 ℃.
5. The method according to claim 4, wherein the particle size of the potassium molybdenum sulfide is 500nm to 5 μm; the particle size of the nickel nitride is 50 nm-0.5 mu m.
6. The production method according to claim 4 or 5, wherein the mass ratio of the potassium molybdenum sulfide to the nickel nitride is 1:0.5 to 2.5.
7. The production method according to any one of claims 4 to 6, wherein the means of dispersion is sonication; preferably, the power of ultrasonic treatment is 100-150W, and the time is 10-30 minutes.
8. The method according to any one of claims 4 to 7, wherein the alkaline solution is at least one selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and preferably has a pH of 8 to 12.
9. The method according to any one of claims 4 to 8, wherein the hydrothermal reaction is carried out for 8 to 24 hours.
10. Use of a potassium molybdenum sulphur/nickel nitride composite material according to any of claims 1 to 3 in oxygen evolution reactions and hydrogen evolution reactions.
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