CN114318392B - MoS (MoS) 2 -NiS 2 NF hydrogen evolution material and preparation method and application thereof - Google Patents
MoS (MoS) 2 -NiS 2 NF hydrogen evolution material and preparation method and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000001257 hydrogen Substances 0.000 title claims abstract description 79
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910018661 Ni(OH) Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000006260 foam Substances 0.000 claims abstract description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 17
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 17
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 10
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of hydrogen energy, in particular to a MoS 2 ‑NiS 2 NF hydrogen evolution material and its preparation method and application. Firstly, dissolving sodium molybdate dihydrate, nickel nitrate hexahydrate and urotropine in deionized water to obtain a first mixed solution; then transferring the first mixed solution to a reaction kettle, taking foam nickel as a carrier, and obtaining MoO through hydrothermal reaction 2 ‑Ni(OH) 2 /NF; finally MoO is carried out 2 ‑Ni(OH) 2 calcining/NF and sulfur powder under anaerobic condition to obtain MoS 2 ‑NiS 2 Hydrogen evolution material/NF. MoS of the invention 2 ‑NiS 2 The N hydrogen evolution material is used for electrocatalytic hydrogen evolution reaction. Compared with the prior art, the MoS prepared by the invention 2 ‑NiS 2 The raw material cost of the NF hydrogen evolution material is low, the preparation mode is simple, the hydrogen evolution effect in alkaline solution is good, and the method is expected to be oriented to industrialized development.
Description
Technical Field
The invention relates to the technical field of hydrogen energy, in particular to a MoS 2 -NiS 2 NF hydrogen evolution material and its preparation method and application.
Background
As fossil fuels are increasingly exhausted, various new energy sources are increasingly utilized. The hydrogen energy is used as a renewable secondary energy source, has wide source, high heat value, cleanness and good combustion stability, and is an energy carrier widely adopted in the next generation after non-renewable energy sources such as fossil fuel and the like. Chemical water splitting is strongly dependent on mass transport and active centers, however, difficulty in facilitating mass transport and exposing sufficient active centers is a major bottleneck for both halves of the overall water splitting reaction, namely: hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER). Alkaline water electrolysis hydrogen production is the most potential technical means leading to hydrogen economy, but the reaction energy consumption is larger due to the existence of hydrogen evolution and oxygen evolution overpotential in the electrolysis process. In order to reduce the energy consumption, it is important to develop a cathode electrode material which is low in cost and has high catalytic activity. The molybdenum sulfide@cobalt-MOF/NF hydrogen evolution material disclosed by the invention of CN 113249753A Jiang Jibo and the like, an in-situ synthesis method and application thereof illustrate that the catalytic hydrogen evolution material is used for hydrogen evolution in alkaline solution, and no method is provided for simultaneously carrying out oxygen evolution reaction. The high efficiency electrolyzed water comprises hydrogen evolution and oxygen evolution reactions, and in particular, the hybrids of bimetallic sulfides exhibit superior catalytic performance compared to the monometallic sulfides. When two or more metal species are combined, more active sites may be exposed, thereby improving electrochemical reaction kinetics.
Currently, noble metal-based electrocatalysts (Pt, ruO 2 And IrO 2 ) Considered to be efficient, ideal HER and OER catalysts, can reduce overpotential and achieve fairly high energy conversion efficiency. However, the drawbacks and high cost of these precious metal-based materials have prevented their large scale application. To address this unfavorable situation, extensive research is underway to find advanced, economical, earth-resource-rich bifunctional electrocatalysts for bulk water splitting, which has remained a significant challenge to date.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a MoS 2 -NiS 2 NF hydrogen evolution material and its preparation method and application.
The invention aims to overcome the problems of the catalytic hydrolysis in the prior art and provides a MoS 2 -NiS 2 An NF hydrogen evolution material, a preparation method thereof and application thereof in electrocatalytic hydrogen evolution. MoS of the invention 2 -NiS 2 As hydrogen evolution catalyst, the NF hydrogen evolution material has lower synthesis cost than most catalysts, and the earth reserve of main elements is sufficient.
In the metal molybdenum, the 3d orbit is in a half-full state, and has strong adsorption effect on hydrogen atoms; in metallic nickel, the d orbitals of the valence layer are not fully filled, and due to the existence of the d orbitals, nickel atoms can easily form complexes, nickel combines with hydroxyl groups to form nickel hydroxide, and oxygen evolution is promoted. MoS (MoS) 2 -NiS 2 After being combined with the foam nickel, the hydrogen evolution performance of the foam nickel is greatly enhanced, the electrochemical performance is improved, and the synthesis method is simple.
The aim of the invention can be achieved by the following technical scheme:
it is an object of the present invention to provide a MoS 2 -NiS 2 The preparation method of the NF hydrogen evolution material comprises the following steps:
(1) Dissolving sodium molybdate dihydrate, nickel nitrate hexahydrate and urotropine in deionized water to obtain a first mixed solution;
(2) Transferring the first mixed solution obtained in the step (1) to a reaction kettle, and carrying out hydrothermal reaction by taking foam nickel as a carrier to obtain MoO2-Ni (OH) 2 /NF；
(3) MoO obtained in the step (2) is processed 2 -Ni(OH) 2 calcining/NF and sulfur powder under anaerobic condition to obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
In one embodiment of the present invention, in step (1), the dosage ratio of sodium molybdate dihydrate, nickel nitrate hexahydrate, urotropin, deionized water is 1mmol:1mmol:1mmol: (40-50) mL.
In one embodiment of the invention, in the step (2), the reaction temperature is 130-180 ℃ and the reaction time is 5-8h in the hydrothermal reaction process.
In one embodiment of the present invention, in step (3), moO 2 -Ni(OH) 2 The mass ratio of the NF to the sulfur powder is 1: (1-10).
In one embodiment of the invention, in step (3), the calcination process is performed in a resistance furnace, wherein the sulfur powder is upstream, moO 2 -Ni(OH) 2 the/NF is downstream.
In one embodiment of the invention, the calcination process is performed under nitrogen.
In one embodiment of the invention, the calcination temperature is 300-500 ℃ and the calcination time is 1-3h during calcination.
A second object of the present invention is to provide a MoS prepared by the above method 2 -NiS 2 Hydrogen evolution material/NF.
A third object of the present invention is to provide a MoS as described above 2 -NiS 2 Use of/NF hydrogen evolution material, said MoS 2 -NiS 2 The NF hydrogen evolution material is used for electrocatalytic hydrogen evolution reaction.
In one embodiment of the invention, in operation, moS is used 2 -NiS 2 The NF hydrogen evolution material is directly used as a working electrode in the reaction and is fixed by an electrode clamp.
In one embodiment of the invention, moS 2 -NiS 2 The NF hydrogen evolution material is washed clean by ethanol and deionized water, and then is put into a vacuum oven for drying for standby.
The purpose of the hydrothermal reaction of the invention is: the high-temperature and high-pressure environment promotes the reaction to be carried out, and the obtained MoO 2 -Ni(OH) 2 the/NF is uniform, has no agglomeration and good crystal form, and can be better loaded on the foam nickel.
The purpose of calcination in the present invention is: calcination can be effectively performed under the protection of nitrogen at high temperature to form MoS on the foam nickel 2 -NiS 2 Obtaining MoS 2 -NiS 2 Hydrogen evolution material/NF.
The invention is characterized in thatPreparation of MoS in strong base solution 2 -NiS 2 The bimetallic sulfide nanoparticles of/NF act as bifunctional electrocatalysts for bulk water splitting. MoS benefits from the synergistic effect of bimetallic sulfides and NF and unique 3D hollow structures 2 -NiS 2 Not only does/NF provide a rich active site, it also provides a variety of pathways for rapid and adequate transport of mass and electrons.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the invention, the foam nickel is sound absorption porous metal with excellent three-dimensional full-through mesh structure performance, the porosity of the foam nickel is about 95%, water or gas can pass through smoothly, the nickel frameworks are hollow and are connected with each other in a metallurgical state, and the foam nickel has the advantages of good stability, high porosity, thermal shock resistance, small bulk density, large specific surface area and the like; the 3d orbit of molybdenum is in a half-full state, and has strong adsorption effect on hydrogen atoms; in the metal nickel, the d orbitals of the valence layer are not fully filled, and due to the existence of the d orbitals, nickel atoms can easily form complexes, and after the complex is combined with the foam nickel, the hydrogen evolution performance of the foam nickel is greatly improved. Therefore, the metal with the unfilled orbit can be combined with the foam nickel, so that the desorption of hydrogen atoms adsorbed on the surface of the electrode is facilitated, and the hydrogen evolution performance of the metal nickel electrode is improved;
(2) Preparation of MoS according to the invention 2 -NiS 2 The NF hydrogen evolution material is of a composite structure, so that the active specific surface area can be increased, and the contact area of the material and the solution can be increased. MoS (MoS) 2 -NiS 2 A strong interaction between the nanoparticle and the porous NF occurs, making it excellent for HER.
(3) Preparation of MoS according to the invention 2 -NiS 2 MoS in NF hydrogen evolution material 2 -NiS 2 The heterogeneous lattice interface in (a) promotes H 2 Dissociation of the O molecules.
(4) Preparation of MoS according to the invention 2 -NiS 2 The raw material cost of the NF hydrogen evolution material is low, the preparation mode is simple, and the material has good stability due to the introduction of non-noble metal elements.
(5) The invention is made ofPreparing MoS 2 -NiS 2 The hydrogen evolution/NF material electrolyzes water in alkaline medium, has good hydrogen evolution effect and lower cost.
Detailed Description
The invention provides a MoS 2 -NiS 2 The preparation method of the NF hydrogen evolution material comprises the following steps:
(1) Dissolving sodium molybdate dihydrate, nickel nitrate hexahydrate and urotropine in deionized water to obtain a first mixed solution;
(2) Transferring the first mixed solution obtained in the step (1) to a reaction kettle, taking foam nickel as a carrier, and performing hydrothermal reaction to obtain MoO 2 -Ni(OH) 2 /NF；
(3) MoO obtained in the step (2) is processed 2 -Ni(OH) 2 calcining/NF and sulfur powder under anaerobic condition to obtain MoS2-NiS 2 Hydrogen evolution material/NF.
In one embodiment of the present invention, in step (1), the dosage ratio of sodium molybdate dihydrate, nickel nitrate hexahydrate, urotropin, deionized water is 1mmol:1mmol:1mmol: (40-50) mL.
In one embodiment of the invention, in the step (2), the reaction temperature is 130-180 ℃ and the reaction time is 5-8h in the hydrothermal reaction process.
In one embodiment of the present invention, in step (3), moO 2 -Ni(OH) 2 The mass ratio of the NF to the sulfur powder is 1: (1-10).
In one embodiment of the invention, in step (3), the calcination process is performed in a resistance furnace, wherein the sulfur powder is upstream, moO 2 -Ni(OH) 2 the/NF is downstream.
In one embodiment of the invention, the calcination process is performed under nitrogen.
In one embodiment of the invention, the calcination temperature is 300-500 ℃ and the calcination time is 1-3h during calcination.
The invention provides a MoS prepared by the method 2 -NiS 2 Hydrogen evolution material/NF.
The invention provides the MoS 2 -NiS 2 /NFApplication of hydrogen evolution material, the MoS 2 -NiS 2 The NF hydrogen evolution material is used for electrocatalytic hydrogen evolution reaction.
In one embodiment of the invention, in operation, moS is used 2 -NiS 2 The NF hydrogen evolution material is directly used as a working electrode in the reaction and is fixed by an electrode clamp.
In one embodiment of the invention, moS 2 -NiS 2 The NF hydrogen evolution material is washed clean by ethanol and deionized water, and then is put into a vacuum oven for drying for standby.
The purpose of the hydrothermal reaction of the invention is: the high-temperature and high-pressure environment promotes the reaction to be carried out, and the obtained MoO 2 -Ni(OH) 2 The NF is uniform, has no agglomeration and good crystal form, and can be better loaded on the foam nickel;
the purpose of calcination in the present invention is: calcination can be effectively performed under the protection of nitrogen at high temperature to form MoS on the foam nickel 2 -NiS 2 Obtaining MoS 2 -NiS 2 Hydrogen evolution material/NF.
The invention prepares MoS in strong alkali solution 2 -NiS 2 The bimetallic sulfide nanoparticles of/NF act as bifunctional electrocatalysts for bulk water splitting. MoS benefits from the synergistic effect of bimetallic sulfides and NF and unique 3D hollow structures 2 -NiS 2 Not only does/NF provide a rich active site, it also provides a variety of pathways for rapid and adequate transport of mass and electrons.
The present invention will be described in detail with reference to specific examples.
The various materials used in the examples of the present invention, unless otherwise specified, are commercially available.
Example 1
Sodium molybdate dihydrate 1.5mmol
Nickel nitrate hexahydrate 1.5mmol
Urotropine 1.5mmol
Deionized water 60ml
10 times MoO of sulfur powder 2 -Ni(OH) 2 mass/NF
MoS 2 -NiS 2 The NF hydrogen evolution material is prepared by the following steps:
1.5mmol of sodium molybdate dihydrate, 1.5mmol of nickel nitrate hexahydrate and 1.5mmol of urotropine are dissolved in 60mL of deionized water, and the solution is ultrasonically treated in an ultrasonic vibration instrument for 5min until stirring and dissolution are carried out, so as to obtain a first mixed solution. After no solid particles are found in the first mixed solution, the first mixed solution is transferred to a high-pressure reaction kettle, and a piece of foam nickel with the thickness of 8mm multiplied by 1mm is put into the high-pressure reaction kettle, and is subjected to hydrothermal treatment at 150 ℃ for 6 hours. Taking out MoO 2 -Ni(OH) 2 After being treated, the/NF is put into a resistance furnace, and nitrogen is introduced to lead the sulfur powder to be upstream and MoO to be 2 -Ni(OH) 2 The sulfur powder is in the downstream of the NF and the sulfur powder is in the amount of MoO 2 -Ni(OH) 2 10 times of the mass of the/NF, calcining for 1h at the temperature of 350 ℃ to finally obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
Example 2
MoS of example 1 2 -NiS 2 The NF hydrogen evolution material was rinsed clean with ethanol and deionized water, dried overnight in a vacuum oven, and dried.
(1) Drying MoS 2 -NiS 2 The NF hydrogen evolution material is clamped by an electrode clamp and directly used as a working electrode for testing.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive out air, and connecting a working electrode, an Ag/AgCl electrode and a stone mill rod electrode to an electrochemical workstation.
Example 3
Sodium molybdate dihydrate 1.5mmol
Nickel nitrate hexahydrate 1.5mmol
Urotropine 1.5mmol
Deionized water 68ml
Sulfur powder 5 times MoO 2 -Ni(OH) 2 mass/NF
MoS 2 -NiS 2 The NF hydrogen evolution material is prepared by the following steps:
dissolving 1.5mmol of sodium molybdate dihydrate, 1.5mmol of nickel nitrate hexahydrate and 1.5mmol of urotropine in 68mL of deionized water, and performing ultrasonic treatment in an ultrasonic vibration instrument for 5min until stirring and dissolving to obtain a first mixtureMixing the solutions. After no solid particles are found in the first mixed solution, the first mixed solution is transferred to a high-pressure reaction kettle, and a piece of foam nickel with the thickness of 8mm multiplied by 1mm is put into the high-pressure reaction kettle, and is subjected to hydrothermal treatment at 130 ℃ for 5 hours. Taking out MoO 2 -Ni(OH) 2 After being treated, the/NF is put into a resistance furnace, and nitrogen is introduced to lead the sulfur powder to be upstream and MoO to be 2 -Ni(OH) 2 The sulfur powder is in the downstream of the NF and the sulfur powder is in the amount of MoO 2 -Ni(OH) 2 5 times of the mass of the/NF, calcining for 2 hours at the temperature of 300 ℃ to finally obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
Example 4
MoS of example 3 2 -NiS 2 The NF hydrogen evolution material was rinsed clean with ethanol and deionized water, dried overnight in a vacuum oven, and dried.
(1) Drying MoS 2 -NiS 2 The NF hydrogen evolution material is clamped by an electrode clamp and directly used as a working electrode for testing.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive out air, and connecting a working electrode, an Ag/AgCl electrode and a stone mill rod electrode to an electrochemical workstation.
Example 5
Sodium molybdate dihydrate 1.5mmol
Nickel nitrate hexahydrate 1.5mmol
Urotropine 1.5mmol
Deionized water 75ml
Sulfur powder 1 time MoO 2 -Ni(OH) 2 mass/NF
MoS 2 -NiS 2 The NF hydrogen evolution material is prepared by the following steps:
1.5mmol of sodium molybdate dihydrate, 1.5mmol of nickel nitrate hexahydrate and 1.5mmol of urotropine are dissolved in 70mL of deionized water, and the solution is ultrasonically treated in an ultrasonic vibration instrument for 5min until stirring and dissolution are carried out, so as to obtain a first mixed solution. After no solid particles are found in the first mixed solution, the first mixed solution is transferred to a high-pressure reaction kettle, and a piece of foam nickel with the thickness of 8mm multiplied by 1mm is put into the high-pressure reaction kettle, and hydrothermal treatment is carried out for 8 hours at 180 ℃. Taking out MoO 2 -Ni(OH) 2 After being treated, the/NF is put into a resistance furnace, and nitrogen is introduced to lead the sulfur powder to be at the upstream，MoO 2 -Ni(OH) 2 The sulfur powder is in the downstream of the NF and the sulfur powder is in the amount of MoO 2 -Ni(OH) 2 Calcining at 500 deg.C for 3 hr to obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
Example 6
MoS of example 5 2 -NiS 2 The NF hydrogen evolution material was rinsed clean with ethanol and deionized water, dried overnight in a vacuum oven, and dried.
(1) Drying MoS 2 -NiS 2 The NF hydrogen evolution material is clamped by an electrode clamp and directly used as a working electrode for testing.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive out air, and connecting a working electrode, an Ag/AgCl electrode and a stone mill rod electrode to an electrochemical workstation.
Example 7
Sodium molybdate dihydrate 1.5mmol
Nickel nitrate hexahydrate 1.5mmol
Urotropine 1.5mmol
Deionized water 60ml
10 times MoO of sulfur powder 2 -Ni(OH) 2 mass/NF
MoS 2 -NiS 2 The NF hydrogen evolution material is prepared by the following steps:
1.5mmol of sodium molybdate dihydrate, 1.5mmol of nickel nitrate hexahydrate and 1.5mmol of urotropine are dissolved in 60mL of deionized water, and the solution is ultrasonically treated in an ultrasonic vibration instrument for 5min until stirring and dissolution are carried out, so as to obtain a first mixed solution. After no solid particles are found in the first mixed solution, the first mixed solution is transferred to a high-pressure reaction kettle, and a piece of foam nickel with the thickness of 8mm multiplied by 1mm is put into the high-pressure reaction kettle, and is subjected to hydrothermal treatment at 130 ℃ for 6 hours. Taking out MoO 2 -Ni(OH) 2 After being treated, the/NF is put into a resistance furnace, and nitrogen is introduced to lead the sulfur powder to be upstream and MoO to be 2 -Ni(OH) 2 the/NF is downstream. The amount of sulfur powder is MoO 2 -Ni(OH) 2 10 times of the mass of the/NF, calcining for 1h at the temperature of 350 ℃ to finally obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
Example 8
MoS of example 7 2 -NiS 2 The NF hydrogen evolution material was rinsed clean with ethanol and deionized water, dried overnight in a vacuum oven, and dried.
(1) Drying MoS 2 -NiS 2 The NF hydrogen evolution material is clamped by an electrode clamp and directly used as a working electrode for testing.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive out air, and connecting a working electrode, an Ag/AgCl electrode and a stone mill rod electrode to an electrochemical workstation.
Example 9
Sodium molybdate dihydrate 1.5mmol
Nickel nitrate hexahydrate 1.5mmol
Urotropine 1.5mmol
Deionized water 60ml
10 times MoO of sulfur powder 2 -Ni(OH) 2 mass/NF
MoS 2 -NiS 2 The NF hydrogen evolution material is prepared by the following steps:
1.5mmol of sodium molybdate dihydrate, 1.5mmol of nickel nitrate hexahydrate and 1.5mmol of urotropine are dissolved in 60mL of deionized water, and the solution is ultrasonically treated in an ultrasonic vibration instrument for 5min until stirring and dissolution are carried out, so as to obtain a first mixed solution. After no solid particles are found in the first mixed solution, the first mixed solution is transferred to a high-pressure reaction kettle, and a piece of foam nickel with the thickness of 8mm multiplied by 1mm is put into the high-pressure reaction kettle, and is subjected to hydrothermal treatment at 150 ℃ for 6 hours. Taking out MoO 2 -Ni(OH) 2 After being treated, the/NF is put into a resistance furnace, and nitrogen is introduced to lead the sulfur powder to be upstream and MoO to be 2 -Ni(OH) 2 The sulfur powder is in the downstream of the NF and the sulfur powder is in the amount of MoO 2 -Ni(OH) 2 10 times of the mass of the/NF, calcining for 1h at 300 ℃ to finally obtain MoS 2 -NiS 2 Hydrogen evolution material/NF.
Example 10
MoS of example 9 2 -NiS 2 The NF hydrogen evolution material was rinsed clean with ethanol and deionized water, dried overnight in a vacuum oven, and dried.
(1) Drying MoS 2 -NiS 2 Hydrogen evolution material for NFThe electrode clamp is clamped tightly and directly used as a working electrode for testing.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive out air, and connecting a working electrode, an Ag/AgCl electrode and a stone mill rod electrode to an electrochemical workstation.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (4)
1. MoS (MoS) 2 -NiS 2 The preparation method of the NF hydrogen evolution material is characterized by comprising the following steps:
(1) Dissolving sodium molybdate dihydrate, nickel nitrate hexahydrate and urotropine in deionized water to obtain a first mixed solution;
(2) Transferring the first mixed solution obtained in the step (1) to a reaction kettle, taking foam nickel as a carrier, and performing hydrothermal reaction to obtain MoO 2 -Ni(OH) 2 /NF；
(3) MoO obtained in the step (2) is processed 2 -Ni(OH) 2 calcining/NF and sulfur powder under anaerobic condition to obtain MoS 2 -NiS 2 Hydrogen evolution material/NF;
wherein in the step (1), the dosage ratio of the sodium molybdate dihydrate, the nickel nitrate hexahydrate, the urotropine and the deionized water is 1mmol:1mmol:1mmol: (40-50) mL;
in the step (3), moO 2 -Ni(OH) 2 The mass ratio of the NF to the sulfur powder is 1: (1-10);
in the step (2), in the hydrothermal reaction process, the reaction temperature is 130-180 ℃ and the reaction time is 5-8h;
in step (3), the calcination process is performed in a resistance furnace, wherein sulfur powder is upstream, moO 2 -Ni(OH) 2 The calcination process is carried out in the downstream under the nitrogen environment, the calcination temperature is 300-500 ℃, and the calcination time is 1-3h.
2. MoS prepared by the method of claim 1 2 -NiS 2 Hydrogen evolution material/NF.
3. A MoS as claimed in claim 2 2 -NiS 2 Use of a hydrogen evolution/NF material, characterized in that said MoS 2 -NiS 2 The NF hydrogen evolution material is used for electrocatalytic hydrogen evolution reaction.
4. A MoS according to claim 3 2 -NiS 2 The application of the NF hydrogen evolution material is characterized in that MoS is used in operation 2 -NiS 2 The NF hydrogen evolution material is directly used as a working electrode in the reaction and is fixed by an electrode clamp.
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