CN111659427B - High-efficiency electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF and preparation method thereof - Google Patents
High-efficiency electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF and preparation method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 100
- 239000001257 hydrogen Substances 0.000 title claims abstract description 99
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910020187 CeF3 Inorganic materials 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 203
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 230000009467 reduction Effects 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- 238000011068 loading method Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 16
- 239000002135 nanosheet Substances 0.000 abstract description 10
- 239000012670 alkaline solution Substances 0.000 abstract description 9
- 239000003929 acidic solution Substances 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 31
- 238000006722 reduction reaction Methods 0.000 description 28
- 239000006260 foam Substances 0.000 description 16
- 238000007789 sealing Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 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 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RQYSWULBRFINID-UHFFFAOYSA-N [Mo].[Ce] Chemical compound [Mo].[Ce] RQYSWULBRFINID-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
Electro-catalyst MoO for efficient electrolysis of water to separate out hydrogen in acidic and alkaline solutions2‑CeF3/NF and its preparation method. The preparation method comprises the following steps: firstly, adding a certain molar mass of nickel salt solution into a reaction kettle, and growing Ni (OH) on a porous nickel carrier through hydrothermal reaction2(ii) a Then uniformly mixing molybdenum salt, cerium salt, urea and ammonium salt in a certain proportion, and carrying out secondary hydrothermal reaction to obtain a precursor with a nanosheet structure; finally, the MoO is synthesized by hydrogen reduction treatment2‑CeF3An electrocatalyst material of/NF. The catalyst has a heterojunction structure consisting of molybdenum oxide and cerium fluoride, and has good hydrogen evolution performance in acidic and alkaline solutions.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a high-efficiency electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF and its preparation method.
Background
With the development of society and the continuous promotion of industrialization process, the global energy demand is increased sharply. At present, the problem of environmental pollution and the shortage of energy are important factors for the urgent development of clean energy form, and the development of a clean, efficient and sustainable new energy system is a fundamental way to solve the increasingly severe energy crisis and environmental pollution in the world today. Hydrogen is a renewable clean energy source, and the storage capacity of hydrogen is abundant on the earth, and water with the earth coverage rate of 70% is one of hydrogen storage warehouses. Hydrogen exists as the lightest element on earth in the form of various compounds or organic substances. Hydrogen has a large energy density (about 10 MJ/m)3) Combustion has a good energy conversion efficiency, 2.75 times the energy released by the hydrocarbon fuel. And the products of hydrogen combustion are water which is pollution-free and can be recycled, so that the environmental pollution caused by a large amount of waste gas generated by energy combustion can be reduced, and the worry of environmental departments on the harm of the environment is eliminated. The production and utilization of hydrogen energy is critical to the mitigation of energy and environmental concerns and has attracted considerable attention by researchers. The electrolytic water and hydrogen-oxygen fuel cell is concerned by having unique advantages and application prospects in the preparation and utilization of hydrogen, and the popularization and application of hydrogen production by electrolytic water to consume renewable energy sources such as water and electricity, wind power and photovoltaic power generation with excessive structural property is an important way for optimizing energy consumption structures.
However, the hysteresis of the electrocatalytic reactions such as the oxygen evolution reaction, the hydrogen evolution reaction, and the oxygen reduction reaction, which are involved in the conventional energy conversion devices such as electrolysis water and fuel cells, is one of the important bottlenecks that restrict the development thereof, and the cause of the hysteresis is mainly due to the hysteresis of the catalyst performance. However, noble metal materials such as Pt, Pd, etc. now exhibit excellent HER catalytic activity, but commercial application of noble metal catalysts is limited due to their low content in the earth's crust and high cost. Therefore, it is important to explore the substitution of rich, low cost non-noble metal catalysts in the earth's crust for traditional metal catalysts. Among them, a full hydrolysis catalyst capable of producing hydrogen and oxygen simultaneously is gaining wide attention.
In recent years, considerable research effort has been devoted to the development of low cost non-noble metal electrocatalysts, including transition metal carbides, sulfides, selenides, and oxides in place of noble metal catalysts. Among various transition metal oxides, Mo-based materials have good catalytic activity and thus are receiving increasing attention. However, the Mo-based electrocatalyst has problems in low electrical conductivity, catalytic stability and active specific surface area. Therefore, there is a need for an effective strategy to change the electronic environment on the surface of the catalyst, thereby exposing additional active sites during hydrogen evolution, and thereby increasing the rate of electrocatalytic water decomposition.
The increase in charge transfer rate can accelerate the performance of the electrocatalyst due to strong interactions between different structures at the interface. Interface engineering is considered an effective method to design efficient electrocatalysts, since electrocatalytic reactions typically occur at the interface. Research shows that the heterojunction through interface engineering can promote electron transfer and influence the adsorption/desorption energy of active matter in electrocatalysis reaction, so as to regulate catalytic capacity. Moreover, the synergistic interaction of the two components may also be beneficial to further improve catalytic activity and stability of the heterostructure. Heterogeneous nanostructures show synergistically enhanced kinetics at different active center and electron reconstitution interfaces, superior to their single component electrocatalysts. To solve MoO2Development bottleneck on bifunctional electrocatalysts, Lin Wang et al, Synthesis of N-doped MoO on NF2/Ni3S2Heterojunction (N-MoO)2/Ni3S2NF) exhibit excellent HER and OER activity and still have good stability at high currents. MoO2And Ni3S2The mutual cooperation and strong coupling between the interfaces effectively increase the number of active sites between the interfaces, thereby obviously improving the activity of HER and OER. (L.Wang, J.Cao, C.Lei, Q.Dai, B.Yang, Z.Li, X.Zhang, C.Yuan, L.Lei, Y.Hou, Strongly Coupled 3D N-dotted MoO2/Ni3S2 Hybrid for High Current Density Hydrogen Evolution Electrocatalysis and Biomass Upgrading,ACS Applied Materials&Interfaces,11(2019) 27743-27750). As another example, Gance Yang et al applied the synthesis of POMOF to a self-sacrificial template of FeOOH matrix by in situ growth of phosphomolybdic acid and iron-based complexes (PMo12@ Fe complexes), followed by low temperature phosphating to form MoO2-FeP@C。MoO2Interfacial electron redistribution of-FeP @ C occurs at the interface, where electron accumulation on FeP favors H2Optimization of O and H absorption energy, thereby improving HER activity, and MoO2The accumulation of the upper cavities is beneficial to the absorption of biomass organic matters. The stronger synergistic effect of the nano heterostructure is greatly improved in the aspect of hydrogen evolution performance. (G.Yang, Y.Jiano, H.Yan, Y.Xie, A.Wu, X.Dong, D.Guo, C.Tian, H.Fu, Interfacial Engineering of MoO2-FeP Heterojunction for Highly Efficient Hydrogen Evolution Coupled with Biomass Electrooxidation,Adv Mater,(2020)e2000455.)。
Therefore, the research on the hydrogen evolution performance of the material on the basis of the molybdenum-based catalyst is a problem which needs to be solved urgently at present, but the catalyst combines the excellent hydrogen evolution performance of molybdenum oxide and the excellent conductivity of cerium fluoride, and regulates and controls the rearrangement of electrons at an interface and the production of ion vacancies through the synergistic action between heterojunction interfaces to obtain the electrocatalyst with high-efficiency hydrogen evolution activity.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high-efficiency water electrolysis hydrogen evolution catalyst MoO2-CeF3The catalyst has excellent electrocatalytic hydrogen evolution performance.
The second technical problem to be solved by the invention is to provide the catalyst MoO2-CeF3/NF。
In order to solve the technical problem, the invention provides the high-efficiency water electrolysis hydrogen evolution electrocatalyst MoO2-CeF3The preparation method of/NF comprises the following steps:
(1) pretreating a porous nickel carrier;
(2) weighing nickel salt with a certain molar mass, adding water, and uniformly mixing to obtain a loading solution A;
(3) placing the porous nickel carrier in the loading solution A, and obtaining Ni (OH) growing on the porous nickel carrier through hydrothermal reaction2Washing and drying;
(4) weighing molybdenum salt, cerium salt, urea and ammonium salt, adding water, and mixing uniformly to obtain a load solution B;
(5) will bear Ni (OH)2The porous nickel carrier is placed in the load solution B, a precursor is obtained through secondary hydrothermal reaction, and the precursor is washed and dried;
(6) putting the dried precursor into a furnace, carrying out reaction at a certain temperature through hydrogen reduction treatment, and then cooling to obtain the high-efficiency electrolytic water hydrogen evolution electrocatalyst MoO2-CeF3/NF。
Specifically, in the steps (3) and (5), when the porous nickel support is placed in the supporting solution a or the supporting solution B, it is required to completely immerse the porous nickel support in the supporting solution a or the supporting solution B.
Specifically, in the steps (2) and (4), the nickel salt preferably includes nickel nitrate, the molybdenum salt preferably includes ammonium molybdate, the cerium salt preferably includes cerium nitrate, and the ammonium salt preferably includes ammonium fluoride.
Specifically, the precursor obtained by the secondary hydrothermal reaction in the step (5) has a nanosheet structure.
Specifically, in the step (1), the porous nickel carrier includes foamed nickel.
Specifically, in the step (1), the pretreatment step includes sequentially placing the porous nickel carrier in a dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for ultrasonic treatment, and then performing vacuum drying at a low temperature.
The concentration of the dilute hydrochloric acid solution is 2-4mol/L, preferably 3 mol/L; ultrasonic treating in dilute hydrochloric acid solution for 20-40min, preferably 30 min; ultrasonic treatment in anhydrous alcohol and deionized water for 10-20min, preferably 15 min.
Specifically, in the step (2):
controlling the molar mass of nickel in the nickel nitrate solution to be 5-10 mmol;
the deionized water is used in the supporting solution a in an amount sufficient to dissolve the nickel nitrate and to completely impregnate the support.
Specifically, in the step (3), the temperature of the hydrothermal reaction is controlled to be 150 ℃ and 240 ℃, and the reaction time is controlled to be 8-20 h.
Specifically, in the step (4), the molar ratio of molybdenum to cerium in the loading solution B is controlled to be 20-60: 1; the molar ratio of the molybdenum salt to the urea is 1: 2-6; the molar ratio of the molybdenum salt to the ammonium salt is 1: 2-10.
The deionized water is used in the supporting solution B in an amount sufficient to dissolve the molybdenum salt, cerium salt, urea and ammonium salt, and preferably in an amount sufficient to completely impregnate the support.
Specifically, in the step (5), the temperature of the secondary hydrothermal reaction is controlled to be 160-240 ℃, and the reaction time is 8-20 h.
Specifically, in the step (6), the hydrogen reduction treatment is performed in a tube furnace, and specifically, the step includes placing a container (e.g., a porcelain boat) containing the precursor in the center of the tube furnace.
Specifically, in the step (6), when the hydrogen reduction treatment is performed, H is2The volume ratio of/Ar is 1:7-10, preferably 1: 9; the reaction temperature is controlled to be 400-600 ℃, and the heat preservation time is 2-5 h.
Specifically, in the step (3) and/or (5), the washing step is deionized water washing, and the drying step is drying at 40-60 ℃ for 8-15 h.
The invention also discloses the high-efficiency electrolytic water hydrogen evolution electrocatalyst MoO prepared by the method2-CeF3The catalyst is a heterojunction material of cerium fluoride and molybdenum oxide which is constructed in situ.
The invention relates to an efficient water electrolysis hydrogen evolution electrocatalyst MoO2-CeF3The preparation method comprises the following steps of/NF, firstly growing hexahedral blocks on a porous nickel carrier by a hydrothermal method, and then synthesizing a nanosheet precursor by hydrothermal reaction of molybdenum salt and cerium salt in a certain proportion; is subjected to hydrogen reduction treatment to obtainA heterojunction material of cerium fluoride and molybdenum oxide.
The catalyst is in Ni (OH)2the/NF is grown on the molybdenum-cerium-based precursor nanosheet in situ, so that the intrinsic activity of the material is improved, and meanwhile, the active sites of the material are further increased.
Reducing the in-situ generated molybdenum-cerium-based precursor into CeF by hydrogen reduction3And MoO2Formed MoO2-CeF3the/NF has excellent electro-catalysis hydrogen evolution performance.
Meanwhile, the preparation method of the whole catalyst is simple and feasible, and is suitable for industrial popularization.
Drawings
In order that the present invention may be more readily and clearly understood, the following detailed description of the present invention is provided according to specific embodiment 1 of the present invention, taken in conjunction with the accompanying drawings, in which,
FIG. 1 shows the primary hydrothermal preparation of Ni (OH) in example 12SEM topography of/NF;
FIG. 2 is an SEM topography of a precursor prepared by the secondary hydrothermal method in example 1;
FIG. 3 shows the MoO production by reduction of hydrogen in example 12-CeF3SEM topography of 0.25/NF-450;
FIG. 4 shows MoO obtained in example 12-CeF3-an XRD pattern of 0.25/NF-450;
FIG. 5 shows MoO obtained in example 12-CeF3LSV, Tafel slope plot and current density versus time plot for 0.25/NF-450 materials;
FIG. 6 shows MoO obtained in example 12-CeF3-0.25/NF-450 material compared to other materials in alkaline and acidic solutions for hydrogen evolution performance.
Detailed Description
Example 1
This example describes a high efficiency electrolysis water hydrogen evolution catalyst MoO2-CeF3The preparation method of/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, putting into a 60 ℃ oven for drying for 12h to obtain Ni (OH)2The SEM topography is shown in figure 1;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 0.25mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, putting into a 60 ℃ oven, and drying for 12h to obtain a precursor, wherein an SEM appearance diagram of the precursor is shown in FIG. 2;
(6) putting the dried precursor into a tubular furnace, carrying out hydrogen reduction treatment at the temperature of 450 ℃ for reaction, and then cooling the tubular furnace to room temperature to obtain the high-efficiency electrolytic water hydrogen evolution catalyst, which is recorded as MoO2-CeF3The SEM topography is shown in figure 3, and the XRD pattern is shown in figure 4 of 0.25/NF-450.
As shown in fig. 1, as can be seen from (1) in fig. 1, the structure of the hexagonal form nano-block is uniformly and tightly attached to the nickel foam, so that a large contact area can be provided for the material; as can be seen from (2) in fig. 1, it can be estimated that the diameter of the hexagonal crystal form nano bulk is approximately 3 to 5 μm;
as shown in fig. 2, as can be seen from (1) in fig. 2, the nanosheets distributed vertically and uniformly grow on the surface of the precursor, and the diameter of the nanosheets distributed vertically and uniformly, which can be roughly estimated from (2) in fig. 2, is about 200 nm and 300 nm;
as shown in fig. 3, (1) in fig. 3, it can be seen that after hydrogen reduction, the surface of the material still maintains the structure of the nanosheets, and the structure of the nanosheets vertically and uniformly distributed has extremely high stability and a large specific surface area, so that a large number of active sites can be provided for the material, and adsorption and desorption of the catalytic intermediate H are facilitated; as can be seen from the comparison between (2) in FIG. 3 and (2) in FIG. 2, the nanosheet structure after hydrogen reduction has a volume expansion with a diameter of about 500-1000 nm; the volume enlargement is accompanied with a larger contact area in the catalysis process, which is beneficial to the catalysis.
As shown in FIG. 4, CeF is present in the material3、MoO2And Ni. Wherein, MoO2And CeF3Derived from the product of hydrogen reduction, Ni being base foam nickel, MoO2And CeF3Mainly a composition of nano-sheets.
The high-efficiency electrolytic water hydrogen evolution electrocatalyst obtained in the embodiment is 0.25CeF3/MoO2The LSV and Tafel slope graph and the current density-time relation graph of the/NF-450 material are shown in the attached figure 5; wherein the content of the first and second substances,
FIG. 5 (1) is a LSV graph of hydrogen evolution of the material by electrolyzing water in an alkaline solution, and it can be seen that the hydrogen evolution performance of the material is 18mV at 10 mA/cm;
FIG. 5 (2) is a Tafel slope diagram converted from an LSV diagram of hydrogen evolution by electrolysis of water in an alkaline solution, and it can be seen from the diagram that the Tafel slope of hydrogen evolution of a material in an alkaline solution is 38.91 mA/dec;
in FIG. 5, (3) shows the cycle of hydrogen evolution by electrolyzing water in alkaline solution, and it can be seen that the material is at 10mA/cm2The current density can be kept for 24 hours without obvious change, so that the hydrogen evolution catalyst has good hydrogen evolution cycle performance;
FIG. 5 (4) is an LSV diagram of hydrogen evolution of the material in the acidic solution by electrolyzing water, and it can be seen from the diagram that the hydrogen evolution performance of the material is 10mA/cm2At the time of the operation, the concentration is 41 mV;
FIG. 5 (5) is a Tafel slope diagram converted from an LSV diagram of hydrogen evolution by electrolysis of water in an acidic solution, and it can be seen that the Tafel slope of oxygen evolution of the material is 46.05 mA/dec;
in FIG. 5, (6) shows the cycle of hydrogen evolution by electrolyzing water in the acid solution, and it can be seen that the material is at 10mA/cm2The current density can be kept for 24 hours without obvious change, so that the hydrogen evolution catalyst has good hydrogen evolution cycle performance;
example 2
This example describes a high efficiency electrolysis water evolution hydrogen electrocatalyst MoO2-CeF3The preparation method of/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 0.25mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(6) and putting the dried precursor into a tube furnace, carrying out reaction at the temperature of 400 ℃ through hydrogen reduction treatment, and then cooling the tube furnace to the room temperature.
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm2When the hydrogen evolution overpotential is 29mV, the Tafel slope is 49.77mV/dec measured under alkaline conditions, at a constant value of 10mA/cm2Under the current density, the voltage can still keep stable after 24 hours; in the presence of acidMeasuring the hydrogen evolution overpotential to be 83mV and the Tafel slope to be 77.27mV/dec under the sexual condition; at the same time, the constant current is 10mA/cm2Under the current density, the voltage can still keep stable after 24 hours.
Example 3
This example describes a high efficiency electrolysis water evolution hydrogen electrocatalyst MoO2-CeF3The preparation method of/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 0.25mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(6) and putting the dried precursor into a tube furnace, carrying out reaction at the temperature of 500 ℃ through hydrogen reduction treatment, and then cooling the tube furnace to room temperature.
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm2When the hydrogen evolution overpotential is measured under alkaline conditions to be 30mV, the Tafel slope is 58.72mV/dec, and the constant value is 10mA/cm2Under the current density, the voltage can still keep stable after 24 hours; the hydrogen evolution over-potential is measured to be 62mV under the acidic condition, and the Tafel slope is 64.83mV/dec; at the same time, the constant current is 10mA/cm2Under the current density, the voltage can still keep stable after 24 hours.
Comparative example 1
The material of this comparative example was a material without added cerium (noted as MoO)2/NF-450), the specific preparation process is as follows:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(6) and putting the dried precursor into a tube furnace, carrying out reaction at the temperature of 450 ℃ through hydrogen reduction treatment, and then cooling the tube furnace to the room temperature.
Comparative example 2
The material of this comparative example was a material without molybdenum addition (noted as CeF)3-0.25/NF-450), the specific preparation process is as follows:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 0.25mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(6) and putting the dried precursor into a tube furnace, carrying out reaction at the temperature of 450 ℃ through hydrogen reduction treatment, and then cooling the tube furnace to the room temperature.
Comparative example 3
The material of this comparative example is a 0.5mmol cerium-added material (noted as MoO)2-CeF3-0.5/NF-450), the specific preparation process is as follows:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 0.5mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution B into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(6) and putting the dried precursor into a tube furnace, carrying out reaction at the temperature of 450 ℃ through hydrogen reduction treatment, and then cooling the tube furnace to the room temperature.
Comparative example 4
The material of the comparative example is a material without hydrogen reduction (marked as Precursor), and the specific preparation process comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 1mmol of ammonium molybdate tetrahydrate, 0.25mmol of cerium nitrate hexahydrate, 4mmol of ammonium fluoride and 2mmol of urea, adding 60ml of deionized water, and stirring for 2 hours to obtain a loading solution B;
(5) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; and when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ oven for drying for 12 hours.
Comparative example 5
The material of the comparative example was a material that did not undergo hydrogen reduction and secondary hydrothermal (denoted as Ni (OH))2/NF) and the specific preparation process comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid for 30min, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 7mmol of nickel nitrate hexahydrate, adding 60ml of deionized water, and uniformly stirring to obtain a loading solution A;
(3) transferring the obtained load solution A into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 180 ℃ drying oven for reaction for 12 hours; and when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ oven for drying for 12 hours.
Catalytic materials (noted as MoO) from example 1, respectively2-CeF30.25/NF-450), cerium-free material (noted as MoO) prepared in comparative example 12NF-450), molybdenum-free material prepared in comparative example 2 (noted as CeF30.25/NF-450), material prepared in comparative example 3 plus 0.5mmol of cerium (noted as MoO)2-CeF3-0.5/NF-450), the material prepared in comparative example 4 without hydrogen reduction (noted as Precursor), the material prepared in comparative example 5 without hydrogen reduction and secondary hydrothermal (noted as Ni (OH)2NF), and pure nickel foam (noted NF) and commercial platinum carbon (noted Pt/C) were compared for performance differences, and the results are shown in figure 6.
FIG. 6 (1) is a comparison between the electrocatalytic hydrogen evolution performance of the materials in alkaline solution, and it can be seen that pure Nickel Foam (NF) has the worst performance, because nickel foam is the matrix material, and its hydrogen evolution performance is negligible; without addition of cerium material (noted as MoO)2NF-450), molybdenum-free material prepared in comparative example 2 (noted as CeF30.25/NF-450), material prepared in comparative example 3 plus 0.5mmol of cerium (noted as MoO)2-CeF3-0.5/NF-450), the material prepared in comparative example 4 without hydrogen reduction (noted as Precursor), the material prepared in comparative example 5 without hydrogen reduction and secondary hydrothermal (noted as Ni (OH)2NF) and commercial Pt-C (Pt/C) at 10mA/cm2At the time of the addition, the concentration of the acid is respectively 48mV, 146mV, 31mV, 170mV, 132mV and 28 mV.
FIG. 6 (2) shows the Tafel slope corresponding to the data in FIG. 6 (1), and it can be seen that the material without added cerium (denoted as MoO)2NF-450), molybdenum-free material prepared in comparative example 2 (noted as CeF 3450/NF-450), material prepared in comparative example 3 plus 0.5mmol of cerium (noted as MoO)2-CeF3-0.5/NF-450), the material prepared in comparative example 4 without hydrogen reduction (noted as Precursor), the material prepared in comparative example 5 without hydrogen reduction and secondary hydrothermal (noted as Ni (OH)2NF)/NF) and commercial platinum carbon (Pt/C) have Tafel slopes of 110.88mV/dec, 125.64mV/dec, 48.68mV/dec, 144.75mV/dec, 127.37mV/dec and 41.13mV/dec, respectively.
FIG. 6 (3) is a comparison of the electro-catalytic hydrogen evolution performance of each material in an acidic solution, and it can be seen that pure Nickel Foam (NF) has the worst performance, because the nickel foam is a matrix material, and the hydrogen evolution performance of the nickel foam can be ignored; materials without added cerium (noted as MoO)2NF-450), molybdenum-free material prepared in comparative example 2 (noted as CeF 3450/NF-450), material prepared in comparative example 3 plus 0.5mmol of cerium (noted as MoO)2-CeF3-0.5/NF-450), the material prepared in comparative example 4 without hydrogen reduction (noted as Precursor), the material prepared in comparative example 5 without hydrogen reduction and secondary hydrothermal (noted as Ni (OH)2NF) and commercial Pt-C (Pt/C) at 10mA/cm2The time of the reaction is 83mV, 191mV, 61mV, 252mV, 220mV and 40mV respectively.
FIG. 6 (4) shows the Tafel slope corresponding to the data in FIG. 6 (3), and it can be seen that the material without added cerium (denoted as MoO)2NF-450), molybdenum-free material prepared in comparative example 2 (noted as CeF 3450/NF-450), material prepared in comparative example 3 plus 0.5mmol of cerium (noted as MoO)2-CeF3-0.5/NF-450), the material prepared in comparative example 4 without hydrogen reduction (noted as Precursor), the material prepared in comparative example 5 without hydrogen reduction and secondary hydrothermal (noted as Ni (OH)2NF)/NF) and commercial platinum carbon (Pt/C) have Tafel slopes of 69.73mV/dec, 79.45mV/dec, 55.31mV/dec, 156.86mV/dec, 130.95mV/dec and 34.55mV/dec, respectively.
In conclusion, the catalyst material disclosed by the invention has excellent hydrogen evolution performance in alkaline and acidic solutions.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. Efficient electrolysis water hydrogen evolution catalyst MoO2-CeF3The preparation method of/NF is characterized by comprising the following steps:
(1) pretreating a porous nickel carrier;
(2) weighing nickel salt with a certain molar mass, adding water, and uniformly mixing to obtain a loading solution A;
(3) placing the porous nickel carrier in the loading solution A, obtaining Ni (OH)2 growing on the porous nickel carrier through hydrothermal reaction, washing and drying;
(4) weighing molybdenum salt, cerium salt, urea and ammonium salt, adding water, and mixing uniformly to obtain a load solution B;
(5) will bear Ni (OH)2The porous nickel carrier is placed in the load solution B, a precursor is obtained through secondary hydrothermal reaction, and the precursor is washed and dried;
(6) putting the dried precursor into a furnace, carrying out reaction at a certain temperature through hydrogen reduction treatment, and then cooling to obtain the efficient electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF；
Wherein the porous nickel carrier is foamed nickel; the ammonium salt is ammonium fluoride.
2. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1oO2-CeF3The preparation method of/NF is characterized in that in the step (1), the pretreatment step comprises the step of sequentially placing the porous nickel carrier in dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for carrying outSonication, and subsequent vacuum drying at low temperature.
3. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3The preparation method of/NF is characterized in that in the step (2), the amount of nickel substances in the load solution A is controlled to be 5-10 mmol.
4. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3The preparation method of/NF is characterized in that in the step (3), the temperature of the hydrothermal reaction is controlled to be 150-240 ℃, and the reaction time is 8-20 h.
5. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3The preparation method of/NF is characterized in that in the step (4), the molar ratio of molybdenum to cerium in the loading solution B is controlled to be 20-60: 1; the molar ratio of the molybdenum salt to the urea is 1: 2-6; the molar ratio of the molybdenum salt to the ammonium salt is 1: 2-10.
6. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3The preparation method of/NF is characterized in that in the step (5), the temperature of the secondary hydrothermal reaction is controlled to be 160-240 ℃, and the reaction time is 8-20 h.
7. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3The preparation method of/NF is characterized in that in the step (6), the container containing the precursor is placed in the center of a tube furnace to be subjected to hydrogen reduction treatment.
8. The high-efficiency electrolytic water hydrogen evolution catalyst M according to claim 1 or 2oO2-CeF3Preparation method of/NFA method characterized in that, in the step (6), when the hydrogen reduction treatment is performed, H is2/ArThe volume ratio of (A) to (B) is 1: 7-10; the reaction temperature is 400-600 ℃, and the heat preservation time is 2-5 h.
9. High-efficiency electrolytic water hydrogen evolution catalyst M prepared by the preparation method of any one of claims 1 to 8oO2-CeF3The catalyst is a heterojunction material of cerium fluoride and molybdenum oxide which is constructed in situ.
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