CN110180552B - Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof - Google Patents
Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN110180552B CN110180552B CN201910575475.6A CN201910575475A CN110180552B CN 110180552 B CN110180552 B CN 110180552B CN 201910575475 A CN201910575475 A CN 201910575475A CN 110180552 B CN110180552 B CN 110180552B
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- 239000010949 copper Substances 0.000 title claims abstract description 41
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 26
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 9
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 230000009149 molecular binding Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004677 hydrates Chemical class 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
- 239000008204 material by function Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- B01J35/33—
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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 a copper/cuprous oxide/molybdenum dioxide electrocatalytic material, a preparation method thereof and application thereof in the aspect of hydrogen evolution by electrolyzing water. Firstly, cleaning the foamed nickel, then placing the foamed nickel in an acidic solution containing copper and molybdenum for hydrothermal reaction, and finally placing the foamed nickel in a reducing atmosphere for high-temperature reduction. The material improves the catalytic hydrogen evolution effect and durability under alkaline conditions through the synergistic effect generated by combining metal hydroxide and metal, wherein the hydroxide promotes the dissociation of water, and nearby metal atoms promote hydrogen intermediates to H2Adsorption and binding of molecules.
Description
Technical Field
The invention relates to the technical field of composite functional materials, in particular to a copper/cuprous oxide/molybdenum dioxide electrocatalytic material, a preparation method thereof and application thereof in hydrogen evolution by electrolysis of water.
Background
The hydrogen is a clean and flexible energy carrier, is expected to play a key role in a sustainable energy system in the future, and the electrochemical water cracking technology provides a sustainable development approach for producing the hydrogen. The technology can convert electric energy from renewable energy sources into chemical energy, is a hydrogen conversion technology with a very promising prospect, and has profound significance for effectively and widely utilizing the renewable energy sources. The renewable energy source is characterized by variable and intermittent output, and the key point for realizing high-efficiency water cracking lies in developing a high-activity and durable electrocatalyst for hydrogen evolution reaction.
The alkaline water splitting technology provides a strong support for the commercial production of cost-effective hydrogen. To achieve higher reaction rates, negligible overpotentials are required. Platinum (Pt) is a recognized reference catalyst for the catalytic hydrogen evolution from electrolyzed water, however, due to the scarcity and high cost of platinum, the large-scale industrial application of platinum is severely limited. Therefore, it is of great significance to further explore and develop a high-efficiency and low-cost catalyst for hydrogen evolution by electrolysis of water under alkaline conditions.
The inventor team and other researchers have previously disclosed a number of metal foam-based composites and their use in the catalytic hydrogen evolution from electrolyzed water. In CN108950585A, the copper foam is not used as a support material, it participates in the reaction at the later stage and is transformed into a part of active substances of the catalyst, and the generated sulfide substance is brittle and lacks toughness. The preparation method of the electrochemical material disclosed in CN108754532A is complicated, the generated LDH itself has relatively weak electronic conductivity, and although the electronic conductivity is improved by the post carbon coating treatment, the structure of the LDH may be damaged by the high-temperature carbonization treatment to cover the original active sites. The composite material disclosed in CN106702425A has excellent catalytic activity only in acidic solution, and in addition, the preparation process is complicated, and the electrolytic water reaction requires water molecules to be in full contact with the catalyst. Moreover, the scheme is that the copper electroplating layer on the surface of the formed molybdenum disulfide covers a part of active sites, and the catalytic efficiency of the material is reduced. The catalyst disclosed in CN109468662A is in powder or granule form, and needs to be supported on a glassy carbon electrode by means of an adhesive for electrochemical test and reaction, and active substances may fall off under a high current density state, which affects the catalytic performance.
In conclusion, the existing similar electrocatalytic materials have some problems in the performances, preparation methods and use processes.
Disclosure of Invention
The invention aims to solve the problems of the existing electrolytic water catalytic hydrogen evolution catalytic material, and the non-precious Cu-Mo-O type electrocatalytic material is prepared by combining a hydrothermal method with a high-temperature reduction reaction. The material shows extremely high activity and excellent stability when water is electrolyzed in an alkaline solution for catalyzing hydrogen evolution, and has good application prospect. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the copper/cuprous oxide/molybdenum dioxide electrocatalytic material specifically comprises the following steps: (a) pretreating the three-dimensional foam metal for later use; (b) preparing a mixed solution by using a copper salt and a molybdenum salt, and adding the treated three-dimensional foam metal to perform a hydrothermal reaction to obtain a copper-molybdenum bimetal oxide precursor; (c) and (3) placing the copper-molybdenum bimetal oxide precursor in a reducing atmosphere for reduction.
Further, the three-dimensional foam metal is specifically foam nickel, the porosity of the foam nickel is more than 90%, and the purity of the foam nickel is more than 98%.
Further, the pretreatment of the step (a) comprises soaking and cleaning the three-dimensional foam metal by using at least one of deionized water, an acid solution and an alcohol solvent, wherein the soaking and cleaning temperature does not exceed 200 ℃, and ultrasonic treatment is applied during the soaking and cleaning process so as to enhance the cleaning effect.
Further, the preparation method of the mixed solution in the step (b) is as follows: adding copper salt and molybdenum salt into water, stirring and dissolving, and adjusting the pH value to 2-5 by using dilute hydrochloric acid aqueous solution.
Further, the copper salt is selected from one of copper nitrate, copper chloride, copper sulfate and copper acetate, and is preferably copper nitrate; the molybdenum salt is selected from one of sodium molybdate and ammonium molybdate, and sodium molybdate is preferred. The molar ratio of the copper salt to the molybdenum salt is 0.25-4: 1.
Further, the hydrothermal reaction temperature in the step (b) is 100-200 ℃, and the hydrothermal reaction time is within 24 h.
Further, in the step (c), the reducing atmosphere is hydrogen, the reducing reaction temperature is 200-600 ℃, and the reducing reaction time is within 6 h.
Another object of the present invention is to provide a copper/cuprous oxide/molybdenum dioxide electrocatalytic material prepared according to the above method, which can be used for the catalytic hydrogen evolution of electrolyzed water in alkaline solution.
The catalytic activity of most of the catalysts for catalyzing hydrogen evolution by electrolyzed water under alkaline conditions is usually obviously lower than that under acidic conditions, and the phenomenon can be possibly combined with electrolyzed water in alkaline or acidic solutionThe reaction path difference of hydrogen evolution is related. More precisely, the electrolytic water evolution of hydrogen reaction shows slow kinetics in alkaline solutions, probably due to the fact that the H intermediate is derived from water rather than hydronium ion (H)3O+) Caused by medium release. This problem can be solved by creating a synergistic catalyst by combining metal hydroxides, which promote the dissociation of water, with metal atoms, which promote the hydrogen intermediate to H2Adsorption and binding of molecules.
The potential of molybdenum-based materials as electrocatalysts for hydrogen evolution by water electrolysis catalysis is receiving more and more attention. To date, a great deal of effort has been devoted to lowering the energy barrier (Δ G (H)2O)) water separation step. Research reports that doping of heteroatoms and adjusting the valence state of molybdenum are effective strategies to accelerate the kinetics of alkaline HER reactions, particularly transition metal molybdates (mmoos)4) And hydrates thereof are ideal precursors for the preparation of active rare earth electrocatalysts, because the molybdenum-based materials are highly active and the electronic structure between molybdenum and the heteroatom (M) is adjustable. It was also found that in a 1.0M KOH solution, the oxide contained Mo of a lower valence state (surface Mo)5+And Mo4+) The activity of the precursor is obviously enhanced compared with that of the bimetallic oxide precursor containing Mo with the valence of + 6.
The invention provides copper/cuprous oxide/molybdenum dioxide (Cu/Cu)2O/MoO2) The electro-catalytic hydrogen evolution catalyst takes three-dimensional porous foamed nickel with a net structure as a carrier, so that on one hand, the contact surface area of the catalyst and water is increased, and a good channel is provided for electron transfer; on the other hand, the conductivity of the hybrid catalyst is improved, the dispersibility of the electroactive phase is enhanced, and the electroactive phase has more active sites. Cu/Cu grown in situ on foamed nickel surface2O/MoO2The two-dimensional active nano-sheet has an open framework and is in close contact with a three-dimensional conductive substrate. Due to the synergistic effects of strong interaction, electron transfer and the like at the interface of the metal/oxide, the material shows excellent activity in the aspect of hydrogen evolution; the oxide carrier strongly influences the physical and chemical properties of the metal nanoparticles by providing dual active sites at the metal/oxide interfacePlays a key role in the catalysis process, and finally improves the catalytic activity, selectivity and durability of the catalytic material. Experiments show that the low-valence copper-molybdenum bimetal oxide prepared by the thermal reduction method has better catalytic activity and stability under the alkaline condition. In addition, the invention also has the advantages of cheap and easily obtained raw materials, simple preparation process, lower cost and the like.
Drawings
FIG. 1 shows Cu/Cu obtained in example 1 of the present invention2O/MoO2XRD pattern of (a);
FIG. 2 shows Cu/Cu obtained in example 1 of the present invention2O/MoO2SEM picture of (1);
FIG. 3 shows Cu/Cu obtained in example 1 of the present invention2O/MoO2Working electrode polarization curves and Tafel comparison graphs of the nickel foam of comparative example 1 and the copper-molybdenum bimetal oxide precursor of comparative example 2;
FIG. 4 shows Cu/Cu obtained in example 1 of the present invention2O/MoO2Chronopotentiometry at constant current density in alkaline solution.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
Example 1
(1) And putting the three-dimensional foam nickel into absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min so as to remove oil stains on the surface. Taking out and putting into an autoclave filled with 1mol/L dilute hydrochloric acid aqueous solution, heating to 100 ℃, and carrying out hydrothermal reaction for 6h so as to remove the oxide on the surface. And taking out the foamed nickel after the reaction is finished, and washing the foamed nickel with deionized water for later use.
(2) Deionized water is used as a solvent to prepare a mixed solution of copper nitrate and sodium molybdate, wherein the concentration of the copper nitrate is 0.02mol/L, and the concentration of the sodium molybdate is 0.01 mol/L. And (3) adjusting the pH value of the mixed solution to 3-4 by using 1mol/L dilute hydrochloric acid aqueous solution to obtain a clear and transparent mixed solution. And (3) placing the cleaned foam nickel into an autoclave filled with an acidic mixed solution, and heating to 180 ℃ for hydrothermal reaction for 6 hours. And taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water, and drying to obtain the copper-molybdenum bimetal oxide precursor.
(3) In the hydrogen atmosphere, heating the copper-molybdenum bimetal oxide precursor from room temperature to 450 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h to obtain Cu/Cu2O/MoO2An electrocatalytic material.
Example 2
(1) Putting the three-dimensional foamed nickel into 1mol/L dilute hydrochloric acid aqueous solution, and performing ultrasonic treatment for 20min to remove oxides on the surface; taking out, washing with deionized water, soaking in anhydrous ethanol for about 20min to remove oil, and ultrasonic treating in deionized water for about 10 min.
(2) Deionized water is used as a solvent to prepare a mixed solution of copper nitrate and sodium molybdate, wherein the concentration of the copper nitrate is 0.02mol/L, and the concentration of the sodium molybdate is 0.01 mol/L. And (3) adjusting the pH value of the mixed solution to 3-4 by using 1mol/L dilute hydrochloric acid aqueous solution to obtain a clear and transparent mixed solution. And (3) placing the cleaned foam nickel into an autoclave filled with an acidic mixed solution, and heating to 160 ℃ for hydrothermal reaction for 6 hours. And taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water, and drying to obtain the copper-molybdenum bimetal oxide precursor.
(3) In the hydrogen atmosphere, heating the copper-molybdenum bimetal oxide precursor from room temperature to 450 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h to obtain Cu/Cu2O/MoO2An electrocatalytic material.
Comparative example 1
Putting the three-dimensional foamed nickel into absolute ethyl alcohol, performing ultrasonic treatment for 30min, taking out the three-dimensional foamed nickel, putting the three-dimensional foamed nickel into a high-pressure kettle filled with 1mol/L dilute hydrochloric acid aqueous solution, heating the three-dimensional foamed nickel to 100 ℃, performing hydrothermal reaction for 6h, taking out the foamed nickel after the reaction is finished, and washing the foamed nickel with deionized water for later use.
Comparative example 2
(1) Putting the three-dimensional foamed nickel into absolute ethyl alcohol, performing ultrasonic treatment for 30min, taking out the three-dimensional foamed nickel, putting the three-dimensional foamed nickel into a high-pressure kettle filled with 1mol/L dilute hydrochloric acid aqueous solution, heating the three-dimensional foamed nickel to 100 ℃, performing hydrothermal reaction for 6h, taking out the foamed nickel after the reaction is finished, and washing the foamed nickel with deionized water for later use.
(2) Deionized water is used as a solvent to prepare a mixed solution of copper nitrate and sodium molybdate, wherein the concentration of the copper nitrate is 0.02mol/L, and the concentration of the sodium molybdate is 0.01 mol/L. And (3) adjusting the pH value of the mixed solution to 3 by using 1mol/L dilute hydrochloric acid aqueous solution, putting the cleaned foam nickel into an autoclave filled with the mixed solution, and heating to 180 ℃ for hydrothermal reaction for 6 hours. And taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water, and drying to obtain the copper-molybdenum bimetal oxide precursor.
To fully understand the Cu/Cu obtained in example 12O/MoO2The performance of the electrocatalytic material, which was subjected to XRD and SEM tests, is shown in fig. 1-2. As can be seen from fig. 1, the characteristic peaks of the nickel foam at 44.5 °, 51.8 ° and 76.4 ° of 2 θ, the characteristic peaks of the metal copper at 43.3 °, 50.4 ° and 74.1 ° of 2 θ, the characteristic peaks of the molybdenum dioxide at 26.3 ° and 37 ° of 2 θ, and the characteristic peak of the cuprous oxide at 36.4 ° of 2 θ. FIG. 2 shows Cu/Cu2O/MoO2The SEM photograph of the electrocatalytic material shows that molybdenum dioxide and cuprous oxide are deposited on the surface of the nickel foam in a lamellar structure with non-uniform size.
Cu/Cu from example 1, respectively, using a three-electrode system2O/MoO2The electrocatalytic material, the nickel foam pretreated in the comparative example 1 and the copper-molybdenum bimetallic oxide precursor prepared in the comparative example 2 are used as working electrodes, the saturated calomel electrode is used as a reference electrode, the graphite rod is used as a counter electrode, and the electrolytic hydrogen evolution performance test is carried out in a potassium hydroxide aqueous solution (electrolyte solution) of 1.0mol/L at the temperature of 25 +/-0.3 ℃. Before testing, N was bubbled into KOH solution2Saturation was achieved and the scan rate at the electrochemical workstation (Shanghai Chenghua instruments Co., Ltd., CHI760E) was 2mV/s and the scan voltage ranged from-0.9V to-1.5V (relative to a saturated calomel electrode) as measured, the results are shown in FIG. 3.
FIG. 3(a) is a graph in which curve 1 shows Cu/Cu2O/MoO2The polarization curve of (2) shows that, in the absence of resistance compensation, the hydrogen evolution current density reached-10 mA cm-2The overpotential is only 52 mV; curve 1 in FIG. 3(b) is Cu/Cu2O/MoO2The corresponding Tafel slope has a specific value of 40mV dec-1. FIG. 3(a) Curve 3, which is a polarization curve of the pretreated nickel foam of comparative example 1, shows that the hydrogen evolution current density reaches-10mA·cm-2The overpotential is 299 mV; FIG. 3(b) Curve 3 is a Tafel slope for the nickel foam of comparative example 1, having a specific value of 142mV dec-1. Curve 2 in FIG. 3(a) is a polarization curve of the precursor of comparative example 2, and it can be seen from the graph that the hydrogen evolution current density reached-10 mA cm-2The overpotential is 266 mV; FIG. 3(b), Curve 2, is the Tafel slope of the precursor of comparative example 2, with a specific value of 155mV dec-1. These data all show that the Cu/Cu produced in example 12O/MoO2The hydrogen evolution electrocatalyst has excellent electrocatalytic hydrogen evolution performance in alkaline solution, and can be used for a faster dynamic electrolysis water hydrogen evolution process.
Cu/Cu from example 1 recorded during the electrolytic Hydrogen evolution Performance test2O/MoO2Constant current density timer (condition: -10 mA/cm)2Electrolysis was continued for 24h) at constant current the potential profile is shown in figure 4. As can be seen from the figure, the overpotential is not obviously attenuated in the long-time electrocatalytic hydrogen evolution process under the specific current density, which shows that the Cu/Cu provided by the invention2O/MoO2The catalytic material has good stability of electrocatalytic hydrogen evolution.
Claims (7)
1. The preparation method of the copper/cuprous oxide/molybdenum dioxide electro-catalytic material is characterized by comprising the following steps of: (a) pretreating the three-dimensional foam metal for later use; (b) adding copper salt and molybdenum salt into water, stirring and dissolving, adjusting the pH value to be acidic by utilizing an acid solution to obtain a mixed solution, and adding treated three-dimensional foam metal to perform hydrothermal reaction to obtain a copper-molybdenum bimetallic oxide precursor; (c) placing the copper-molybdenum bimetal oxide precursor in a reducing atmosphere for reduction, wherein the reducing atmosphere is hydrogen, the reducing reaction temperature is 200-600 ℃, and the reducing reaction time is within 6 h; the three-dimensional foam metal is specifically foam nickel.
2. The method of claim 1, wherein: the pretreatment in the step (a) comprises soaking and cleaning the three-dimensional foam metal by using at least one of deionized water, an acid solution and an alcohol solvent, wherein the soaking and cleaning temperature is not more than 200 ℃, and ultrasonic treatment is also applied while soaking and cleaning.
3. The method of claim 1, wherein: the acid solution is specifically dilute hydrochloric acid water solution, and the pH value of the mixed solution is adjusted to 2-5.
4. The method of claim 1, wherein: the copper salt is selected from one of copper nitrate, copper chloride, copper sulfate and copper acetate, the molybdenum salt is selected from one of sodium molybdate and ammonium molybdate, and the molar ratio of the copper salt to the molybdenum salt is 0.25-4: 1.
5. The method of claim 1, wherein: the hydrothermal reaction temperature of the step (b) is 100-.
6. A copper/cuprous oxide/molybdenum dioxide electrocatalytic material characterized by being prepared according to any of the methods of claims 1-5.
7. Use of the copper/cuprous oxide/molybdenum dioxide electrocatalytic material of claim 6, in the electrolysis of water in alkaline solution for catalytic hydrogen evolution.
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| CN111659427B (en) * | 2020-06-09 | 2021-03-23 | 江西理工大学 | High-efficiency electrolytic water hydrogen evolution catalyst MoO2-CeF3/NF and preparation method thereof |
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