CN110180552A - Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application - Google Patents
Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application Download PDFInfo
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- CN110180552A CN110180552A CN201910575475.6A CN201910575475A CN110180552A CN 110180552 A CN110180552 A CN 110180552A CN 201910575475 A CN201910575475 A CN 201910575475A CN 110180552 A CN110180552 A CN 110180552A
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- copper
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- molybdenum
- hydrogen
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000010949 copper Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 12
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 15
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 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
- 150000002751 molybdenum Chemical class 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001476 alcoholic effect Effects 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
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 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
- 230000004044 response Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229910000906 Bronze Inorganic materials 0.000 claims 1
- 239000010974 bronze Substances 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012962 cracking technique Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 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
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal molybdate Chemical class 0.000 description 1
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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Application the present invention relates to a kind of copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof and in terms of electrolysis water liberation of hydrogen.Nickel foam is started the cleaning processing first, then places it in hydro-thermal reaction in the acid solution of cupric and molybdenum, finally places it in the reduction of reducing atmosphere high temperature.The material improves its catalytic hydrogen evolution effect and durability under alkaline condition by the synergistic effect that metal hydroxyl and metal bonding generate, and wherein hydroxyl promotes the dissociation of water, and neighbouring metallic atom promotes hydrogen intermediate to H2The absorption and combination of molecule.
Description
Technical field
The present invention relates to composite functional material technical fields, and in particular to a kind of copper/cuprous oxide/molybdenum dioxide electro-catalysis
Material and preparation method thereof and the application in terms of electrolysis water catalytic hydrogen evolution.
Background technique
Hydrogen is a kind of cleaning, flexible energy carrier, is expected to play crucial make in following sustainable energy system
A kind of approach of sustainable development is provided with, electro-chemical water cracking technique hydrogen producing of making a living.The technology can be by electric energy from can
The renewable sources of energy are converted into chemical energy, are a kind of very promising hydrogen transformation technologies, this for it is effective and it is extensive utilize renewable energy
Source has far reaching significance.The characteristics of renewable energy is that its output is changeable and intermittent, realizes that dynamical water-splitting key exists
In developing the high activity for evolving hydrogen reaction, durable elctro-catalyst.
Alkaline water cracking technique provides strong support with cost-benefit hydrogen to commercially produce.Reach
Higher reaction rate needs insignificant overpotential.Platinum (Pt) is the baseline catalyst of generally acknowledged electrolysis water catalytic hydrogen evolution, so
And due to the scarcity and Gao Chengben of platinum, be severely limited its heavy industrialization application.Therefore, it further explores and opens
Electrolysis water catalytic hydrogen evolution catalyst under hair alkaline condition efficiently, inexpensive is of great significance.
Before this, inventor team and other researchers have been disclosed many metal foam based composites and
Its application in terms of electrolysis water catalytic hydrogen evolution.In CN108950585A, foam copper is not intended as carrier supported material,
Later period participates in a part of active material that reaction is transformed into catalyst, and the sulfidic material generated is crisp, lacks toughness.
Electrochemical material preparation method disclosed in CN108754532A is complex, and LDH of generation itself has relatively weak electronics
Conductibility, although the processing of later period carbon coating improves electron conduction, the structure that high temperature cabonization processing may destroy LDH is covered
Lid script active site.Composite material disclosed in CN106702425A only has excellent catalytic activity in an acidic solution, this
Its outer preparation process is complicated, and electrolysis water reaction needs hydrone to come into full contact with catalyst.Moreover, the program is in shape
At molybdenum disulfide electroplating surface layers of copper can cover a part of active site, reduce the catalytic efficiency of material.CN109468662A
Disclosed catalyst be powder or graininess, need to be supported on by adhesive on glass-carbon electrode carry out electro-chemical test and
Reaction, active material may fall off under high current density state, influence its catalytic performance.
In conclusion there are some problems in performance, preparation method, use process in existing similar electrocatalysis material.
Summary of the invention
It is an object of the invention to solve the above problem existing for existing electrolysis water catalytic hydrogen evolution catalysis material, pass through hydro-thermal
A kind of non-precious Cu-Mo-O type electrocatalysis material has been made in the reaction of method combination high temperature reduction.The material is electrolysed in alkaline solution
High activity and excellent stability are shown when water catalytic hydrogen evolution, with good application prospect.To achieve the above object,
The technical solution adopted in the present invention is specific as follows:
Copper/cuprous oxide/molybdenum dioxide electrocatalysis material preparation method, specifically includes the following steps: (a) steeps three-dimensional
Foam metal is pre-processed, spare；(b) prepare mixed solution using mantoquita, molybdenum salt, be added the three-dimensional foam metal handled well into
Row hydro-thermal reaction obtains copper-molybdenum bimetallic oxide presoma；(c) copper-molybdenum bimetallic oxide presoma is placed in reducing atmosphere
Middle reduction.
Further, the three-dimensional foam metal is specially nickel foam, and porosity is 90% or more, purity be 98% with
On.
Further, step (a) pretreatment is including the use of at least one of deionized water, acid solution, alcoholic solvent
Soaking and washing is carried out to three-dimensional foam metal, soaking and washing temperature is no more than 200 DEG C, and it is clear to enhance during which to apply ultrasonic treatment
Wash effect.
Further, the preparation method of mixed solution is as follows in step (b): mantoquita and molybdenum salt are added to the water, and it is molten to stir
Solution, adjusts its pH to 2-5 using diluted hydrochloric acid aqueous solution.
Further, the mantoquita is selected from one of copper nitrate, copper chloride, copper sulphate, copper acetate, preferably copper nitrate；
The molybdenum salt is selected from one of sodium molybdate, ammonium molybdate, preferably sodium molybdate.The molar ratio of mantoquita and molybdenum salt is 0.25-4:1.
Further, 100-200 DEG C of step (b) hydrothermal temperature, the hydro-thermal reaction time be for 24 hours within.
Further, reducing atmosphere is hydrogen in step (c), and reduction reaction temperature is 200-600 DEG C, the reduction reaction time
Within 6h.
Another object of the present invention is to provide a kind of copper/cuprous oxide obtained according to the method described above/molybdenum dioxide electricity
Catalysis material, the material can be used for the electrolysis water catalytic hydrogen evolution in alkaline solution.
The catalytic activity of most of electrolysis water catalytic hydrogen evolution catalyst under alkaline condition is generally significantly lower than acid condition
Under, this phenomenon may be related with the response path difference of electrolysis water liberation of hydrogen in alkalinity or acid solution.More precisely, it is electrolysed
Water evolving hydrogen reaction shows slow dynamic characteristic in alkaline solution, it may be possible to due to H intermediary from water rather than from
Hydrogen ion (H3O+) in release caused by.This problem can be generated by the combination of metal hydroxyl and metallic atom and be cooperateed with
Catalyst solves, and wherein metal hydroxyl promotes the dissociation of water, and neighbouring metallic atom promotes hydrogen intermediate to H2Point
The absorption and combination of son.
Molybdenum base material has been to be concerned by more and more people as the potentiality of electrolysis water catalytic hydrogen evolution elctro-catalyst.To being at present
Only, a large amount of to make great efforts to have been devoted to reduce energy barrier (Δ G (H2O water separating step)).Research report doping hetero atom
Valence state with adjustment molybdenum is the available strategy for accelerating alkalinity HER kinetics, especially transition metal molybdate (MMoO4) and
Its hydrate is the ideal presoma for preparing active rare earth electrocatalyst, this is because molybdenum base material activity protrusion and molybdenum and miscellaneous original
Electronic structure between sub (M) is adjustable.Research also found, in 1.0M KOH solution, the lower Mo of valence state is contained in oxide
(the Mo on surface5+And Mo4+) be remarkably reinforced than the bimetallic oxide predecessor activity containing valence state for+6 Mo.
Copper/cuprous oxide/molybdenum dioxide (Cu/Cu provided by the invention2O/MoO2) electrocatalytic hydrogen evolution catalyst is with net
The three-dimensional porous foams nickel of shape structure is carrier, on the one hand increases the contact surface area of catalyst and water, mentions for electronics transfer
Better channels are supplied；On the other hand the electric conductivity for improving hybrid catalyst, enhances the dispersibility of electroactive phase, makes it have
More active sites.In the Cu/Cu of nickel foam surface in situ growth2O/MoO2Two-dimentional active nano piece has open-framework, with
Three-dimensional conductive substrate has close contact.Since at metal/oxide interface, there are the collaborations such as strong interaction, electron transmission
Effect makes the material show superior activity in terms of hydrogen evolution；Oxide carrier at metal/oxide interface by above mentioning
For double activated site, the strong physics and chemical property for influencing metal nanoparticle, to play crucial make in catalytic process
With finally improving the catalytic activity, selectivity and durability of the catalysis material.What experiment showed to prepare by thermal reduction method
Lower valency copper-molybdenum bimetallic oxide, shows better catalytic activity and stability under alkaline condition.In addition to this, this hair
It is bright that also there are the beneficial effects such as raw material is cheap and easy to get, preparation process is simple, cost is relatively low.
Detailed description of the invention
Fig. 1 is Cu/Cu made from the embodiment of the present invention 12O/MoO2XRD diagram；
Fig. 2 is Cu/Cu made from the embodiment of the present invention 12O/MoO2SEM figure；
Fig. 3 is Cu/Cu made from the embodiment of the present invention 12O/MoO2, 1 nickel foam of comparative example, 2 copper-molybdenum bimetallic oxygen of comparative example
The working electrode polarization curve and Tafel comparison diagram of compound presoma；
Fig. 4 is Cu/Cu made from the embodiment of the present invention 12O/MoO2Time-measuring electric potential in aqueous slkali under constant current density is bent
Line chart.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Embodiment 1
(1) three-dimensional foam nickel is put into ultrasound 30min in dehydrated alcohol, to remove the greasy dirt on surface.It is put into after taking-up
In autoclave equipped with 1mol/L diluted hydrochloric acid aqueous solution, 100 DEG C of hydro-thermal reaction 6h are heated to, to remove the oxide on surface.
To take out nickel foam after reaction, it is washed with deionized water spare.
(2) using deionized water as solvent, the mixed solution of copper nitrate, sodium molybdate is prepared, wherein the concentration of copper nitrate is
0.02mol/L, the concentration of sodium molybdate are 0.01mol/L.The pH to 3- of mixed solution is adjusted with the diluted hydrochloric acid aqueous solution of 1mol/L
4, obtain the mixed solution of clear.Cleaned nickel foam is placed in the autoclave equipped with acidic mixed solution, is heated
To 180 DEG C of hydro-thermal reaction 6h.Nickel foam is taken out after reaction, it is dry after being washed with deionized water, obtain copper-molybdenum bimetallic oxygen
Compound presoma.
(3) in hydrogen atmosphere, copper-molybdenum bimetallic oxide presoma is risen to the heating rate of 5 DEG C/min from room temperature
450 DEG C, 2h is kept at this temperature, obtains Cu/Cu2O/MoO2Electrocatalysis material.
Embodiment 2
(1) three-dimensional foam nickel is put into ultrasound 20min in 1mol/L diluted hydrochloric acid aqueous solution to remove the oxide on surface；
Be washed with deionized water after taking-up, be subsequently placed into dehydrated alcohol and impregnate 20min or so so as to degreasing degreasing, be finally putting into from
Ultrasound 10min or so in sub- water.
(2) using deionized water as solvent, the mixed solution of copper nitrate, sodium molybdate is prepared, wherein the concentration of copper nitrate is
0.02mol/L, the concentration of sodium molybdate are 0.01mol/L.The pH to 3- of mixed solution is adjusted with the diluted hydrochloric acid aqueous solution of 1mol/L
4, obtain the mixed solution of clear.Cleaned nickel foam is placed in the autoclave equipped with acidic mixed solution, is heated
To 160 DEG C of hydro-thermal reaction 6h.Nickel foam is taken out after reaction, it is dry after being washed with deionized water, obtain copper-molybdenum bimetallic oxygen
Compound presoma.
(3) in hydrogen atmosphere, copper-molybdenum bimetallic oxide presoma is risen to the heating rate of 5 DEG C/min from room temperature
450 DEG C, 2h is kept at this temperature, obtains Cu/Cu2O/MoO2Electrocatalysis material.
Comparative example 1
Three-dimensional foam nickel is put into ultrasound 30min in dehydrated alcohol, is put into after taking-up equipped with 1mol/L diluted hydrochloric acid aqueous solution
Autoclave in, be heated to 100 DEG C of hydro-thermal reaction 6h, to take out nickel foam after reaction, be washed with deionized water spare.
Comparative example 2
(1) three-dimensional foam nickel is put into ultrasound 30min in dehydrated alcohol, is put into after taking-up water-soluble equipped with 1mol/L dilute hydrochloric acid
In the autoclave of liquid, 100 DEG C of hydro-thermal reaction 6h are heated to, to take out nickel foam after reaction, are washed with deionized water spare.
(2) using deionized water as solvent, the mixed solution of copper nitrate, sodium molybdate is prepared, wherein the concentration of copper nitrate is
0.02mol/L, the concentration of sodium molybdate are 0.01mol/L.The pH to 3 of mixed solution is adjusted with the diluted hydrochloric acid aqueous solution of 1mol/L,
Cleaned nickel foam is placed in the autoclave equipped with mixed solution, 180 DEG C of hydro-thermal reaction 6h are heated to.It takes after reaction
Nickel foam out, it is dry after being washed with deionized water, obtain copper-molybdenum bimetallic oxide presoma.
To fully understand Cu/Cu made from embodiment 12O/MoO2The performance of electrocatalysis material has carried out XRD and SEM to it
Test, as a result as shown in Figs. 1-2.The characteristic peak of 2 θ to be at 44.5 °, 51.8 °, 76.4 ° be nickel foam as shown in Figure 1,2 θ are
It is the characteristic peak of metallic copper at 43.3 °, 50.4 °, 74.1 °, it is the characteristic peak of molybdenum dioxide that 2 θ, which are at 26.3 °, 37 °, and 2 θ are
It is the characteristic peak of cuprous oxide at 36.4 °.Fig. 2 is Cu/Cu2O/MoO2The SEM photograph of electrocatalysis material, as can be seen from Figure
Molybdenum dioxide and cuprous oxide are deposited in foam nickel surface with the inhomogenous lamellar structure of size.
Using three-electrode system, respectively with Cu/Cu made from embodiment 12O/MoO2Electrocatalysis material, comparative example 1 pre-process
Later copper-molybdenum bimetallic oxide presoma made from nickel foam, comparative example 2 is working electrode, and saturated calomel electrode is reference
Electrode, graphite rod are to carry out in 25 ± 0.3 DEG C of potassium hydroxide aqueous solutions (electrolyte solution) in 1.0mol/L to electrode
It is electrolysed Hydrogen Evolution Performance test.Before test, N is passed through into KOH solution2Reach saturation, electrochemical workstation when test
The sweep speed of (Shanghai Chen Hua Instrument Ltd., CHI760E) is 2mV/s, and scanning voltage range is -0.9V extremely -1.5V (phase
For saturated calomel electrode), as a result as shown in Figure 3.
Fig. 3 (a) curve 1 is Cu/Cu2O/MoO2Polarization curve, as seen from the figure in the case where no resnstance transformer, when
Liberation of hydrogen current density reaches -10mAcm-2When overpotential be only 52mV；Curve 1 is Cu/Cu in Fig. 3 (b)2O/MoO2It is corresponding
Tafel slope, specific value 40mVdec-1.Fig. 3 (a) curve 3 is in comparative example 1 by the pole of pretreatment nickel foam
Change curve, as seen from the figure when liberation of hydrogen current density reaches -10mAcm-2When overpotential be 299mV；Fig. 3 (b) curve 3 is comparison
The Tafel slope of 1 nickel foam of example, specific value 142mVdec-1.Curve 2 is 2 presoma of comparative example in Fig. 3 (a)
Polarization curve, as seen from the figure when liberation of hydrogen current density reaches -10mAcm-2When overpotential be 266mV；Fig. 3 (b) curve 2 is pair
The Tafel slope of 2 presoma of ratio, specific value 155mVdec-1.These data show made from embodiment 1
Cu/Cu2O/MoO2Electrocatalytic Activity for Hydrogen Evolution Reaction agent has excellent electrocatalytic hydrogen evolution performance, faster dynamics electrolysis in alkaline solution
Elutriation hydrogen process.
Cu/Cu made from the embodiment 1 recorded in electrolysis Hydrogen Evolution Performance test process2O/MoO2Constant current density timing (item
Part: -10mA/cm2Continued electrolysis is for 24 hours under constant current) potential curve figure is as shown in Figure 4.It can be seen from the figure that in specific electricity
Under current density during long-time electrocatalytic hydrogen evolution, overpotential does not have obvious decaying, illustrates Cu/Cu provided by the invention2O/MoO2
Catalysis material has good electrocatalytic hydrogen evolution stability.
Claims (10)
1. bronze medal/cuprous oxide/molybdenum dioxide electrocatalysis material preparation method, it is characterised in that the following steps are included: (a) is to three
Dimension foam metal is pre-processed, spare；(b) mixed solution is prepared using mantoquita, molybdenum salt, the three-dimensional foam gold handled well is added
Belong to and carry out hydro-thermal reaction, obtains copper-molybdenum bimetallic oxide presoma；(c) copper-molybdenum bimetallic oxide presoma is placed in reduction
It is restored in atmosphere.
2. preparation method as described in claim 1, it is characterised in that: step (a) it is described pretreatment including the use of deionized water,
At least one of acid solution, alcoholic solvent carry out soaking and washing to three-dimensional foam metal, and soaking and washing temperature is no more than 200 DEG C,
Ultrasonic treatment is also applied with while soaking and washing.
3. preparation method as described in claim 1, it is characterised in that: the three-dimensional foam metal is specially nickel foam.
4. preparation method as described in claim 1, it is characterised in that the preparation method of mixed solution in step (b) specifically:
Mantoquita and molybdenum salt are added to the water stirring and dissolving, adjust its pH using acid solution as acidity.
5. preparation method as claimed in claim 2 or 4, it is characterised in that: the acid solution is specially diluted hydrochloric acid aqueous solution, is mixed
The pH for closing solution is adjusted to 2-5.
6. preparation method as described in claim 1, it is characterised in that: the mantoquita be selected from copper nitrate, copper chloride, copper sulphate,
One of copper acetate, the molybdenum salt are selected from one of sodium molybdate, ammonium molybdate, and the molar ratio of mantoquita and molybdenum salt is 0.25-4:
1。
7. preparation method as described in claim 1, it is characterised in that: step (b) hydrothermal temperature is 100-200 DEG C, water
The thermal response time be for 24 hours within.
8. preparation method as described in claim 1, it is characterised in that: reducing atmosphere is hydrogen, reduction reaction temperature in step (c)
Degree is 200-600 DEG C, and the reduction reaction time is within 6h.
9. a kind of copper/cuprous oxide/molybdenum dioxide electrocatalysis material, it is characterised in that the material is according to described in claim 1-8
Any method is prepared.
10. copper/cuprous oxide/molybdenum dioxide electrocatalysis material described in claim 9 is for electrolysis water catalysis analysis in alkaline solution
The application of hydrogen.
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