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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
copper
preparation
molybdenum
hydrogen
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910575475.6A
Other languages
Chinese (zh)
Other versions
CN110180552B (en
Inventor
喻发全
童晶
薛亚楠
王建芝
谌伟民
蔡宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN201910575475.6A priority Critical patent/CN110180552B/en
Publication of CN110180552A publication Critical patent/CN110180552A/en
Application granted granted Critical
Publication of CN110180552B publication Critical patent/CN110180552B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/84Catalysts 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
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/885Molybdenum and copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33Electric or magnetic properties
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen 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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (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

Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application
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.
CN201910575475.6A 2019-06-28 2019-06-28 Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof Active CN110180552B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910575475.6A CN110180552B (en) 2019-06-28 2019-06-28 Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910575475.6A CN110180552B (en) 2019-06-28 2019-06-28 Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110180552A true CN110180552A (en) 2019-08-30
CN110180552B CN110180552B (en) 2022-05-10

Family

ID=67724176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910575475.6A Active CN110180552B (en) 2019-06-28 2019-06-28 Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110180552B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586135A (en) * 2019-09-24 2019-12-20 河南师范大学 Containing Mn0.5Cd0.5S and Cu2Preparation method of O-supported photocatalyst
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
CN114231955A (en) * 2021-12-24 2022-03-25 燕山大学 Modified foam copper and preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474258A (en) * 2013-09-16 2013-12-25 哈尔滨工程大学 Method for preparing super capacitor electrode material with foamed nickel loaded with Cu and Cu2O
CN105957730A (en) * 2016-05-25 2016-09-21 东南大学 Preparation and application of copper oxide-cuprous oxide-copper ternary composite electrode material
CN106861708A (en) * 2017-03-10 2017-06-20 江西师范大学 It is a kind of to produce non-precious metal catalyst of hydrogen and preparation method thereof completely for hydrazine borine
US20170349447A1 (en) * 2016-05-23 2017-12-07 University Of Connecticut Mesoporous metal oxides, preparation and applications thereof
CN108754532A (en) * 2018-05-29 2018-11-06 武汉工程大学 A kind of iron of molybdenum doping/nickel layer shape array@nickel foam based combined electrode materials and the preparation method and application thereof
CN108796535A (en) * 2018-05-29 2018-11-13 武汉工程大学 One kind having three metallic coppers-cobalt-molybdenum/nickel foam porous electrode material and the preparation method and application thereof
WO2019018709A1 (en) * 2017-07-21 2019-01-24 Temple University-Of The Commonwealth System Of Higher Education Novel multi-metal catalysts and devices and methods of use thereof
CN109468662A (en) * 2018-12-11 2019-03-15 温州大学 The preparation method of copper-molybdenum composite material and its application in electrolysis water liberation of hydrogen catalyst

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474258A (en) * 2013-09-16 2013-12-25 哈尔滨工程大学 Method for preparing super capacitor electrode material with foamed nickel loaded with Cu and Cu2O
US20170349447A1 (en) * 2016-05-23 2017-12-07 University Of Connecticut Mesoporous metal oxides, preparation and applications thereof
CN105957730A (en) * 2016-05-25 2016-09-21 东南大学 Preparation and application of copper oxide-cuprous oxide-copper ternary composite electrode material
CN106861708A (en) * 2017-03-10 2017-06-20 江西师范大学 It is a kind of to produce non-precious metal catalyst of hydrogen and preparation method thereof completely for hydrazine borine
WO2019018709A1 (en) * 2017-07-21 2019-01-24 Temple University-Of The Commonwealth System Of Higher Education Novel multi-metal catalysts and devices and methods of use thereof
CN108754532A (en) * 2018-05-29 2018-11-06 武汉工程大学 A kind of iron of molybdenum doping/nickel layer shape array@nickel foam based combined electrode materials and the preparation method and application thereof
CN108796535A (en) * 2018-05-29 2018-11-13 武汉工程大学 One kind having three metallic coppers-cobalt-molybdenum/nickel foam porous electrode material and the preparation method and application thereof
CN109468662A (en) * 2018-12-11 2019-03-15 温州大学 The preparation method of copper-molybdenum composite material and its application in electrolysis water liberation of hydrogen catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MIN KUANG ET AL.: ""CuCo Hybrid Oxides as Bifunctional Electrocatalyst for Efficient Water Splitting"", 《ADVANCED FUNCTIONAL MATERIALS》 *
周鲁萍等: ""电催化氢气析出Mo基催化剂研究进展"", 《新型工业化》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586135A (en) * 2019-09-24 2019-12-20 河南师范大学 Containing Mn0.5Cd0.5S and Cu2Preparation method of O-supported photocatalyst
CN110586135B (en) * 2019-09-24 2022-04-26 河南师范大学 Containing Mn0.5Cd0.5S and Cu2Preparation method of O-supported photocatalyst
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
CN114231955A (en) * 2021-12-24 2022-03-25 燕山大学 Modified foam copper and preparation method and application thereof
CN114231955B (en) * 2021-12-24 2022-08-30 燕山大学 Modified foam copper and preparation method and application thereof

Also Published As

Publication number Publication date
CN110180552B (en) 2022-05-10

Similar Documents

Publication Publication Date Title
CN109055972B (en) Mn doped Ni3S2Nano-array hydrogen evolution catalyst and preparation method and application thereof
CN113481529B (en) Iron and cobalt modified nickel phosphide nanosheet array and preparation method thereof
CN110180552A (en) Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application
CN110694665B (en) Preparation method and application of manganese and nitrogen doped octa-sulfur-nonacobalt electrocatalyst
CN109225270A (en) A kind of Ni3S2@NiV-LDH heterojunction structure bifunctional electrocatalyst, Preparation method and use
CN110699702B (en) Hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst and preparation method and application thereof
CN111871421A (en) Nickel-iron-molybdenum hydrotalcite nanowire bifunctional electrocatalyst and preparation method thereof
CN109277110B (en) Irregular spherical V-doped Ni3S2/NF oxygen evolution electric catalyst and preparation method thereof
CN110468427A (en) A kind of self-supporting doping metals hydroxide nano plate electrode material, preparation method and the usage
CN108671923A (en) Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water
CN109371419B (en) V-doped Ni with self-assembled short rods into dendritic shape3S2/NF electrode material and preparation method thereof
CN108950585A (en) A kind of MoS2@Cu2S@foam copper composite nano materials and its preparation method and application
CN111701607A (en) MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof
CN112575348B (en) NF-NiFeOx(OH)y-S electrode, its preparation and application as OER catalytic material
CN113279005A (en) Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution
CN114438545A (en) Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst
CN113957456A (en) Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof
CN111054412B (en) Synergistic modified composite electrocatalyst and application thereof in ethanol oxidation
CN109731580A (en) A kind of W18O49The preparation method of/NF self-supporting electrocatalysis material
CN116219484A (en) Efficient bimetallic nitride/hydroxide heterostructure electrocatalyst, preparation method and application
CN112403503B (en) Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material
CN109136979A (en) The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation
CN114318410A (en) Cobalt-based water electrolysis catalyst, preparation method thereof and application thereof in water electrolysis
CN113897635A (en) MOFs-derived nickel-cobalt double hydroxide array electrocatalytic oxygen evolution material and preparation method thereof
CN113684493A (en) Method for preparing efficient electrolytic water hydrogen evolution catalyst by chemical plating method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant