CN111558387A - Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution - Google Patents
Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution Download PDFInfo
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- molybdenum carbide
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 415
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 211
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 208
- 239000002131 composite material Substances 0.000 title claims abstract description 127
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 71
- 239000001301 oxygen Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000006260 foam Substances 0.000 claims description 100
- 239000000463 material Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 14
- -1 molybdenum salt Chemical class 0.000 claims description 14
- 150000002751 molybdenum Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 10
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 239000002526 disodium citrate Substances 0.000 claims description 2
- 235000019262 disodium citrate Nutrition 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000011056 performance test Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 229910003178 Mo2C Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
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- 238000001179 sorption measurement Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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Abstract
The invention discloses a molybdenum carbide/foamed nickel composite material, a preparation method thereof and application thereof in electrocatalysis oxygen evolution. The preparation method comprises the steps of preparing a molybdenum carbide precursor solution, covering a molybdenum carbide precursor on the foamed nickel, and calcining the molybdenum carbide precursor to prepare the molybdenum carbide/foamed nickel composite material. The molybdenum carbide/foamed nickel composite material has the advantages of large specific surface area, stable structure, good electrocatalytic performance and the like, is a novel electrocatalyst which has good oxygen evolution effect and stable performance, can be widely used for electrocatalytic oxygen evolution, can be directly used as an electrode material for electrocatalytic oxygen evolution reaction, and has high use value and good application prospect. The preparation method of the molybdenum carbide/foamed nickel composite material has the advantages of controllable preparation process, simple preparation process, low preparation cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of electrocatalytic oxygen evolution materials, and relates to a molybdenum carbide/foamed nickel composite material, a preparation method thereof and application thereof in electrocatalytic oxygen evolution.
Background
The water splitting reaction provides a promising approach for the development of renewable energy sources, mainly in the form of hydrogen fuels. The bottleneck of the water splitting reaction is the oxidation half-reaction, i.e. the Oxygen Evolution Reaction (OER), which involves the participation of four consecutive electron and proton transfer steps and has a very high thermodynamic potential and a slow kinetic coefficient. Currently, Ru-/Ir-based oxides are widely regarded as the most effective catalysts for oxygen evolution reactions due to their excellent long-term catalytic activity, however, their wide commercial application is greatly hindered due to their scarcity and high cost. Thus, there is a need for efficient, low cost electrocatalysts that can simultaneously reduce overpotentials, accelerate reaction rates, and drive multi-electron and multi-proton oxidation reactions in oxygen evolution reactions.
Currently, molybdenum carbide is mainly used for Hydrogen Evolution Reaction (HER) or Oxygen Reduction Reaction (ORR) as an electrocatalyst, and the development of oxygen evolution electrocatalysts based on molybdenum carbide remains a challenging issue, mainly due to the d-band of MoThe electronic structure is similar to that of noble metal Pt, and Pt is known as the most ideal hydrogen evolution reaction electrocatalyst, and when the catalyst is used for oxygen evolution reaction, the surface of the material inevitably suffers from oxygen evolution corrosion, so that the oxygen evolution performance is reduced, therefore, the key point for realizing the high-efficiency oxygen evolution activity of the molybdenum carbide-based electrocatalyst is to solve the problem of the stability of the material in an electrolyte solution. In addition, the following problems also exist in the preparation of the molybdenum carbide-based catalyst (particularly nanocrystalline phase): molybdenum carbide nanocrystals polymerize and/or grow disproportionately at higher reaction temperatures, and the molybdenum carbide surface is rapidly oxidized to molybdenum oxide (MoO) when exposed to airx) Species, the above problems, on the one hand, reduce the catalytic performance, on the other hand, complicate the study of the reaction mechanism, and are not favorable for the popularization and application of the molybdenum carbide-based catalyst. For the improvement strategy of the molybdenum carbide-based catalyst, such as metal or nonmetal doping, heterostructure formation and the like, although the improvement strategy can improve the oxygen evolution activity of the molybdenum carbide-based catalyst, the aggregation/corrosion of the molybdenum carbide-based material in the actual application process can cause the loss of the catalytic activity, and the problem is still not effectively solved; meanwhile, the adopted heterostructure strategy makes the preparation of the material more complicated on one hand and the oxygen evolution reaction mechanism of the material more complicated on the other hand; more seriously, the doping-introduced hetero atoms may cover active sites on the molybdenum carbide, and the doping elements may be oxidized or overflow from the material in the catalytic reaction, so that the catalytic performance of the material is remarkably reduced. In addition, the conductivity of the electrode material is a key in the design of the electrocatalyst, and the conductivity of the pure molybdenum carbide is poor, so that the pure molybdenum carbide is often required to be coated on a conductive substrate, such as a silicon dioxide or glassy carbon electrode, but the conductive substrate materials are lack of chemical bond connection, so that the molybdenum carbide is easy to fall off during electrocatalysis, and the catalytic performance is reduced, namely the existing molybdenum carbide-based composite material has the problem of poor stability. Therefore, how to overcome the problems in the existing molybdenum carbide-based composite material is to obtain a preparation process with stable structure, good electrocatalytic performance, controllable preparation processThe molybdenum carbide-based electrocatalyst for oxygen evolution, which is simple and low in preparation cost, has important significance for improving the electrocatalytic oxygen evolution performance to expand the application range of new energy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a molybdenum carbide/foamed nickel composite material with stable structure and good electrocatalytic performance, and also provides a preparation method of the molybdenum carbide/foamed nickel composite material with controllable preparation process, simple preparation process and low preparation cost and application of the molybdenum carbide/foamed nickel composite material as an electrocatalyst in electrocatalytic oxygen evolution.
In order to solve the technical problems, the invention adopts the technical scheme that:
a molybdenum carbide/nickel foam composite comprising molybdenum carbide and nickel foam; the molybdenum carbide is loaded on the nickel foam.
In the molybdenum carbide/foamed nickel composite material, the mass ratio of molybdenum carbide to foamed nickel in the molybdenum carbide/foamed nickel composite material is further improved to be 0.5-2.0%.
In the molybdenum carbide/foamed nickel composite material, the molybdenum carbide is blocky; the average grain diameter of the molybdenum carbide is 0.5-3.0 μm.
As a general technical concept, the present invention also provides a preparation method of the above molybdenum carbide/nickel foam composite material, comprising the steps of:
(1) mixing foamed nickel with an aqueous solution of molybdenum salt/citrate, and performing ultrasonic dispersion to obtain a molybdenum carbide precursor solution;
(2) carrying out thermal impregnation on the molybdenum carbide precursor solution obtained in the step (1) to obtain a foamed nickel material with the surface covered with the molybdenum carbide precursor;
(3) and (3) calcining the foamed nickel material with the surface covered with the molybdenum carbide precursor obtained in the step (2) to obtain the molybdenum carbide/foamed nickel composite material.
In the preparation method, the molar ratio of the molybdenum salt to the citrate in the aqueous solution of the molybdenum salt/citrate is 1-6: 1; the mass of the molybdenum salt in the aqueous solution of the molybdenum salt/citrate is 10-80% of that of the foamed nickel; the molybdenum salt in the molybdenum salt/citrate aqueous solution is sodium molybdate or ammonium molybdate; the citrate in the molybdenum salt/citrate aqueous solution is disodium citrate or trisodium citrate.
In a further improvement of the above preparation method, in step (1), the foamed nickel further comprises the following treatment before use: putting the foamed nickel into acetone for ultrasonic treatment for 0.5 to 1 hour, and then putting the foamed nickel into a hydrochloric acid solution for ultrasonic treatment for 0.5 to 1 hour; the concentration of the hydrochloric acid solution is 0.5-3.0M; the ultrasonic dispersion time is 0.5-2 h;
in the step (2), the temperature of the hot dipping is 40-80 ℃; the hot dipping time is 5-10 h;
in the step (3), the calcination is carried out in an inert atmosphere; the inert atmosphere is N2Or Ar; the calcining temperature is 500-800 ℃; the calcining time is 0.5-2 h.
As a general technical concept, the invention also provides an application of the molybdenum carbide/foamed nickel composite material or the molybdenum carbide/foamed nickel composite material prepared by the preparation method in electrocatalytic oxygen evolution.
The application is further improved, and comprises the following steps: molybdenum carbide/foamed nickel composite material is used as a working electrode to construct a three-electrode system, and electrocatalytic reaction is carried out in an electrolyte solution to separate out oxygen.
In the above application, further improvement, the electrolyte solution is a neutral solution or an alkaline solution; the concentration of the electrolyte solution is 0.5M-1.0M.
In the above application, further improvement, the neutral solution is K2SO4Solutions or Na2SO4A solution; the alkaline solution is KOH solution or NaOH solution.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a molybdenum carbide/foamed nickel composite material, which comprises molybdenum carbide and foamed nickel; molybdenum carbide is supported on nickel foam. According to the invention, foam nickel is taken as a carrier, molybdenum carbide is loaded on the foam nickel, on one hand, the foam nickel is a three-dimensional porous metal network frame carrier material and is a perfect platform for the growth of molybdenum carbide, and the molybdenum carbide can stably and uniformly disperse and grow on the foam nickel by in-situ growth of the molybdenum carbide on the foam nickel, so that the close contact between the molybdenum carbide and the foam nickel is ensured, the shedding of a molybdenum carbide catalyst in a catalysis process is avoided, the specific surface area of a composite material is increased, catalytic active sites (Mo sites) are increased, and under the electric excitation, the Mo sites in the molybdenum carbide serve as an electron trap to enrich electrons on a Mo surface, thereby realizing the electron transfer from the molybdenum carbide to the foam nickel and improving the electro-catalytic oxygen evolution performance; on the other hand, the foamed nickel is a conductive material with good conductivity, can provide more electron transfer paths, can realize the efficient transfer of electrons between the molybdenum carbide and the foamed nickel in the electrocatalysis process, and can further improve the electrocatalysis oxygen evolution performance; in addition, the porous grid structure of the foamed nickel is free radicals such as OH and the like and O in the oxygen evolution process2The adsorption and the release provide a large number of favorable channels, so that the molybdenum carbide is loaded on the foamed nickel, the electrocatalytic activity of the material can be improved, the composite material has better electrocatalytic performance, and the addition of the foamed nickel can also effectively protect the molybdenum carbide nano structure from aggregation and corrosion, so that the composite material has better stability. The molybdenum carbide/foamed nickel composite material has the advantages of large specific surface area, stable structure, good electrocatalytic performance and the like, is a novel electrocatalyst which has good oxygen evolution effect and stable performance and can be widely used for electrocatalytic oxygen evolution, does not need to be transferred to other substrates when being used for electrocatalytic oxygen evolution, can be directly used as an electrode material for electrocatalytic oxygen evolution reaction, and has high use value and good application prospect.
(2) In the molybdenum carbide/foamed nickel composite material, the composite material has better stability and catalytic activity by optimizing the mass ratio of the molybdenum carbide to the foamed nickel to be 0.5-2.0%, because the molybdenum carbide loaded with less quantity cannot provide enough catalytic activity sites, effective catalytic activity is difficult to obtain, and the molybdenum carbide loaded with too much quantity can cause the molybdenum carbide to aggregate and grow on the surface of the foamed nickel, so that the tightness among the molybdenum carbide is increased, the transmission of free radicals such as OH and the like is hindered, and the catalytic activity is reduced.
(3) The invention also provides a preparation method of the molybdenum carbide/foamed nickel composite material, firstly, the foamed nickel and the aqueous solution of molybdenum salt/citrate are mixed, ultrasonically dispersed, the precursor solution is completely dissolved and dispersed, and is uniformly contacted with the foamed nickel to form the precursor solution, then the precursor solution is hot dipped, the water in the solution is removed, the molybdenum carbide precursor (molybdenum salt/citrate mixed solid) is covered on the surface of the foam nickel, the foam nickel material with the surface evenly covered with the molybdenum carbide precursor is formed, finally, the foam nickel material with the surface covered with the molybdenum carbide precursor is calcined, at this time, molybdenum salt and citrate react on the foamed nickel to generate molybdenum carbide solid in situ and the molybdenum carbide solid is loaded on the foamed nickel, thereby preparing the molybdenum carbide/foamed nickel composite material with stable and uniform dispersion growth of molybdenum carbide on the foamed nickel. The preparation method has the advantages of controllable preparation process, simple preparation process, low preparation cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) In the preparation method of the molybdenum carbide/foamed nickel composite material, the temperature (40-80 ℃) and the time (5-10 hours) of thermal soaking are optimized, so that a molybdenum carbide precursor (molybdenum salt/citrate mixed solid) can be ensured to be more dispersed and uniformly covered on the surface of foamed nickel, and the uniform dispersion growth of molybdenum carbide on the foamed nickel is more facilitated, because the thermal soaking temperature is too high, the rapid evaporation of water can cause the evaporation of the molybdenum salt or citrate along with the water, the subsequent preparation of molybdenum carbide is not facilitated, and the rapid evaporation of the water can cause the rapid concentration of a solution, the aggregation of the molybdenum salt or citrate on the foamed nickel and the subsequent uniform dispersion growth of molybdenum carbide on the foamed nickel are not facilitated; the preparation time of the material can be prolonged due to the excessively low hot dipping temperature, so that the preparation efficiency is low and the preparation period is long; meanwhile, by controlling the calcining temperature (500-800 ℃) and the calcining time (0.5-2 h) in the preparation process of the molybdenum carbide/foamed nickel, the uniform dispersion and the particle size of the molybdenum carbide on the foamed nickel can be ensured, and the preparation of the molybdenum carbide/foamed nickel composite material with stable structure and good electro-catalytic performance is facilitated.
(5) The invention also provides an application of the molybdenum carbide/foamed nickel composite material in electrocatalysis oxygen evolution, the molybdenum carbide/foamed nickel composite material is taken as a working electrode to construct a three-electrode system, and electrocatalysis reaction is carried out in an electrolyte solution to evolve oxygen. In the invention, a molybdenum carbide/foamed nickel composite material is used as an oxygen evolution electrocatalyst, electrons are enriched in a current collector (namely foamed nickel) in the electrocatalysis process, and OH generated in an alkaline medium-Preferentially attach to the active sites of molybdenum carbide and then separate from other OH groups-Reacting to generate other intermediate substances (OH, O and OOH), and oxidizing the intermediate substances to O2And (4) releasing. The method for performing electrocatalytic oxygen evolution by utilizing the molybdenum carbide/foamed nickel composite material has the advantages of simple process, low energy consumption, good oxygen evolution effect and the like, and has important significance for improving the electrocatalytic oxygen evolution performance and expanding the application range of oxygen as new energy.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) is determined.
FIG. 2 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF).
FIG. 3 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF) in which a is NF and b is Mo2C@NF。
FIG. 4 is a drawing showingMolybdenum carbide/foamed nickel composite material (Mo) prepared in example 1 of the present invention2C @ NF).
FIG. 5 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2N of C @ NF) and blank foam Nickel (NF)2Adsorption isotherm and pore size distribution profile, wherein a is N2Adsorption isotherm diagram, b is pore size distribution diagram.
FIG. 6 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2LSV plot (a) of C @ NF) versus blank Nickel Foam (NF), Mo2LSV comparison graph (b) of C @ NF composite material after 5000 cyclic voltammetry, and Mo2SEM image (C) of C @ NF composite after 5000 cyclic voltammetry.
FIG. 7 shows a Mo carbide/foam nickel composite material (Mo) obtained in example 1 of the present invention2C @ NF) versus blank Nickel Foam (NF) Tafel plot.
FIG. 8 shows a Mo carbide/foam nickel composite material (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF).
FIG. 9 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF), the inner panel is a cyclic voltammogram of NF.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1:
a molybdenum carbide/nickel foam composite material comprises molybdenum carbide and nickel foam, wherein the molybdenum carbide is loaded on the nickel foam.
In this example, the mass ratio of molybdenum carbide to nickel foam in the molybdenum carbide/nickel foam composite material was 1.5%.
In this embodiment, the molybdenum carbide has a block structure and is a cubic particle; the average particle size of the molybdenum carbide was 0.5. mu.m.
The preparation method of the molybdenum carbide/foamed nickel composite material in the embodiment of the invention comprises the following steps:
0.18g of a sample having an area of 2 × 2cm2The foamed nickel is sequentially soaked in acetone and 1.0M hydrochloric acid solution, ultrasonic treatment is carried out for 0.5h respectively, and then the foamed nickel is cleaned and dried; immersing the pretreated foamed nickel into 40mL of aqueous solution of ammonium molybdate/trisodium citrate (the aqueous solution contains 0.2mmol of ammonium molybdate and 0.1mmol of trisodium citrate), and performing ultrasonic dispersion for 0.5h to obtain a molybdenum carbide precursor solution; then, thermally dipping the molybdenum carbide precursor solution for 5 hours in a water bath at the temperature of 60 ℃ to obtain a foamed nickel material with the surface covered with the molybdenum carbide precursor; placing the foamed nickel material with the surface covered with the molybdenum carbide precursor into a tubular furnace, calcining for 1h at 600 ℃ in Ar atmosphere to obtain the molybdenum carbide/foamed nickel composite material, namely Mo2C@NF。
An application of the molybdenum carbide/nickel foam composite material prepared in the embodiment in electrocatalytic oxygen evolution includes the following steps: a three-electrode system is constructed by taking a molybdenum carbide/foamed nickel composite material as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and an electrocatalytic reaction is carried out in a 1.0M KOH solution (an electrolyte solution, the pH value is 13.7) to separate out oxygen.
In this example, the blank Nickel Foam (NF) material after pretreatment was used as a control group, and electrocatalytic oxygen evolution was performed under the same conditions.
In this example, all electrodes were calibrated to reversible hydrogen electrodes.
FIG. 1 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) is determined. The presence of Ni, Mo, C, N and O can be seen in fig. 1, indicating that molybdenum carbide was successfully loaded onto the nickel foam.
FIG. 2 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF). As can be seen from fig. 2, the diffraction peaks at 37.1 °, 43.2 ° and 62.7 ° correspond to the (002), (101) and (110) basal planes of cubic molybdenum carbide, respectively, indicating successful growth of molybdenum carbide on nickel foam.
FIG. 3 is a drawing showingMolybdenum carbide/foamed nickel composite material (Mo) prepared in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF) in which a is NF and b is Mo2C @ NF. As can be seen from FIG. 3, Mo2C was successfully grown on blank NF, and Mo2C showed a distinct blocky structure, being a cubic particle, which is consistent with the results of XRD analysis, and Mo2The average particle size of C was 0.5. mu.m.
FIG. 4 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF). As can be seen from FIG. 4, the striped lattice spacing is 0.24nm, corresponding to Mo2Basal plane of C crystal (002), showing Mo2And C, successful synthesis.
FIG. 5 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2N of C @ NF) and blank foam Nickel (NF)2Adsorption isotherm and pore size distribution profile, wherein a is N2Adsorption isotherm diagram, b is pore size distribution diagram. As can be seen from fig. 5a, all isotherms exhibit the typical Langmuir type IV characteristics with an intrinsic hysteresis loop, indicating the mesostructural nature of the material. Furthermore, N2The absorption increased sharply at high relative pressure (P/P0 ═ 0.9), indicating the presence of micropores in the sample from the NF network structure voids. NF and Mo2The specific surface areas of C @ NF were 2.15 and 3.08m, respectively2g-1Thus, a larger specific surface area can provide more active sites for the oxygen evolution reaction. In terms of pore size distribution (FIG. 5b), Mo2C @ NF has relatively wider pore size distribution in the range of 6-120nm than NF, and higher porosity is favorable for shortening the diffusion path of electrons and ions, which shows that Mo2The larger pore structure in C @ NF provides a favorable path for the rapid transmission of free radicals such as OH and the like to an active center, and contributes to the improvement of the electrocatalytic performance.
FIG. 6 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2LSV plot (a) of C @ NF) versus blank Nickel Foam (NF), Mo2LSV comparison graph (b) of C @ NF composite material after 5000 cyclic voltammetry, and Mo2SEM image (C) of C @ NF composite after 5000 cyclic voltammetry. As can be seen from FIG. 6a, the electrocatalytic performance was measuredThe test results show that Mo is relative to NF (1.79V vs RHE)2The current density can reach 10mAcm when the electrocatalytic oxygen evolution overpotential of C @ NF is only 1.57V-2The result shows that the molybdenum carbide/foamed nickel composite material has better electrocatalytic performance. As can be seen in FIG. 6b, after 5000 cyclic voltammetry, at 10mA cm-2At current density, Mo2The overpotential of C @ NF was not significantly increased, indicating that Mo2Excellent stability of the C @ NF composite. In addition, Mo after 5000 cyclic voltammetry2SEM image (5C) of C @ NF composite showing Mo2C still maintained the characteristic blocky structure without significant exfoliation, which further confirms that Mo was produced2The C @ NF composite material has stable structure.
FIG. 7 shows a Mo carbide/foam nickel composite material (Mo) obtained in example 1 of the present invention2C @ NF) versus blank Nickel Foam (NF) Tafel plot. As can be seen from FIG. 7, Mo2Slope of C @ NF was 72mV dec-1Significantly lower than NF (205mV dec)-1) This means that Mo is present in the oxygen evolution reaction2C @ NF possesses better kinetic properties and higher catalytic activity. In addition, the exchange current density (j) calculated by extrapolating Tafel plots0) Is a key parameter that reflects the number of active sites and indicates the intrinsic properties of the catalyst. Calculated Mo2J of C @ NF0A value of 7.4 × 10-3mA cm-2J significantly higher than NF0Value (2.3 × 10)-3mAcm-2) Showing Mo2The current density of the C @ NF surface is greater and a lower driving force is required to trigger the oxygen evolution reaction.
FIG. 8 shows a Mo carbide/foam nickel composite material (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF). In fig. 8, the impedance curves each show a typical semi-circle, with the semi-circle diameter representing the polarization resistance resulting from electron transfer (i.e., the charge transfer resistance R)ct) To overcome the activation barrier of the electrode reaction. As can be seen from FIG. 8, Mo2The polarization resistance of C @ NF was 1.846. OMEGA. lower than that of NF (1.982. OMEGA.), indicating that Mo2The C @ NF surface has better electron binding state and smaller RctValue helpsThe electronic structure of the electrode material is adjusted, and the electrocatalytic oxygen evolution performance is improved.
FIG. 9 shows a molybdenum carbide/nickel foam composite (Mo) obtained in example 1 of the present invention2C @ NF) and blank Nickel Foam (NF), the inner panel is a cyclic voltammogram of NF. In FIG. 9, the cyclic voltammograms are all non-rectangular, indicating a reversible redox reaction. As can be seen from FIG. 9, Mo2The C @ NF electrode exhibited a higher peak current density and a larger closed area, indicating that the Mo is2The redox current density of the C @ NF electrode is better.
Example 2:
a molybdenum carbide/nickel foam composite substantially the same as example 1 except that: the mass ratio of molybdenum carbide to nickel foam in the molybdenum carbide/nickel foam composite material of example 2 was 1.2%.
A method for preparing the molybdenum carbide/nickel foam composite material in the embodiment is substantially the same as that in embodiment 1, except that: the preparation of example 2 used an aqueous solution of ammonium molybdate/trisodium citrate containing 0.1mmol of ammonium molybdate and 0.1mmol of trisodium citrate.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.65V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Example 3:
a molybdenum carbide/nickel foam composite substantially the same as example 1 except that: the mass ratio of molybdenum carbide to nickel foam in the molybdenum carbide/nickel foam composite material of example 3 was 1.8%.
A method for preparing the molybdenum carbide/nickel foam composite material in the embodiment is substantially the same as that in embodiment 1, except that: the preparation of example 3 used an aqueous solution of ammonium molybdate/trisodium citrate containing 0.3mmol of ammonium molybdate and 0.1mmol of trisodium citrate.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.63V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Example 4:
a molybdenum carbide/nickel foam composite substantially the same as example 1 except that: the mass ratio of molybdenum carbide to nickel foam in the molybdenum carbide/nickel foam composite material of example 4 was 2.0%.
A method for preparing the molybdenum carbide/nickel foam composite material in the embodiment is substantially the same as that in embodiment 1, except that: the preparation of example 4 used an aqueous solution of ammonium molybdate/trisodium citrate containing 0.4mmol of ammonium molybdate and 0.1mmol of trisodium citrate.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.68V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Electrocatalytic performance of the molybdenum carbide/nickel foam composites prepared in comparative examples 1, 2, 3 and 4, the results show that: when the molar ratio of the molybdenum salt to the citrate is 1-6: 1, the molybdenum carbide generated on the surface of the foamed nickel has better load capacity and a better morphological structure, particularly, when the molar ratio of the molybdenum salt to the citrate is 2: 1, the molybdenum carbide generated on the surface of the foamed nickel has the best load capacity and the best morphological structure, so that the molybdenum carbide/foamed nickel composite material has better electrocatalytic performance, and the molybdenum carbide/foamed nickel composite material is used as an electrocatalyst, so that electrocatalytic oxygen evolution can be performed under lower overpotential, namely, a lower driving force is needed to trigger an oxygen evolution reaction, and energy consumption is saved. In addition, in the invention, by optimizing the mass ratio of molybdenum carbide to nickel foam to be 0.5-2.0%, the composite material has better stability and catalytic activity, because less molybdenum carbide (for example, the mass ratio of molybdenum carbide to nickel foam is less than 0.5%) can not provide enough catalytic active sites, and effective catalytic activity is difficult to obtain, while too much molybdenum carbide (for example, the mass ratio of molybdenum carbide to nickel foam is higher than 2.0%) can cause the molybdenum carbide to aggregate and grow on the surface of the nickel foam, so that the compactness between the molybdenum carbides is increased, and the transmission of free radicals such as OH is hindered, thereby reducing the catalytic activity.
Example 5:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation method of example 5, the calcination temperature was 500 ℃.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.64V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Example 6:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation method of example 6, the calcination temperature was 700 ℃.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.69V-2The molybdenum carbide/foamed nickel composite material has good performanceThe material has good stability after 5000 times of cyclic voltammetry.
Example 7:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation method of example 7, the calcination temperature was 800 ℃.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.71V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Electrocatalytic performance of the molybdenum carbide/nickel foam composites prepared in comparative examples 1, 5, 6 and 7, the results show that: when the calcination temperature of the molybdenum carbide/foamed nickel composite material is 500-800 ℃, the molybdenum carbide generated on the surface of the foamed nickel has a better crystal structure, and particularly, when the calcination temperature of the molybdenum carbide/foamed nickel composite material is 600 ℃, the molybdenum carbide generated on the surface of the foamed nickel has an optimal crystal structure, so that the molybdenum carbide/foamed nickel composite material has better electrocatalytic performance.
Example 8:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation process of example 8, the calcination time was 0.5 h.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.65V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Example 9:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation of example 9, the calcination time was 1.5 h.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.67V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Example 10:
a method for preparing a molybdenum carbide/nickel foam composite material, which is the same as the method in the example 1, except that: in the preparation process of example 10, the calcination time was 2 hours.
The molybdenum carbide/nickel foam composite material prepared above was used as a working electrode for electrocatalytic oxygen evolution, and the other conditions were the same as in example 1.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.69V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
Electrocatalytic performance of the molybdenum carbide/nickel foam composites prepared in comparative examples 1, 8, 9 and 10, the results show that: when the calcination time of the molybdenum carbide/foamed nickel composite material is 0.5 h-2 h, the molybdenum carbide generated on the surface of the foamed nickel has a better crystal structure, and particularly, when the calcination time of the molybdenum carbide/foamed nickel composite material is 1h, the molybdenum carbide generated on the surface of the foamed nickel has an optimal crystal structure, so that the molybdenum carbide/foamed nickel composite material has better electrocatalytic performance.
According to the invention, by controlling the calcination temperature (500-800 ℃) and the calcination time (0.5-2 h) in the preparation process of the molybdenum carbide/foamed nickel, the uniform dispersion and the particle size of molybdenum carbide on the foamed nickel can be ensured, and the preparation of the molybdenum carbide/foamed nickel composite material with stable structure and good electrocatalytic performance is facilitated, because the molybdenum carbide precursor cannot be completely reacted when the calcination temperature is too low (such as below 500 ℃), and the molybdenum carbide precursor can be rapidly carbonized at high temperature to generate a byproduct (such as MoC) when the calcination temperature is too high (such as above 800 ℃), and the metal grid structure of the foamed nickel can be damaged when the calcination temperature is above 800 ℃, so that the foamed nickel is fragile and cannot support the growth of the molybdenum carbide; in addition, too short a calcination time (e.g., less than 0.5h) may result in incomplete growth of molybdenum carbide, while too long a calcination time (e.g., more than 2h) may result in agglomeration of the formed molybdenum carbide bulk structure at high temperature, which may hinder the transfer of free radicals such as OH, thereby reducing catalytic activity.
Example 11:
the application of the molybdenum carbide/foamed nickel composite material in electrocatalytic oxygen evolution comprises the following steps: the molybdenum carbide/nickel foam composite material prepared in example 1 was used as a working electrode, a platinum wire was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode to construct a three-electrode system in 1.0M Na2SO4The solution (electrolyte solution, pH 7.0) undergoes an electrocatalytic reaction to precipitate oxygen.
The electrocatalytic performance test result shows that Mo2The current density of the C @ NF can reach 10mA cm when the electrocatalytic oxygen evolution overpotential is 1.74V-2The results show that the molybdenum carbide/foamed nickel composite material has good electrocatalytic performance, and the material maintains good stability after 5000 cyclic voltammetry.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A molybdenum carbide/nickel foam composite, wherein the molybdenum carbide/nickel foam composite comprises molybdenum carbide and nickel foam; the molybdenum carbide is loaded on the nickel foam.
2. The molybdenum carbide/nickel foam composite material according to claim 1, wherein the mass ratio of molybdenum carbide to nickel foam in the molybdenum carbide/nickel foam composite material is 0.5 to 2.0%.
3. The molybdenum carbide/nickel foam composite of claim 1 or 2, wherein the molybdenum carbide is in bulk; the average grain diameter of the molybdenum carbide is 0.5-3.0 μm.
4. A method for preparing the molybdenum carbide/nickel foam composite material according to any one of claims 1 to 3, comprising the following steps:
(1) mixing foamed nickel with an aqueous solution of molybdenum salt/citrate, and performing ultrasonic dispersion to obtain a molybdenum carbide precursor solution;
(2) carrying out thermal impregnation on the molybdenum carbide precursor solution obtained in the step (1) to obtain a foamed nickel material with the surface covered with the molybdenum carbide precursor;
(3) and (3) calcining the foamed nickel material with the surface covered with the molybdenum carbide precursor obtained in the step (2) to obtain the molybdenum carbide/foamed nickel composite material.
5. The preparation method according to claim 4, wherein in the step (1), the molar ratio of the molybdenum salt to the citrate in the molybdenum salt/citrate aqueous solution is 1-6: 1; the mass of the molybdenum salt in the aqueous solution of the molybdenum salt/citrate is 10-80% of that of the foamed nickel; the molybdenum salt in the molybdenum salt/citrate aqueous solution is sodium molybdate or ammonium molybdate; the citrate in the molybdenum salt/citrate aqueous solution is disodium citrate or trisodium citrate.
6. The method according to claim 4 or 5, wherein in the step (1), the foamed nickel further comprises the following treatment before use: putting the foamed nickel into acetone for ultrasonic treatment for 0.5 to 1 hour, and then putting the foamed nickel into a hydrochloric acid solution for ultrasonic treatment for 0.5 to 1 hour; the concentration of the hydrochloric acid solution is 0.5-3.0M; the ultrasonic dispersion time is 0.5-2 h;
in the step (2), the temperature of the hot dipping is 40-80 ℃; the hot dipping time is 5-10 h;
in the step (3), the calcination is carried out in an inert atmosphere; the inert atmosphere is N2Or Ar; the calcining temperature is 500-800 ℃; the calcining time is 0.5-2 h.
7. Use of the molybdenum carbide/nickel foam composite material according to any one of claims 1 to 3 or the molybdenum carbide/nickel foam composite material prepared by the preparation method according to any one of claims 4 to 6 in electrocatalytic oxygen evolution.
8. Use according to claim 7, characterized in that it comprises the following steps: molybdenum carbide/foamed nickel composite material is used as a working electrode to construct a three-electrode system, and electrocatalytic reaction is carried out in an electrolyte solution to separate out oxygen.
9. Use according to claim 8, wherein the electrolyte solution is a neutral or alkaline solution; the concentration of the electrolyte solution is 0.5M-1.0M.
10. Use according to claim 9, wherein the neutral solution is K2SO4Solutions or Na2SO4A solution; the alkaline solution is KOH solution or NaOH solution.
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