CN112138685A - Composite catalytic material, preparation method thereof, electrode and application - Google Patents
Composite catalytic material, preparation method thereof, electrode and application Download PDFInfo
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- CN112138685A CN112138685A CN202011104038.5A CN202011104038A CN112138685A CN 112138685 A CN112138685 A CN 112138685A CN 202011104038 A CN202011104038 A CN 202011104038A CN 112138685 A CN112138685 A CN 112138685A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 118
- 239000000463 material Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 85
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 239000013384 organic framework Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000010926 purge Methods 0.000 claims description 45
- 238000005303 weighing Methods 0.000 claims description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 25
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 22
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 abstract description 30
- 239000001301 oxygen Substances 0.000 abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 29
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 58
- 229910052573 porcelain Inorganic materials 0.000 description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- 239000007789 gas Substances 0.000 description 23
- 229910052786 argon Inorganic materials 0.000 description 21
- 239000012621 metal-organic framework Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
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- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RJFAYQIBOAGBLC-BYPYZUCNSA-N Selenium-L-methionine Chemical compound C[Se]CC[C@H](N)C(O)=O RJFAYQIBOAGBLC-BYPYZUCNSA-N 0.000 description 2
- RJFAYQIBOAGBLC-UHFFFAOYSA-N Selenomethionine Natural products C[Se]CCC(N)C(O)=O RJFAYQIBOAGBLC-UHFFFAOYSA-N 0.000 description 2
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- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229960002718 selenomethionine Drugs 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- HYAVEDMFTNAZQE-UHFFFAOYSA-N (benzyldiselanyl)methylbenzene Chemical compound C=1C=CC=CC=1C[Se][Se]CC1=CC=CC=C1 HYAVEDMFTNAZQE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- -1 chalcogenide compound Chemical class 0.000 description 1
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of materials, and particularly discloses a composite catalytic material, and a preparation method, an electrode and application thereof. The composite catalytic material provided by the embodiment of the invention shows excellent catalytic performance and circulation stability when being applied to a catalytic electrolysis water oxygen evolution reaction, and by using a cobalt-iron bimetallic organic framework compound as a precursor, the bimetallic components meet the charge ratio, the bimetallic components in the cobalt-iron bimetallic selenide can be accurately regulated and controlled, and the problem that the metal components cannot be accurately regulated and controlled because the existing metal selenide catalytic material is mostly prepared by a hydrothermal method and a solvothermal method is solved. Moreover, the provided preparation method is simple, is realized by simple stirring, washing, drying, roasting and selenizing, has strong controllability and low cost, is suitable for industrial production, and has good market application prospect.
Description
Technical Field
The invention relates to the field of materials, in particular to a composite catalytic material, and a preparation method, an electrode and application thereof.
Background
As the main problems related to the sustainable development of human society, hydrogen gas has a high chemical energy density and is stronger than fossil fuels such as natural gas and kerosene due to the increasing consumption of fossil fuels and the increasing environmental problems such as global warming, and the combustion product of hydrogen gas is only water and does not release harmful substances into the atmosphere during combustion, and thus it is considered to be the most promising and environmentally friendly fuel required by the earth and the environment at present.
At present, the energy efficiency of the commercial hydrogen production technology is relatively low, and in the hydrogen production process, the hydrogen and the carbon, sulfur, nitrogen oxide and other polluting gases are generated together, so that the hydrogen production technology does not meet the requirement of environmental protection. The electrochemical water decomposition is an effective method for solving the problems, and is one of effective technologies for relieving the energy crisis and reducing the carbon emission. However, the half-reaction of the water electrolysis hydrogen production anode is relatively complex, and a four-electron and four-proton transfer process is involved in the process of generating oxygen molecules, so that the slow reaction kinetics limit the practical application of water electrolysis hydrogen production. Therefore, the search for the development of an efficient and economical catalyst for the electrolytic water oxygen evolution reaction is an important step in pushing this technology to practical application.
At present, a plurality of catalytic materials are available on the market for water electrolysis anodes, wherein the bimetallic selenide is an important chalcogenide compound, has good conductivity and higher edge active sites, can effectively promote the rapid transfer of protons in the water electrolysis process, is very critical to the improvement of the water electrolysis performance, and therefore has great application potential in the catalytic electrochemical decomposition of water. Nevertheless, the performance of metal selenides as catalysts for the electrolytic water-evolution of oxygen is still unsatisfactory. In recent years, researchers mainly adopt the following construction strategies to improve the performance of the catalyst for the electrolytic water oxygen evolution reaction: (1) doping metal ions to modulate the chemical state of the metal active site such as electron density; (2) the particle size of the catalyst is reduced to a nanometer scale, and crystal face exposure with different activities is realized; (3) the composite material is compounded with non-metal materials such as carbon, nitrogen, phosphorus and the like to improve the conductivity, realize the construction of a new active site and the like.
However, the existing preparation method of the metal selenide catalytic material is still very limited, the traditional preparation method of the bimetallic selenide is mostly prepared by a hydrothermal method and a solvothermal method, the loss of metal ions in the reaction process can not meet the stoichiometric ratio, the adjustment of the components is uncontrollable, and the problem that the metal components can not be accurately adjusted and controlled exists, which restricts the development of the metal selenide electrocatalyst.
Disclosure of Invention
The embodiment of the invention aims to provide a composite catalytic material, and aims to solve the problem that the existing metal selenide catalytic material proposed in the background art is mostly prepared by a hydrothermal method and a solvothermal method, and cannot accurately regulate and control metal components.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a composite catalytic material, in particular to a cobalt-iron bimetallic selenide and carbon composite nano material, the main components of which are the cobalt-iron bimetallic selenide and carbon, the composite catalytic material is prepared by taking a cobalt-iron bimetallic organic framework compound precursor as a corresponding metal source and a carbon source and roasting the precursor and a selenium source; the precursor of the cobalt-iron bimetallic organic framework compound comprises raw materials of cobalt nitrate hexahydrate, ferric nitrate nonahydrate, dimethyl imidazole, sodium hydroxide and methanol.
Another objective of an embodiment of the present invention is to provide a method for preparing a composite catalytic material, where the method includes the following steps:
weighing a cobalt-iron bimetallic organic framework compound precursor according to a proportion, placing the precursor at one end of a container, weighing a selenium source at the other end of the container, and then roasting together in an inert gas purging atmosphere to obtain the composite catalytic material; wherein the roasting is carried out at a temperature rising speed of 4-6 ℃/min to 500-700 ℃ and kept for 1-3 hours.
The invention synthesizes the cobalt-iron bimetallic selenide and carbon composite nano material by providing a simple, quick and low-cost method, and the cobalt-iron bimetallic selenide and carbon composite nano material is used as a catalytic material for the electrolytic water oxygen evolution reaction, shows better electrocatalytic activity and stability of the oxygen evolution reaction, and provides a new idea for the synthesis of the metal selenide and the application of the metal selenide in the catalysis of the electrolytic water oxygen evolution reaction.
Another object of the embodiments of the present invention is to provide a composite catalytic material prepared by the above method for preparing a composite catalytic material.
It is another object of an embodiment of the present invention to provide an electrode, which includes the above composite catalytic material, a glassy carbon electrode material, and a dispersion solution, wherein the raw materials of the dispersion solution include ethanol, water, and perfluorosulfonic acid polymer.
The embodiment of the invention also aims to provide an application of the electrode in hydrogen production by catalytic electrolysis of water.
Compared with the prior art, the invention has the beneficial effects that:
the composite catalytic material prepared by the embodiment of the invention has excellent catalytic performance, compared with other bimetallic selenides, the composite catalytic material uses a cobalt-iron bimetallic organic framework compound as a precursor, the bimetallic components accord with the charge ratio, the bimetallic components in the cobalt-iron bimetallic selenide can be accurately regulated and controlled, and the problem that the metal components cannot be accurately regulated and controlled due to the fact that most of the existing metal selenide catalytic materials are prepared by a hydrothermal method and a solvothermal method is solved. Moreover, the preparation method of the composite catalytic material is simple, the composite catalytic material is realized by simple stirring, washing, drying, roasting and selenizing, the whole process is simple, the controllability is strong, the cost is low, and the composite catalytic material is suitable for industrial production.
Drawings
Fig. 1 is an X-ray diffraction pattern of precursor 1 and precursor 2 provided in the example of the present invention.
Fig. 2 is a scanning electron microscope image of the precursor 1 provided in the embodiment of the present invention.
Fig. 3 is a scanning electron microscope image of the precursor 2 provided in the embodiment of the present invention.
Fig. 4 is an X-ray diffraction pattern of composite material 1 and composite material 2 provided in the example of the present invention.
Fig. 5 is a transmission electron microscope image of the composite material 1 provided in the embodiment of the present invention.
Fig. 6 is a transmission electron microscope image of the composite material 2 provided in the embodiment of the present invention.
FIG. 7 is a linear sweep voltammogram of a catalytic electrolytic water-oxygen evolution reaction of the composite catalytic material provided by the embodiment of the invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The composite catalytic material provided by the embodiment of the invention, in particular to a cobalt-iron bimetallic selenide and carbon composite nano material, belongs to a functional catalytic material, and mainly comprises a composite of the cobalt-iron bimetallic selenide and carbon, wherein the composite catalytic material is prepared by taking a cobalt-iron bimetallic organic framework compound precursor as a corresponding metal source and a carbon source and roasting the precursor and the carbon source; the precursor of the cobalt-iron bimetallic organic framework compound comprises raw materials of cobalt nitrate hexahydrate, ferric nitrate nonahydrate, dimethyl imidazole, sodium hydroxide and methanol.
The composite catalytic material provided by the embodiment of the invention uses the cobalt-iron bimetallic organic framework compound as a precursor, the bimetallic component meets the feed ratio, the bimetallic component in the cobalt-iron bimetallic selenide can be accurately regulated and controlled, and the composite catalytic material is applied to the catalytic electrolysis water oxygen evolution reaction and shows excellent catalytic performance and cycling stability.
As another preferred embodiment of the present invention, the selenium source is selected from any one of selenium powder, selenomethionine or dibenzyl diselenide, and preferably, the selenium source may specifically adopt selenium powder.
As another preferred embodiment of the present invention, the raw materials of the cobalt-iron bimetallic organic framework compound precursor include cobalt nitrate hexahydrate, iron nitrate nonahydrate, dimethyl imidazole, sodium hydroxide and a proper amount of methanol.
Furthermore, a series of cobalt-iron double-metal selenides and carbon composite nano materials are obtained by adjusting the adding amount of cobalt nitrate hexahydrate and ferric nitrate nonahydrate under the same other conditions.
As another preferred embodiment of the present invention, in the cobalt-iron bimetallic organic framework compound precursor, the amount of the ferric nitrate nonahydrate is added, specifically, the molar amount of the iron metal in the ferric nitrate nonahydrate accounts for the total molar amount of the metals in the cobalt-iron bimetallic organic framework compound precursor, and the molar amount of the iron metal in the ferric nitrate nonahydrate accounts for 0 to 60 percent of the total molar amount of the metals in the cobalt-iron bimetallic organic framework compound precursor.
As another preferred embodiment of the present invention, in the cobalt-iron bimetallic organic framework compound precursor, the weight ratio of the cobalt nitrate hexahydrate to the iron nitrate nonahydrate is 1-3: 0.3-2.5.
As another preferred embodiment of the invention, in the composite catalytic material, the mass percentage of the carbon content is 3% -15%. Namely, in the finally obtained cobalt-iron bimetallic selenide and carbon composite nano material, the mass percent of carbon is 3-15%.
As another preferred embodiment of the present invention, the preparation method of the precursor of the cobalt-iron bimetallic organic framework compound at least comprises the following steps:
weighing cobalt nitrate hexahydrate and ferric nitrate nonahydrate according to a proportion, dissolving the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate in methanol to obtain a solution A, and weighing dimethyl imidazole and sodium hydroxide, dissolving the dimethyl imidazole and the sodium hydroxide in the methanol to obtain a solution B;
pouring the solution B into the solution A under the stirring condition, uniformly stirring and mixing, and standing to obtain a mixture;
and step three, washing the mixture for at least 3 times by using methanol, centrifuging, taking the precipitate, and drying in vacuum to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
Preferably, the preparation of the precursor of the cobalt-iron bimetallic organic framework compound at least comprises the following steps:
step one, weighing 1.048-2.358 g of cobalt nitrate hexahydrate and 0.363-2.182 g of ferric nitrate nonahydrate to be dissolved in 80-100 ml of methanol to obtain a solution A, and weighing 2-3 g of dimethylimidazole and 0.1-2 g of sodium hydroxide to be dissolved in 20-40 ml of methanol to obtain a solution B;
step two, pouring the solution B into the solution A under the stirring condition, continuously stirring for 2-10 minutes, and standing for 6-24 hours;
and step three, washing the obtained product with methanol for at least 3 times, wherein the centrifugal rotating speed is 7000 revolutions per minute, and then drying the product in a vacuum oven at 50-70 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
The embodiment of the invention also provides a preparation method of the composite catalytic material, which comprises the following steps:
weighing a cobalt-iron bimetallic organic framework compound precursor according to a proportion, placing the precursor in one end of a container (which can be a porcelain boat or other high-temperature-resistant container, specifically selected according to requirements, and not limited herein), weighing a selenium source, placing the selenium source in the other end of the container, and then roasting together in an inert gas purging atmosphere to obtain the composite catalytic material; wherein the roasting is carried out at a temperature rising speed of 4-6 ℃/min to 500-700 ℃ and kept for 1-3 hours.
As another preferred embodiment of the present invention, the inert gas purging atmosphere is an inert atmosphere provided by purging an inert gas selected from at least one of nitrogen, argon or helium.
As another preferred embodiment of the present invention, the container has one end for placing the selenium source located upstream of the purge gas and one end for placing the precursor of the ferrocobalt bimetallic organic framework compound located downstream of the purge gas, and the distance between the two ends is not more than 1 cm.
As another preferred embodiment of the invention, in the preparation method of the composite catalytic material, the method further comprises the step of purging with inert gas for at least half an hour before roasting.
Preferably, before roasting, inert gas is used for blowing for at least half an hour, then the temperature is raised to 600 ℃ at the temperature raising speed of 5 ℃/min, and after roasting for 2 hours at the temperature of 600 ℃, the temperature is naturally reduced, and the composite catalytic material, namely the cobalt-iron bimetallic selenide and carbon composite nano material, is obtained.
Further preferably, the preparation method of the composite catalytic material comprises the following steps: weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a precursor of the ferrocobalt bimetallic organic framework compound is positioned at the downstream of the purge gas, and the distance between the selenium powder and the purge gas is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material.
The embodiment of the invention also provides the composite catalytic material prepared by the preparation method of the composite catalytic material.
The embodiment of the invention also provides application of the composite catalytic material in catalyzing electrolysis of water to generate oxygen. Specifically, the composite catalytic material can be used in the fields of energy and environment, and is a novel catalyst material for the electrolytic water oxygen evolution reaction.
The embodiment of the invention also provides an electrode, which comprises the composite catalytic material, a glassy carbon electrode material and a dispersion solution, wherein the raw materials of the dispersion solution comprise ethanol, water and perfluorosulfonic acid polymer.
As another preferred embodiment of the present invention, the weight ratio of the composite catalytic material to the dispersion solution is 1-10: 800-1000.
As another preferred embodiment of the present invention, the weight ratio of ethanol, water and perfluorosulfonic acid polymer in the raw materials of the dispersion solution is 40-60:40-50: 4-5.
As another preferred embodiment of the present invention, the preparation method of the electrode is to mix ethanol, water and perfluorosulfonic acid polymer uniformly to prepare a dispersion solution, then add the composite catalytic material to mix uniformly (ultrasound for at least 20 minutes), then drop the mixture on a polished and washed glassy carbon electrode material (which may be an existing glassy carbon electrode product), and dry the mixture to obtain the electrode, specifically, the working electrode for electrolytic water oxygen evolution reaction.
Preferably, the preparation method of the electrode comprises the following steps: polishing a glassy carbon electrode with the diameter of 5mm by using 50-nanometer aluminum oxide polishing powder, and washing the polished glassy carbon electrode by using deionized water and ethanol for later use; then weighing 4 mg of the composite catalytic material, dissolving the composite catalytic material in a mixed solution containing 500 microliters of ethanol, 450 microliters of deionized water and 50 microliters of perfluorosulfonic acid type polymer solution, carrying out ultrasonic treatment for at least 20 minutes to obtain a uniform mixture, uniformly dripping 10 microliters of the uniform mixture on the polished glassy carbon electrode, and naturally airing.
As another preferred embodiment of the present invention, when the composite catalytic material is prepared into an electrode for a catalytic electrolysis water oxygen evolution reaction test, the electrolysis water oxygen evolution reaction test is performed by using the CHI760 electrochemical workstation manufactured by chenhua corporation of shanghai. The test adopts a three-electrode system, wherein an Hg/HgO electrode is a reference electrode, a carbon rod is a counter electrode, a glassy carbon electrode dripped with the composite catalytic material is the counter electrode, and an electrolyte solution is a 1mol/L KOH solution.
The embodiment of the invention also provides application of the electrode in hydrogen production by catalytic electrolysis of water.
The application principle and technical effect of the composite catalytic material of the present invention will be further described below by referring to specific examples. In the following examples, when the composite catalytic material is prepared into an electrode for a catalytic electrolysis water oxygen evolution reaction test, the electrolysis water oxygen evolution reaction test is performed by using a CHI760 electrochemical workstation manufactured by shanghai chenhua corporation, and the test adopts a three-electrode system, wherein an Hg/HgO electrode is a reference electrode, a carbon rod is a counter electrode, an electrode prepared from the composite catalytic material is a counter electrode, an electrolyte solution is a 1mol/L KOH solution, and other operation parameters refer to the existing device operation instructions. When the composite catalytic material is prepared into an electrode, the preparation method of the electrode comprises the following steps: polishing a glassy carbon electrode with the diameter of 5mm by using 50-nanometer aluminum oxide polishing powder, and washing the polished glassy carbon electrode by using deionized water and ethanol for later use; then weighing 4 mg of the composite catalytic material, dissolving the composite catalytic material in a mixed solution containing 500 microliters of ethanol, 450 microliters of deionized water and 50 microliters of perfluorosulfonic acid type polymer solution, carrying out ultrasonic treatment for at least 20 minutes to obtain a uniform mixture, uniformly dripping 10 microliters of the uniform mixture on the polished glassy carbon electrode, and naturally airing.
Example 1
A composite catalytic material is prepared by the following specific preparation method:
1) 2.619 g of cobalt nitrate hexahydrate are weighed out and dissolved in 90 ml of methanol to obtain solution A, and 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide are weighed out and dissolved in 30 ml of methanol to obtain solution B.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain a cobalt metal organic framework compound precursor, which is marked as precursor 1.
3) Weighing 40 mg of the obtained cobalt metal organic framework compound precursor, placing the cobalt metal organic framework compound precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material, which is marked as composite material 1.
The implementation effect is as follows: the specific result of the test of the catalytic electrolysis water oxygen evolution reaction of the electrode made of the composite catalytic material prepared in the embodiment is shown in fig. 7, the composite material 1 is marked as the linear sweep voltammetry of the catalytic electrolysis water oxygen evolution reaction of the composite material 1, and when the current density is 10 mA × cm-2The overpotential was 0.285V. It can be seen that it shows good catalytic activity for the electrolytic water oxygen evolution reaction.
Example 2
A composite catalytic material is prepared by the following specific preparation method:
1) 2.358 g of cobalt nitrate hexahydrate and 0.363 g of ferric nitrate nonahydrate were weighed out in 90 ml of methanol to obtain solution A, and 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide were weighed out in 30 ml of methanol to obtain solution B.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material, which is marked as a composite material 3.
The implementation effect is as follows: the specific results of the catalytic electrolysis water oxygen evolution reaction test on the electrode made of the composite catalytic material prepared in the embodiment are shown in fig. 7, the composite material 3 is marked as the linear sweep voltammetry curve of the catalytic electrolysis water oxygen evolution reaction of the composite material 3, and when the current density is 10 mA × cm-2The overpotential was 0.291V. It can be seen that it shows good catalytic activity for the electrolytic water oxygen evolution reaction.
Example 3
A composite catalytic material is prepared by the following specific preparation method:
1) solution A was prepared by dissolving 2.095 g of cobalt nitrate hexahydrate and 0.727 g of ferric nitrate nonahydrate in 90 ml of methanol, and solution B was prepared by dissolving 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide in 30 ml of methanol.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material.
Example 4
A composite catalytic material is prepared by the following specific preparation method:
1) solution A was prepared by dissolving 1.833 g of cobalt nitrate hexahydrate, 1.091 g of ferric nitrate nonahydrate in 90 ml of methanol, and solution B was prepared by dissolving 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide in 30 ml of methanol.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain a precursor of the cobalt-iron bimetallic organic framework compound, which is marked as a precursor 2.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material, which is marked as composite material 2.
The implementation effect is as follows: the specific results of the catalytic electrolysis water oxygen evolution reaction test on the electrode made of the composite catalytic material prepared in the embodiment are shown in fig. 7, the composite material 2 is marked as the linear sweep voltammetry curve of the catalytic electrolysis water oxygen evolution reaction of the composite material 2, and when the current density is 10 mA × cm-2The overpotential was 0.234V. It can be seen that it shows good catalytic activity for the electrolytic water oxygen evolution reaction.
Example 5
A composite catalytic material is prepared by the following specific preparation method:
1) 1.572 g of cobalt nitrate hexahydrate and 1.454 g of ferric nitrate nonahydrate were weighed out in 90 ml of methanol to obtain solution A, and 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide were weighed out in 30 ml of methanol to obtain solution B.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material.
Example 6
A composite catalytic material is prepared by the following specific preparation method:
1) 1.310 g of cobalt nitrate hexahydrate and 1.818 g of ferric nitrate nonahydrate were weighed out and dissolved in 90 ml of methanol to obtain solution A, and 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide were weighed out and dissolved in 30 ml of methanol to obtain solution B.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the rate of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material, which is marked as a composite material 4.
The implementation effect is as follows: the specific results of the catalytic electrolysis water oxygen evolution reaction test on the electrode made of the composite catalytic material prepared in the embodiment are shown in fig. 7, the mark of the composite material 4 is the linear sweep voltammetry of the catalytic electrolysis water oxygen evolution reaction of the composite material 4, and when the current density is 10 mA × cm-2The overpotential was 0.267V. It can be seen that it shows good catalytic activity for the electrolytic water oxygen evolution reaction.
Example 7
A composite catalytic material is prepared by the following specific preparation method:
1) solution A was prepared by dissolving 1.048 g of cobalt nitrate hexahydrate and 2.182 g of ferric nitrate nonahydrate in 90 ml of methanol, and solution B was prepared by dissolving 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide in 30 ml of methanol.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 600 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material.
Example 8
A composite catalytic material is prepared by the following specific preparation method:
1) solution A was prepared by dissolving 1.833 g of cobalt nitrate hexahydrate, 1.091 g of ferric nitrate nonahydrate in 90 ml of methanol, and solution B was prepared by dissolving 2.592 g of dimethylimidazole and 0.9 g of sodium hydroxide in 30 ml of methanol.
2) And pouring the solution B into the solution A under the stirring condition, continuously stirring for 5 minutes, standing for 12 hours, washing the obtained product for at least 3 times by using methanol, wherein the centrifugal rotation speed is 6000 revolutions per minute, and drying in a vacuum oven at 60 ℃ for at least 12 hours to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
3) Weighing 40 mg of the obtained precursor of the cobalt-iron bimetallic organic framework compound, placing the precursor at one end of a porcelain boat, and weighing 80 mg of commercial selenium powder at the other end of the porcelain boat; placing the porcelain boat into a tube furnace, and roasting in an argon purging atmosphere; when a sample in the porcelain boat is roasted, one end of selenium powder is positioned at the upstream of a purge gas, one end of a cobalt metal organic framework compound precursor is positioned at the downstream of the purge gas, and the distance between the two is not more than 1 cm; before roasting the sample in the porcelain boat, purging with argon for at least half an hour, then raising the temperature to 500 ℃ at the temperature raising speed of 5 ℃/min, keeping the temperature of 500 ℃ for roasting for 2 hours, and naturally cooling to obtain the composite catalytic material.
Example 9
The same procedure as in example 8 was repeated, except that the temperature was raised to 700 ℃ at a rate of 5 ℃/min and the calcination was carried out at 700 ℃ for 2 hours, as compared with example 8.
Example 10
The precursor 1 prepared in example 1 and the precursor 2 prepared in example 4 are subjected to X-ray diffraction characterization and are compared with standard data, and specific results are shown in fig. 1, so that a significant diffraction peak exists, that is, a metal organic framework compound is prepared.
Scanning electron microscope characterization is performed on the precursor 1 prepared in example 1, and specific results are shown in fig. 2. Scanning electron microscope characterization was performed on the precursor 2 prepared in example 4, and the specific results are shown in fig. 3. It can be seen that the resulting metal-organic framework compound has a uniform structure.
Example 11
When the composite material 1 prepared in example 1 and the composite material 2 prepared in example 4 are subjected to X-ray diffraction characterization and compared with standard cobalt selenide data, specific results are shown in fig. 4, and it can be seen that a significant diffraction peak exists.
The composite material 1 prepared in example 1 was subjected to transmission electron microscopy characterization, and the specific results are shown in fig. 5. The composite material 2 prepared in example 4 was subjected to transmission electron microscopy characterization, and the specific results are shown in fig. 6. It can be seen that in the formed composite catalytic material, the cobalt-iron bimetallic selenide nano particles are uniformly dispersed on the carbon material, so that the invention can accurately regulate and control the bimetallic components in the cobalt-iron bimetallic selenide.
Example 12
The same as example 2 except that selenium powder was replaced with selenomethionine, compared to example 2.
Example 13
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 0% by mole of the iron metal in the iron nitrate nonahydrate to the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 14
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 20% by mole of the iron metal in the iron nitrate nonahydrate based on the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 15
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 30% by mole of the iron metal in the iron nitrate nonahydrate to the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 16
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 40% by mole of the iron metal in the iron nitrate nonahydrate to the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 17
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 50% by mole of the iron metal in the iron nitrate nonahydrate based on the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 18
The same procedure as in example 12 was repeated, except that iron nitrate nonahydrate was added in an amount of 60% by mole of the iron metal in the iron nitrate nonahydrate to the total metal in the cobalt-iron bimetallic organic framework compound precursor, as compared with example 12.
Example 19
Same as example 2 except that the amount of the iron nitrate nonahydrate was added in a ratio of cobalt nitrate hexahydrate to iron nitrate nonahydrate of 1:0.3 by weight as compared with example 2.
Example 20
Same as example 2 except that the amount of the ferric nitrate nonahydrate was added in a ratio of cobalt nitrate hexahydrate to ferric nitrate nonahydrate of 3:0.3 by weight as compared with example 2.
Example 21
Same as example 2 except that the amount of the iron nitrate nonahydrate was added in a ratio of cobalt nitrate hexahydrate to iron nitrate nonahydrate of 3:2.5 by weight as compared with example 2.
Example 22
Same as example 2 except that the amount of the iron nitrate nonahydrate was added in a ratio of cobalt nitrate hexahydrate to iron nitrate nonahydrate of 2:2.5 by weight as compared with example 2.
Example 23
Same as example 2 except that the amount of the iron nitrate nonahydrate was added in a ratio of cobalt nitrate hexahydrate to iron nitrate nonahydrate of 3:1 by weight as compared with example 2.
Example 24
The same as example 2, except that the carbon content in the composite catalytic material was 3% by mass, was used as compared with example 2.
Example 25
The same as example 2, except that the carbon content in the composite catalytic material was 15% by mass, was used as compared with example 2.
Example 26
The same procedure as in example 4 was repeated, except that the calcination was carried out at a temperature-raising rate of 4 ℃/min to 500 ℃ for 1 hour, as compared with example 4.
Example 27
The same procedure as in example 4 was repeated, except that the calcination was carried out at a temperature-raising rate of 6 ℃/min to 700 ℃ for 3 hours, as compared with example 4.
Example 28
The same procedure as in example 4 was repeated, except that the calcination was carried out at a temperature-raising rate of 4 ℃/min to 700 ℃ for 1 hour, as compared with example 4.
Example 29
The same as example 4 except that the argon gas was replaced with nitrogen gas, as compared with example 4.
Example 30
The same as example 4 except that helium was used instead of argon, as compared with example 4.
Example 31
The same as example 4 except that the weight ratio of the composite catalytic material to the dispersion solution at the time of electrode preparation was 1:800 and the weight ratio of ethanol, water and perfluorosulfonic acid polymer in the raw material of the dispersion solution was 40:40:4, compared with example 4.
Example 32
The same as example 4 except that the weight ratio of the composite catalytic material to the dispersion solution at the time of electrode preparation was 10:1000, and the weight ratio of ethanol, water and perfluorosulfonic acid polymer in the raw material of the dispersion solution was 60:50:5, compared with example 4.
Example 33
The same as example 4 except that the weight ratio of the composite catalytic material to the dispersion solution at the time of electrode preparation was 5:900 and the weight ratio of ethanol, water and perfluorosulfonic acid polymer in the raw material of the dispersion solution was 50:45:4.5, compared with example 4.
Compared with the results reported in the literature, the invention has the following beneficial effects:
the invention is realized by simple stirring, washing, drying, roasting and selenizing, the whole process is simple, the controllability is strong, the cost is low, and the invention is suitable for industrial production.
Compared with other bimetallic selenides, the invention uses the cobalt-iron bimetallic organic framework compound as the precursor, the bimetallic components accord with the feed ratio, and the bimetallic components in the cobalt-iron bimetallic selenide can be accurately regulated and controlled.
The cobalt-iron bimetallic selenide and carbon composite nano material prepared by the invention is applied to the catalytic electrolysis water oxygen evolution reaction, shows excellent catalytic performance and cycle stability, and has good market application prospect.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. The composite catalytic material is characterized in that the main component of the composite catalytic material is a composite of cobalt-iron bimetallic selenide and carbon, and the composite catalytic material is prepared by taking a cobalt-iron bimetallic organic framework compound precursor as a corresponding metal source and a carbon source and roasting the precursor and a selenium source; the precursor of the cobalt-iron bimetallic organic framework compound comprises raw materials of cobalt nitrate hexahydrate, ferric nitrate nonahydrate, dimethyl imidazole, sodium hydroxide and methanol.
2. The composite catalytic material of claim 1, wherein the molar amount of iron in the ferric nitrate nonahydrate in the cobalt-iron bimetallic organic framework compound precursor is 0-60% of the total molar amount of metals in the cobalt-iron bimetallic organic framework compound precursor.
3. The composite catalytic material of claim 1, wherein the weight ratio of the cobalt nitrate hexahydrate to the iron nitrate nonahydrate in the cobalt-iron bimetallic organic framework compound precursor is 1-3: 0.3-2.5.
4. The composite catalytic material according to claim 1, characterized in that the carbon content in the composite catalytic material is between 3% and 15% by mass.
5. The composite catalytic material of claim 1, wherein the preparation method of the precursor of the ferrocobalt bimetallic organic framework compound at least comprises the following steps:
weighing cobalt nitrate hexahydrate and ferric nitrate nonahydrate according to a proportion, dissolving the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate in methanol to obtain a solution A, and weighing dimethyl imidazole and sodium hydroxide, dissolving the dimethyl imidazole and the sodium hydroxide in the methanol to obtain a solution B;
step two, pouring the solution B into the solution A under the condition of stirring, uniformly mixing, and standing to obtain a mixture;
and step three, washing and centrifuging the mixture, and drying the precipitate in vacuum to obtain the precursor of the cobalt-iron bimetallic organic framework compound.
6. A method for preparing a composite catalytic material according to any of claims 1 to 5, comprising the steps of: weighing a cobalt-iron bimetallic organic framework compound precursor according to a proportion, placing the precursor at one end of a container, weighing a selenium source at the other end of the container, and then roasting together in an inert gas purging atmosphere to obtain the composite catalytic material; wherein the roasting is carried out at a temperature rising speed of 4-6 ℃/min to 500-700 ℃ and kept for 1-3 hours.
7. A composite catalytic material prepared by the method for preparing the composite catalytic material according to claim 6.
8. An electrode comprising the composite catalytic material of claim 1 or 2 or 3 or 4 or 5 or 7, and a glassy carbon electrode material and a dispersion solution comprising as raw materials ethanol, water and perfluorosulfonic acid polymer.
9. The electrode according to claim 8, wherein the electrode is prepared by uniformly mixing ethanol, water and perfluorosulfonic acid polymer to obtain a dispersion solution, adding the composite catalytic material, uniformly mixing, dripping the mixture on a polished and washed glassy carbon electrode material, and drying to obtain the electrode.
10. Use of an electrode according to claim 8 or 9 for the catalytic electrolysis of water to produce hydrogen.
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