CN111569907A - Bimetal composite material and preparation method and application thereof - Google Patents
Bimetal composite material and preparation method and application thereof Download PDFInfo
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- CN111569907A CN111569907A CN202010356624.2A CN202010356624A CN111569907A CN 111569907 A CN111569907 A CN 111569907A CN 202010356624 A CN202010356624 A CN 202010356624A CN 111569907 A CN111569907 A CN 111569907A
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 26
- 229910052960 marcasite Inorganic materials 0.000 claims description 25
- 229910052683 pyrite Inorganic materials 0.000 claims description 25
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical group [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229920000428 triblock copolymer Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002073 nanorod Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229920006030 multiblock copolymer Polymers 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- 229910052573 porcelain Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002341 toxic gas Substances 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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- 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)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of nano materials and catalysts, and discloses a bimetal composite material and a preparation method and application thereof. The preparation method of the bimetal composite material comprises the following steps: (1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution; (2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor; (3) vulcanizing the bimetal precursor to obtain a bimetal composite material; wherein the first metal is iron and the second metal is nickel or cobalt. The preparation method is simple to operate and convenient for industrial production, and the bimetallic composite material prepared by the method has a nano-rod-shaped structure, so that the structural stability and catalytic activity of the material can be improved. Meanwhile, the bimetal composite material provided by the invention is used in the electrocatalytic oxygen evolution reaction, and has better catalytic activity and faster catalytic dynamic performance.
Description
Technical Field
The invention relates to the technical field of nano materials and catalysis, in particular to a bimetal composite material and a preparation method and application thereof.
Background
The clean energy hydrogen is considered as an ideal new energy source which can replace fossil energy, and the hydrogen production by water electrolysis is a method with potential application value for solving energy crisis and environmental problems due to the characteristics of small environmental pollution, high gas production purity and the like. Due to the hysteresis of the reaction kinetics, the oxygen evolution half-reaction is a critical step in the electrolysis of water and, in order to increase the reaction rate, a catalyst is required to accelerate the reaction.
The traditional oxygen evolution catalyst, such as Ir, Ru and other noble metal-based materials, has excellent catalytic activity, but is not beneficial to large-scale application of industrial electrolyzed water due to rare reserves and high price. Therefore, the development of the high-efficiency oxygen evolution catalyst capable of replacing noble metals has good practical application significance.
At present, transition metal sulfide is widely used as a material of an electrocatalytic oxygen evolution reaction catalyst due to the characteristics of low cost and good conductivity, and particularly, iron, nickel and cobalt which are rich in natural resources and low in price are widely used. Thus, iron-based, nickel-based and cobalt-based catalyst materials of various compositions and morphologies are synthesized and used for electrocatalytic hydrogen or oxygen evolution reactions.
Disclosure of Invention
The invention aims to solve the problems of high preparation cost and low catalytic activity of an oxygen evolution catalyst in the prior art, and provides a bimetallic composite material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a bimetal composite, the method comprising the steps of:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) vulcanizing the bimetal precursor to obtain a bimetal composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
Preferably, the mixing in step (1) comprises: (a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A; (b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B; (c) and carrying out third mixing on the solution A and the solution B to obtain the mixed solution.
Preferably, the conditions under which the solvent volatilizes to self-assemble comprise: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1-10h, preferably 2-6 h.
The invention also provides a bimetal composite material prepared by the preparation method.
Preferably, the bimetallic composite has a nanorod structure.
In a third aspect, the invention provides a use of the bimetallic composite material in electrocatalytic oxygen evolution reaction.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method mainly adopts a solvent volatilization self-assembly preparation method, and the preparation process is simple and easy to operate and is convenient for industrial production;
(2) the invention adopts transition metals of iron, nickel and cobalt as raw materials, reduces the catalytic cost, and simultaneously, the synergistic effect between the double metals ensures that the double metal composite material has better catalytic activity and faster catalytic dynamic performance;
(3) the bimetal composite material provided by the invention is of a nano rod-shaped structure, and is beneficial to improving the structural stability and catalytic activity of the material.
Drawings
FIG. 1 is FeS obtained in example 12/NiS2An X-ray diffraction pattern (XRD pattern) of material S1;
FIG. 2 is FeS obtained in example 12/NiS2Scanning electron micrographs (SEM images) of material S1;
FIG. 3 is FeS obtained in example 22/CoS2An X-ray diffraction pattern (XRD pattern) of material S2;
FIG. 4 is FeS obtained in example 22/CoS2Scanning electron micrograph (SEM picture) of material S2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing a bimetallic composite, comprising the steps of:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) vulcanizing the bimetal precursor to obtain a bimetal composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
The invention adopts transition metals (iron and nickel, iron and cobalt) as active components, so that the catalytic cost is reduced on one hand, and the bimetal has synergistic effect on the other hand, thereby being more beneficial to improving the catalytic activity.
In the present invention, there is a wide selection range for the first metal compound and the second metal compound, preferably, the first metal compound and the second metal compound are each independently a soluble metal compound, further preferably, the first metal compound is selected from at least one of iron chloride, iron sulfate, and iron nitrate, the second metal compound is selected from at least one of nickel chloride, nickel sulfate, and nickel nitrate, or the second metal compound is selected from at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate, more preferably, the first metal compound is iron nitrate, the second metal compound is nickel nitrate, or the second metal compound is cobalt nitrate.
According to the present invention, in order for the bimetallic composite to have a uniform morphological structure and a porous structure, preferably, the surfactant is a block copolymer.
In the present invention, there is a wide selection range of the block copolymer, preferably, the block copolymer is at least one selected from a diblock copolymer, a triblock copolymer and a multiblock copolymer, preferably a triblock copolymer, further preferably, the triblock copolymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, more preferably P123, wherein the molecular formula of P123 is PEO20PPO70PEO20And the molecular weight is 5800. The surfactant described in the examples is exemplified by P123, but the invention is not limited thereto.
The block copolymer of the present invention may be obtained commercially or may be prepared in a laboratory, and the present invention is not particularly limited thereto.
According to the present invention, preferably, the acid is an inorganic acid, further preferably at least one selected from the group consisting of nitric acid, sulfuric acid, and hydrochloric acid, and more preferably nitric acid, such as concentrated nitric acid, dilute nitric acid.
Preferably, the organic alcohol is an organic alcohol having a carbon number of 1-5, more preferably at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol and butanol, and still more preferably n-butanol.
According to the present invention, preferably, the molar ratio of the first metal compound, the second metal compound and the surfactant is 1: 0.1-1.5: 0.01 to 0.1, more preferably 1: 0.8-1.2: 0.02 to 0.06, more preferably 1: 1: 0.02-0.06.
Preferably, the molar ratio of the first metal compound to the organic alcohol is 1: 5 to 50, more preferably 1: 15-30. The preferred embodiment is more beneficial to obtaining the bimetal composite material with the nano structure with uniform appearance.
Preferably, the volume ratio of the acid to the organic alcohol is 1: 1 to 15, more preferably 1: 5-10. The use of this preferred embodiment is more advantageous for the stabilization of micelles in solution.
In the present invention, the mixing manner in the step (1) is not particularly limited as long as the first metal compound, the second metal compound, the surfactant, the acid and the organic alcohol are uniformly mixed, wherein the mixing is selected from one-step mixing and/or step-by-step mixing, and the one-step mixing refers to directly mixing the first metal compound, the second metal compound, the surfactant, the acid and the organic alcohol according to a certain ratio; the step mixing is to mix the first metal compound with part of the surfactant, part of the acid and part of the organic alcohol, mix the second metal compound with the rest of the surfactant, the rest of the acid and the rest of the organic alcohol, and mix the mixed solution containing the first metal compound with the mixed solution containing the second metal compound.
In order to further improve the structural stability and catalytic activity of the bimetal composite, preferably, the mixing in step (1) comprises:
(a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A;
(b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B;
(c) and carrying out third mixing on the solution A and the solution B to obtain the mixed solution.
According to the present invention, preferably, the conditions of the first mixing, the second mixing and the third mixing each independently include: the temperature is 20-60 ℃, preferably 30-50 ℃; the time is 10-60min, preferably 20-40 min.
In the present invention, the first mixing method is not particularly limited as long as the first metal compound is uniformly mixed with part of the surfactant, part of the acid, and part of the organic alcohol. Preferably, part of the surfactant, part of the acid and part of the organic alcohol are mixed first, and then the first metal compound is added. The preferred first mixing mode is favorable for the full action of the metal precursor and the surfactant and finally the formation of the bimetal composite material with uniform morphology.
In the present invention, the second mixing method is not particularly limited as long as the second metal compound is uniformly mixed with the remaining part of the surfactant, the remaining part of the acid, and the remaining part of the organic alcohol. Preferably, the remaining part of the surfactant, the remaining part of the acid and the remaining part of the organic alcohol are mixed first, and then the second metal compound is added. And the optimal second mixing mode is adopted, so that the full action of the metal precursor and the surfactant is facilitated, and the formation of the bimetal composite material with uniform morphology is finally facilitated.
In the present invention, the third mixing method is not particularly limited as long as the solution a and the solution B are uniformly mixed. Preferably, the solution A and the solution B are stirred for 10-60min at the temperature of 20-60 ℃ to obtain a mixed solution.
In a preferred embodiment of the invention, the surfactant, the acid and the organic alcohol are added in two portions, respectively, in steps (a) and (b), with a wide range of ratios of the two portions. Preferably, the molar ratio of the partial surfactant of step (a) to the remaining surfactant of step (b) is 1: 0.1 to 5; the volume ratio of the partial acid of the step (a) to the residual acid of the step (b) is 1: 0.1 to 5; the volume ratio of the part of organic alcohol in the step (a) to the rest of organic alcohol in the step (b) is 1: 0.1-5, but the present invention is not limited thereto.
According to the present invention, preferably, the conditions under which the solvent volatilizes for self-assembly include: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1-10h, preferably 2-6 h. The optimal conditions are adopted, so that the nano-structure material with uniform morphology can be obtained quickly. In the examples of the present invention, the solvent evaporation is carried out in an oven by self-assembly, but the present invention is not limited thereto.
According to the present invention, preferably, the step (2) further comprises: and sequentially cooling, washing, separating and drying the product of the solvent volatilization self-assembly, and then roasting. The cooling, washing and separating means are not particularly limited, and are all conventional technical means in the art, and the present invention is not particularly described.
According to a preferred embodiment of the present invention, the solvent is volatilized from the self-assembled product, naturally cooled to room temperature, washed with ethanol 3 to 5 times, and then centrifuged.
In the present invention, the drying environment is not particularly limited. Preferably, the drying is performed under air conditions, vacuum conditions, freezing conditions, and further preferably under vacuum conditions.
In the present invention, there is a wide range of selection of the conditions for the drying and firing, and preferably, the conditions for the drying include: the temperature is 20-80 ℃, preferably 30-60 ℃; the time is 10 to 24 hours, preferably 12 to 20 hours; the roasting conditions comprise: the temperature is 100-450 ℃, and the preferred temperature is 100-250 ℃; the time is 5-20h, preferably 8-15 h.
According to a preferred embodiment of the present invention, the dried product is calcined in a muffle furnace at a temperature of 2-10 ℃/min to 450 ℃ for 5-20 h.
According to the present invention, the operation manner of the sulfidation treatment is not particularly limited, so as to enable the metals in the bimetallic precursor to be respectively converted into sulfides, and preferably, the sulfidation treatment includes: contacting the bimetallic precursor with a sulfur source.
In the present invention, in order to fully vulcanize the material and obtain a purer sulfide material, the vulcanization is preferably performed under air-insulated conditions, further preferably, the vulcanization treatment is performed in an inert atmosphere or vacuum, more preferably in an inert atmosphere provided by an inert gas, wherein the inert gas is at least one selected from nitrogen, helium and argon, preferably nitrogen.
Preferably, the conditions of the vulcanization treatment include: the temperature is 200-600 ℃, preferably 250-400 ℃, and the time is 1-10h, preferably 1-4 h.
In the present invention, there is a wide selection range for the sulfur source, preferably the sulfur source is selected from sulfur powder and/or hydrogen sulfide. Since hydrogen sulfide is a toxic gas as a gas, the sulfur source is more preferably sulfur powder.
Preferably, the mass ratio of the sulfur source to the bimetallic precursor is 10-60: 1, preferably 25 to 60: 1. the preferred mass ratio is more favorable for the bimetallic precursor to be sulfided.
According to a preferred embodiment of the present invention, the bimetallic precursor is mixed with a sulfur source in a ratio of 10-60: 1, placing the mixture in a porcelain boat, placing the porcelain boat in a tubular furnace, continuously introducing nitrogen, setting a tubular furnace program, heating to 200-600 ℃ at a heating rate of 1-10 ℃/min, and reacting for 1-10h to obtain the bimetallic sulfide material.
In the invention, in order to further improve the vulcanization effect of the bimetal precursor, preferably, the sulfur source is in contact with the bimetal precursor in two parts, wherein one part of the sulfur source and the bimetal precursor are mixed and then placed in a porcelain boat and a tubular furnace; and the rest part of the sulfur source is positioned upstream of the inert gas, wherein the mass ratio of a part of the sulfur source to the rest part of the sulfur source is 1: 2-50, preferably 1: 5-15.
According to a preferred embodiment of the invention, the bimetal precursor and a part of sulfur source are uniformly mixed and then placed in a porcelain boat and a tubular furnace, nitrogen is continuously introduced, a tubular furnace program is set, the temperature is raised to 200-600 ℃ at the temperature raising rate of 1-10 ℃/min, and the reaction is carried out for 1-10 h; and adding residual sulfur powder on the upstream of the inert gas flow direction, wherein the mass ratio of a part of sulfur source to the residual part of sulfur source is 1: 2-50.
In a second aspect, the present invention provides a bimetallic composite prepared by the above method.
According to the invention, preferably, the bimetals in the bimetal composite are all in sulfide form, and the chemical formula of the bimetal composite is FeS2/RS2Wherein R is nickel element or cobalt element.
According to the present invention, preferably, the bimetal composite has a nanorod structure. The composite material provided by the invention has a stable morphology structure.
According to a preferred embodiment of the present invention, when the bimetal is iron and nickel, the bimetal composite material is FeS2/NiS2Material, and said FeS2/NiS2The material has a nanorod structure.
According to a preferred embodiment of the present invention, when the bimetal is iron and cobalt, the bimetal composite material is FeS2/CoS2Material, and said FeS2/CoS2The material has a nanorod structure.
In a third aspect, the invention provides a use of the bimetallic composite material in electrocatalytic oxygen evolution reaction.
In the invention, the bimetal composite material is used in the electrocatalytic oxygen evolution reaction, and due to the synergistic effect of the bimetal, the bimetal sulfide material has good catalytic activity and faster catalytic dynamic performance.
The present invention will be described in detail below by way of examples.
P123(PEO20PPO70PEO20Molecular weight 5800) was purchased from Sigma Aldrich (Sigma-Aldrich).
Example 1
(1) 1.16g P123, 1.32mL concentrated nitric acid, 11mL n-butanol, and 0.01mol iron nitrate (Fe (NO)3)3·9H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution A; 1.45g P123, 1.53mL concentrated nitric acid, 13mL n-butanol and 0.01mol nickel nitrate (Ni (NO)3)2·6H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution B; mixing the solution A and the solution B in a constant-temperature water bath at 40 ℃ and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution into a 120 ℃ drying oven, heating for 3.5h, cooling to room temperature, washing with ethanol for 3 times, centrifugally separating, drying in a 40 ℃ vacuum drying oven for 12h, and roasting the dried product in a muffle furnace at a temperature rise rate of 5 ℃/min to 150 ℃ for 12h to obtain an iron/nickel precursor;
(3) uniformly mixing 20mg of iron/nickel precursor and 100mg of sulfur powder, placing the mixture in a porcelain boat, placing the porcelain boat in a tube furnace, and continuously introducing N2Adding a porcelain boat containing 0.5g of sulfur powder at the air inlet end, setting a tube furnace program, heating to 300 ℃ at a heating rate of 2 ℃/min, roasting for 2h at the temperature, and cooling to obtain FeS2/NiS2Material S1.
Wherein, the FeS2/NiS2The XRD pattern of material S1 is shown in FIG. 1, wherein the diffraction peaks of 2 theta at 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 ° and 56.3 ° are respectively assigned to FeS2The (111), (200), (210), (211), (220) and (311) crystal planes of (JCPDS No. 42-1340); diffraction peaks of 2 theta at 31.6 degrees, 35.3 degrees, 38.8 degrees, 45.3 degrees and 53.6 degrees, which are respectively assigned to NiS2The (200), (210), (211), (220) and (311) crystal planes of (JCPDS No. 11-0099).
The FeS2/NiS2An SEM image of material S1 is shown in FIG. 2, which shows the FeS2/NiS2The material S1 has a nanorod structure.
Example 2
(1) 1.16g P123, 1.32mL concentrated nitric acid, 11mL n-butanol, and 0.01mol iron nitrate (Fe (NO)3)3·9H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution A; 1.45g P123, 1.53mL concentrated nitric acid, 13mL n-butanol and 0.01mol cobalt nitrate (Co (NO)3)2·6H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution B; mixing the solution A and the solution B in a constant-temperature water bath at 40 ℃ and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution into a 120 ℃ drying oven, heating for 3.5h, cooling to room temperature, washing with ethanol for 3 times, centrifugally separating, drying in a 40 ℃ vacuum drying oven for 12h, and roasting the dried product in a muffle furnace at a temperature rise rate of 5 ℃/min to 150 ℃ for 12h to obtain an iron/cobalt precursor;
(3) uniformly mixing 20mg of iron/cobalt precursor and 100mg of sulfur powder, placing the mixture in a porcelain boat, placing the porcelain boat in a tube furnace, and continuously introducing N2Adding a porcelain boat containing 1g of sulfur powder at the air inlet end, setting a tube furnace program, heating to 300 ℃ at the heating rate of 2 ℃/min, roasting for 2h at the temperature, and cooling to obtain FeS2/CoS2Material S2.
Wherein, the FeS2/CoS2The XRD pattern of material S2 is shown in FIG. 3, in which the diffraction peaks at 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 ° and 53.6 ° of 2 θ are assigned to FeS2The (111), (200), (210), (211), (220) and (311) crystal planes of (JCPDS No. 42-1340); diffraction peaks of 2 theta at 32.3 °, 36.2 °, 39.8 °, 46.3 ° and 54.9 ° assigned to CoS, respectively2The (200), (210), (211), (220) and (311) crystal planes (JCPDS No. 41-1471).
The FeS2/CoS2An SEM image of material S2 is shown in FIG. 4, which shows the FeS2/CoS2The material S2 has a nanorod structure.
Comparative example 1
The procedure is as in example 1, except that 0.01mol of nickel nitrate (Ni (NO) is not added3)2·6H2O) to obtain FeS2Material D1.
Comparative example 2
The procedure is as in example 1, except that 0.01mol of iron nitrate (Fe (NO) is not added3)3·9H2O) to obtain NiS2Material D2.
Comparative example 3
The procedure is as in example 2, except that 0.01mol of iron nitrate (Fe (NO) is not added3)3·9H2O) to give CoS2Material D3.
Test example
The bimetallic composites (S1-S2 and D1-D3) prepared in examples 1-2 and comparative examples 1-3 were subjected to the preparation of an electrocatalyst working electrode, which comprises:
(1) preparing a working electrode solution: respectively adding 4mg of bimetal composite materials S1-S2 and D1-D3 into a mixed solution containing Nafion solution (16 muL, 5 wt%), isopropanol (264 muL) and deionized water (520 muL), and carrying out ultrasonic treatment for 10-20min to obtain a working electrode solution;
(2) preparation of a working electrode: dripping the working electrode solution (12 mu L) onto a newly polished rotary disc glassy carbon electrode, and airing to obtain oxygen evolution catalysts P1-P2 and Q1-Q3;
(3) construction of a three-electrode system: and (3) constructing a three-electrode system by taking the oxygen evolution catalyst as a working electrode, taking a 1mol/L KOH solution as an electrolyte, taking a carbon rod as a counter electrode and taking Hg/HgO electrodes as reference electrodes respectively.
The electrochemical workstation of a three-electrode system CHI760E is adopted, the electrolyte is KOH solution (1mol/L), the three-electrode system using the bimetallic composite material is subjected to an electrocatalyst performance test, and the test result is shown in Table 1, wherein the overpotential is that the current density reaches 10mA/cm2The required overpotential.
TABLE 1
The results of table 1 show that when the bimetallic composite material provided by the invention is used in an oxygen evolution catalyst, the overpotential is low and the tafel slope value is small, that is, the bimetallic composite material provided by the invention has good catalytic activity and fast catalytic kinetics performance.
By comparing the oxygen evolution performance test results of the oxygen evolution catalysts P1, Q1 and Q2 in 1mol/L KOH, it can be known that:
(1) when the current density reaches 10mA/cm2Then, the bimetallic sulfide FeS2/NiS2The overpotential required is 370mV compared with the single metal sulfide FeS2(510mV) and NiS2(450mV) when the two materials are respectively used as catalysts, the overpotential required for achieving the current density is small, and the results show that the bimetallic sulfide (FeS)2/NiS2) When the catalyst is used as a catalyst, the catalyst has higher oxygen evolution catalytic performance;
(2) bimetallic sulfide FeS2/NiS2The Tafel slope value of the catalyst is 71mV/dec, which is higher than that of a single metal sulfide FeS2(105mV/dec) and NiS2The Tafel slope values of (109mV/dec) were all small, and the above results indicate that the bimetallic sulfide material (FeS)2/NiS2) Has faster catalytic kinetic performance when being used as a catalyst.
By comparing the oxygen evolution performance test results of the oxygen evolution catalysts P2, Q1 and Q3 in 1mol/L KOH, it can be known that:
(1) when the current density reaches 10mA/cm2Then, the bimetallic sulfide FeS2/CoS2The overpotential required is 370mV compared with the single metal sulfide FeS2(510mV) and CoS2(428mV) when the two materials are used as catalysts respectively, the overpotential required for achieving the current density is small, and the results show that the bimetallic sulfide (FeS)2/CoS2) When used as a catalyst, the catalyst has higher oxygen evolution catalytic performance.
(2) Bimetallic sulfide FeS2/CoS2The Tafel slope value of the catalyst is 69mV/dec, which is higher than that of a single metal sulfide FeS2(105mV/dec) and CoS2The Tafel slope values of (78mV/dec) are all small, aboveResults show bimetallic sulfide material (FeS)2/CoS2) Has faster catalytic kinetic performance when being used as a catalyst.
From the above results, it can be concluded that the bimetallic sulfide material has better catalytic activity and faster catalytic kinetics performance as an oxygen evolution catalyst due to the synergistic effect between the metallic iron and the nickel or the metallic iron and the cobalt in the bimetallic composite material.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of making a bimetallic composite, the method comprising the steps of:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) vulcanizing the bimetal precursor to obtain a bimetal composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
2. The method of claim 1, wherein the first metal compound and the second metal compound are each independently a soluble metal compound;
preferably, the first metal compound is selected from at least one of ferric chloride, ferric sulfate and ferric nitrate;
preferably, the second metal compound is selected from at least one of nickel chloride, nickel sulfate and nickel nitrate, or,
preferably, the second metal compound is selected from at least one of cobalt chloride, cobalt sulfate and cobalt nitrate;
preferably, the surfactant is a block copolymer;
preferably, the block copolymer is selected from at least one of a diblock copolymer, a triblock copolymer and a multiblock copolymer, preferably a triblock copolymer;
preferably, the triblock copolymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, more preferably P123;
preferably, the acid is selected from at least one of nitric acid, sulfuric acid, and hydrochloric acid;
preferably, the organic alcohol is an organic alcohol of C1-C5, and further preferably at least one selected from methanol, ethanol, propanol, isopropanol, and butanol.
3. The method according to claim 1 or 2, wherein the molar ratio of the first metal compound, the second metal compound and the surfactant is 1: 0.1-1.5: 0.01 to 0.1, preferably 1: 0.8-1.2: 0.02-0.06;
preferably, the molar ratio of the first metal compound to the organic alcohol is 1: 5 to 50, more preferably 1: 15-30 parts of;
preferably, the volume ratio of the acid to the organic alcohol is 1: 1 to 15, more preferably 1: 5-10.
4. The method of any one of claims 1-3, wherein the mixing in step (1) comprises:
(a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A;
(b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B;
(c) carrying out third mixing on the solution A and the solution B to obtain a mixed solution;
preferably, the conditions of the first mixing, the second mixing and the third mixing each independently comprise: the temperature is 20-60 ℃, preferably 30-50 ℃; the time is 10-60min, preferably 20-40 min.
5. The method of claim 1, wherein the conditions under which the solvent volatilizes self-assembly comprise: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1 to 10 hours, preferably 2 to 6 hours;
preferably, step (2) further comprises: sequentially cooling, washing, separating and drying the product of the solvent volatilization self-assembly, and then roasting;
preferably, the drying is carried out under air conditions, vacuum conditions, freezing conditions, preferably under vacuum conditions;
preferably, the drying conditions include: the temperature is 20-80 ℃, preferably 30-60 ℃; the time is 10 to 24 hours, preferably 12 to 20 hours;
preferably, the conditions of the calcination include: the temperature is 100-450 ℃, and the preferred temperature is 100-250 ℃; the time is 5-20h, preferably 8-15 h.
6. The method of claim 1, wherein the curing process comprises: contacting the bimetallic precursor with a sulfur source;
preferably, the vulcanization treatment is carried out in an inert atmosphere or vacuum, preferably in an inert atmosphere, the inert atmosphere being provided by an inert gas;
preferably, the inert gas is selected from at least one of nitrogen, helium and argon, further preferably nitrogen;
preferably, the conditions of the vulcanization treatment include: the temperature is 200-600 ℃, preferably 250-400 ℃, and the time is 1-10h, preferably 1-4 h.
7. The process according to claim 6, wherein the sulphur source is selected from sulphur powder and/or hydrogen sulphide, preferably sulphur powder;
preferably, the mass ratio of the sulfur source to the bimetallic precursor is 10-60: 1, preferably 25 to 60: 1.
8. a bimetallic composite produced by the method of any one of claims 1 to 7.
9. The bimetallic composite of claim 8, wherein the bimetals in the bimetallic composite are both present in sulfide form and the chemical formula of the bimetallic composite is FeS2/RS2Wherein R is nickel element or cobalt element;
preferably, the bimetallic composite has a nanorod structure.
10. Use of the bimetallic composite of claim 8 or 9 in electrocatalytic oxygen evolution reactions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403503A (en) * | 2020-11-27 | 2021-02-26 | 电子科技大学 | Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material |
| CN113388847A (en) * | 2021-07-06 | 2021-09-14 | 青岛科技大学 | Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof |
| CN114457377A (en) * | 2022-02-21 | 2022-05-10 | 郑州轻工业大学 | Preparation method and application of transition bimetal sulfide solid solution water electrolysis catalyst |
| CN115106103A (en) * | 2022-07-27 | 2022-09-27 | 广西民族大学 | Composite catalyst for flue gas treatment and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57113836A (en) * | 1980-11-17 | 1982-07-15 | Nat Res Dev | Manufacture of electrolytic catalyst |
| US20150259810A1 (en) * | 2014-03-17 | 2015-09-17 | California Institute Of Technology | Hydrogen evolution reaction catalysis |
| WO2017091955A1 (en) * | 2015-11-30 | 2017-06-08 | South University Of Science And Technology Of China | Bifunctional electrocatalyst for water splitting and preparation method thereof |
| CN110314690A (en) * | 2019-07-16 | 2019-10-11 | 广州大学 | Bimetallic sulfide Ni with heterogeneous interface coupling3S2/ FeS composite material and preparation method and application |
| CN110538663A (en) * | 2019-09-03 | 2019-12-06 | 国电新能源技术研究院有限公司 | Preparation method of porous NiS2 nanosheet and NiS2 material |
-
2020
- 2020-04-29 CN CN202010356624.2A patent/CN111569907A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57113836A (en) * | 1980-11-17 | 1982-07-15 | Nat Res Dev | Manufacture of electrolytic catalyst |
| US20150259810A1 (en) * | 2014-03-17 | 2015-09-17 | California Institute Of Technology | Hydrogen evolution reaction catalysis |
| WO2017091955A1 (en) * | 2015-11-30 | 2017-06-08 | South University Of Science And Technology Of China | Bifunctional electrocatalyst for water splitting and preparation method thereof |
| CN110314690A (en) * | 2019-07-16 | 2019-10-11 | 广州大学 | Bimetallic sulfide Ni with heterogeneous interface coupling3S2/ FeS composite material and preparation method and application |
| CN110538663A (en) * | 2019-09-03 | 2019-12-06 | 国电新能源技术研究院有限公司 | Preparation method of porous NiS2 nanosheet and NiS2 material |
Non-Patent Citations (4)
| Title |
|---|
| CHEN ZHAO ET AL.: "Nanostructured Fe-Ni Sulfide: A Multifunctional Material for Energy Generation and Storage", 《CATALYSTS》 * |
| YUANJUN LIU ET AL.: "Small sized Fe-Co sulfide nanoclusters anchored on carbon for oxygen evolution", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 高文君等: "CoS2和CoP材料的合成及其催化析氧应用", 《现代化工》 * |
| 高文君等: "多孔NiS_2和Ni_2P纳米片的制备及其析氧催化性能研究", 《化工新型材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403503A (en) * | 2020-11-27 | 2021-02-26 | 电子科技大学 | Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material |
| CN113388847A (en) * | 2021-07-06 | 2021-09-14 | 青岛科技大学 | Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof |
| CN114457377A (en) * | 2022-02-21 | 2022-05-10 | 郑州轻工业大学 | Preparation method and application of transition bimetal sulfide solid solution water electrolysis catalyst |
| CN115106103A (en) * | 2022-07-27 | 2022-09-27 | 广西民族大学 | Composite catalyst for flue gas treatment and preparation method and application thereof |
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