CN109621981A - A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide and its preparation method and application - Google Patents
A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide and its preparation method and application Download PDFInfo
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- CN109621981A CN109621981A CN201811288260.8A CN201811288260A CN109621981A CN 109621981 A CN109621981 A CN 109621981A CN 201811288260 A CN201811288260 A CN 201811288260A CN 109621981 A CN109621981 A CN 109621981A
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- catalyst
- sulfide
- cobalt
- elctro
- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000001301 oxygen Substances 0.000 title claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 43
- 238000004458 analytical method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 33
- 239000010941 cobalt Substances 0.000 claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- 239000011701 zinc Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 29
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002070 nanowire Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 5
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000012149 noodles Nutrition 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical group O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical group [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses compound analysis oxygen elctro-catalysts of a kind of metal oxide-sulfide and its preparation method and application.The elctro-catalyst is to coat composite material made of cobalt acid zinc nano wire as nickel cobalt sulfide nanometer sheet.Preparation method synthesizes cobalt acid zinc nano wire with hydro-thermal reaction first, in conjunction with electrochemical deposition sulfide nanometer sheet, cobalt acid zinc nano wire is coated with nickel cobalt sulfide nanometer sheet, that is, prepares the compound analysis oxygen elctro-catalyst of metal oxide-sulfide with nucleocapsid clad structure.Elctro-catalyst of the invention is due to specially designed chemical composition and microstructure, improve the active site and surface area of composite catalyst, there is very high oxygen evolution activity and stability compared to other oxides and sulphide electrocatalyst, and preparation method is simple and convenient, using the base metal raw material of low cost, be conducive to Oxygen anodic evolution catalyst needed for synthesizing electrolysis water reaction on a large scale, there is good popularization and application foreground.
Description
Technical field
The invention belongs to catalyst material technical fields.More particularly, to a kind of compound analysis of metal oxide-sulfide
Oxygen elctro-catalyst and its preparation method and application.
Background technique
The energy and environment are two key factors for maintaining human social.With the day of traditional fossil energy
Gradually exhausted and atmosphere pollution and greenhouse effects with fossil energy burning generation, it is a kind of clean renewable there is an urgent need to find
The energy carrys out substitute fossil fuels.
Hydrogen Energy is pollution-free as one kind, and the energy of high-energy density is attracted attention.Electrochemical decomposition water hydrogen manufacturing has operation
Simply, the advantages of converting rate is high, does not discharge exhaust gas is expected to replace the vapor reforming hydrogen production technology of highly energy-consuming.However mesh
Preceding water electrolysis hydrogen production cost is much higher than conventional catalyst hydrogen producing technology, is largely determined by expensive needed for electrolysis water liberation of hydrogen and oxygen evolution reaction
Metallic catalyst.Wherein Oxygen anodic evolution reaction is that one thermodynamically unfavourable and the slow electrode reaction of dynamics, overpotential are remote
It is reacted higher than cathode hydrogen evolution, needs to reduce overpotential using catalyst, improve reaction rate, so that whole raising electrolysis water is anti-
The efficiency answered.
Currently, most effective commercialization analysis oxygen elctro-catalyst is iridium dioxide and ruthenic oxide, but both noble metals
Catalyst is due to reserves rareness and expensive and limit the large-scale application of water electrolysis hydrogen production technology.In addition, also having at present
Report that some cheap transition metal oxides, the materials such as sulfide can be used as the elctro-catalyst of Oxygen anodic evolution reaction, but this
The performance distance noble metal catalyst of a little materials still has certain distance.
Therefore, development cost is cheap and at the same time the Oxygen anodic evolution elctro-catalyst with high activity and stability is with important
Meaning.
Summary of the invention
At high cost, active low and/or stability that the technical problem to be solved by the present invention is to overcome existing analysis oxygen elctro-catalysts
It is simple and convenient, low in cost and have very high oxygen separated activity and stability to provide a kind of preparation method for the defect and deficiency of difference
Metal oxide-sulfide composite anode analyses oxygen elctro-catalyst.
The object of the present invention is to provide a kind of compound analysis oxygen elctro-catalysts of metal oxide-sulfide.
Another object of the present invention is to provide the preparation method of the compound analysis oxygen elctro-catalyst.
Still a further object of the present invention is to provide the application of the compound analysis oxygen elctro-catalyst.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide is to coat cobalt acid zinc nanometer by nickel cobalt sulfide nanometer sheet
Composite material made of line.
Preferably, the diameter of the cobalt acid zinc nano wire is 60nm~120nm.
It is highly preferred that the diameter of the cobalt acid zinc nano wire is 100 nm.
Preferably, the nickel cobalt sulfide nanometer sheet with a thickness of 100nm~150nm.
It is highly preferred that the nickel cobalt sulfide nanometer sheet with a thickness of 120 nm.
In addition, the preparation method of the compound analysis oxygen elctro-catalyst of metal oxide-sulfide is: first with hydro-thermal reaction
Cobalt acid zinc nano wire is first synthesized, in conjunction with electrochemical deposition sulfide nanometer sheet, is received with nickel cobalt sulfide nanometer sheet cladding cobalt acid zinc
Rice noodles prepare the compound analysis oxygen elctro-catalyst of metal oxide-sulfide with nucleocapsid clad structure.
Specifically, the preparation method of the compound analysis oxygen elctro-catalyst of the metal oxide-sulfide, includes the following steps:
S1. the mixed aqueous solution for configuring zinc nitrate, cobalt nitrate, ammonium fluoride and urea, is transferred to polytetrafluoroethyllining lining not
It becomes rusty in steel hydrothermal reaction kettle, a piece of clean nickel foam is added, heat 4~6 hours at 100~150 DEG C, before obtaining growing and having
The nickel foam of body is driven, after taking out clean dry, is heat-treated 1.5~3 hours for 350~500 DEG C in air, obtains cobalt acid zinc nanometer
Line；
S2. with cyclic voltammetry electrochemical deposition nickel cobalt sulfide nanometer sheet in three-electrode system: growth has cobalt acid zinc nanometer
For the nickel foam of piece as working electrode, graphite rod is auxiliary electrode, and silver/silver chloride electrode is reference electrode；Electrolyte is nitric acid
Cobalt, nickel nitrate and thiocarbamide；Nickel foam clean dry is taken out after reaction, obtains the cobalt acid zinc nanometer of nickel cobalt sulfide nanometer sheet cladding
Line, i.e., the described compound analysis oxygen elctro-catalyst of metal oxide-sulfide.
Wherein it is preferred to which the molar ratio of zinc nitrate and cobalt nitrate is 1:1~3 in mixed aqueous solution described in step S1.
It is highly preferred that the molar ratio of zinc nitrate and cobalt nitrate is 1:2 in mixed aqueous solution described in step S1.
Preferably, in mixed aqueous solution described in step S1, the molar ratio of ammonium fluoride and urea is 1:2~3.
It is highly preferred that the molar ratio of ammonium fluoride and urea is 2:5 in mixed aqueous solution described in step S1.
It is highly preferred that zinc nitrate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 1 in mixed aqueous solution described in step S1:
1~3:2:4~6.
It is highly preferred that zinc nitrate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 1 in mixed aqueous solution described in step S1:
2:2:5.
Preferably, nitric acid zinc concentration described in step S1 is 0.01 mol/L~0.03mol/L.
It is highly preferred that nitric acid zinc concentration described in step S1 is 0.02 mol/L.
Preferably, the concentration of cobalt nitrate described in step S1 is 0.03 mol/L~0.05mol/L.
It is highly preferred that the concentration of cobalt nitrate described in step S1 is 0.04 mol/L.
Preferably, the concentration of ammonium fluoride described in step S1 is 0.02 mol/L~0.06mol/L.
It is highly preferred that the concentration of ammonium fluoride described in step S1 is 0.04 mol/L.
Preferably, the concentration of urea described in step S1 is 0.05 mol/L~0.2mol/L.
It is highly preferred that the concentration of urea described in step S1 is 0.1 mol/L.
Preferably, the area of nickel foam described in step S1 is 2cm2-8cm2。
It is highly preferred that the area of nickel foam described in step S1 is 4 cm2。
Preferably, in step S1 be added nickel foam after, be heat 4~6 hours at 100~150 DEG C, obtain grow have before
The nickel foam of body is driven, after taking out clean dry, is heat-treated 1.5~3 hours for 350~500 DEG C in air, obtains cobalt acid zinc nanometer
Line.
It is highly preferred that after nickel foam is added in step S1 being heated 5 hours at 120 DEG C, obtaining growth has presoma
Nickel foam after taking out clean dry, is heat-treated 2 hours for 400 DEG C in air, obtains cobalt acid zinc nano wire.
Preferably, the electric potential scanning range of cyclic voltammetry described in step S2 is -1.2V~0.2V(relative to reference electricity
Pole), scanning speed is 4~6mV/s.
It is highly preferred that scanning speed described in step S2 is 5mV/s.
Preferably, the scanning circle number of cyclic voltammetry described in step S2 is 10~20 circles.
It is highly preferred that the scanning circle number of cyclic voltammetry described in step S2 is 15 circles.
Preferably, in electrolyte described in step S2, cobalt nitrate: nickel nitrate: the molar ratio of thiocarbamide is 1:1~2:10~50.
It is highly preferred that cobalt nitrate: nickel nitrate: the molar ratio of thiocarbamide is 1:1.5:20 in electrolyte described in step S2.
Preferably, in electrolyte described in step S2, the concentration of cobalt nitrate is 0.005 mol/L~0.02mol/L.
It is highly preferred that the concentration of cobalt nitrate is 0.01 mol/L in electrolyte described in step S2.
In addition, the compound analysis oxygen elctro-catalyst of metal oxide-sulfide prepared by the above method and its in electricity
The application in terms of water hydrogen manufacturing is solved, it also all should be within protection scope of the present invention.Specifically, mainly it is applied to electrolytic water device
Oxygen anodic evolution reaction.
The invention has the following advantages:
(1) present invention is by combining hydro-thermal reaction and electrochemical deposition method to synthesize a kind of oxide-sulfide composite electro catalytic
Agent can easily adjust the chemical composition and microscopic appearance and its size of composite catalyst by controlling reaction condition, thus
Regulate and control the performance of catalyst.
(2) composite catalyst of the present invention has special nucleocapsid clad structure, and composite catalyst can led with growth in situ
In electrically good porous foam nickel set fluid, so that above-mentioned catalyst has excellent stability and high-specific surface area, it can
Generate more active sites.
(3) compared to other report catalyst, catalyst provided by the invention have synthetic method it is simply controllable, it is low at
This, catalytic activity is high, can be effectively reduced the overpotential of Oxygen anodic evolution reaction, while being conducive to make on a large scale on a current collector
It is standby, there are industrial applications potentiality.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction pattern of 1 gained elctro-catalyst of embodiment.
Fig. 2 is the transmission electron microscope photo of 1 gained elctro-catalyst of embodiment, and wherein (a) and (b) and (c) are respectively low
Times and high power transmission electron microscope photo.
Fig. 3 is the electrocatalysis characteristic picture of 1 gained elctro-catalyst of embodiment, wherein the linear scan that (a) is catalyst lies prostrate
Pacify curve, (b) is the Tafel curve of elctro-catalyst.
Fig. 4 is the stability picture of 1 gained elctro-catalyst of embodiment.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
Embodiment 1
1, the preparation of the compound analysis oxygen elctro-catalyst of metal oxide-sulfide of the present invention
(1) 0.02 mol/L zinc nitrate, 0.04 mol/L cobalt nitrate, 0.04 mol/L ammonium fluoride and 0.1 mol/L urea are configured
Mixed aqueous solution 30mL, be transferred in the stainless steel hydrothermal reaction kettle with polytetrafluoroethyllining lining of 40 mL, be added one
The clean nickel foam of piece, nickel foam area are 4 cm2.Hydrothermal reaction kettle is placed in baking oven, heating maintenance 5 is small at 120 DEG C
When.The nickel foam with presoma is taken out, is heat-treated 2 hours with 400 DEG C in air after cleaning drying, obtaining growth has cobalt sour
The nickel foam of zinc nano wire.
(2) with cyclic voltammetry electrochemical deposition nickel cobalt sulfide nanometer sheet in three-electrode system: having cobalt sour with growth
For the nickel foam of zinc nano wire as working electrode, graphite rod is auxiliary electrode, and silver/silver chloride electrode is reference electrode, and current potential is swept
Retouching range is -1.2 V-0.2 V(relative to reference electrode), scanning speed is 5 mV/s, and scanning circle number is 15 circles.Electrolyte is
0.01 mol/L cobalt nitrate, 0.015 mol/L nickel nitrate and 0.2 mol/L thiourea solution.Nickel foam is taken out after reaction to clean
It is dry, obtain the cobalt acid zinc nano wire of nickel cobalt sulfide nanometer sheet cladding, i.e., the described compound analysis oxygen electricity of metal oxide-sulfide
Catalyst.
2, structural analysis
The X-ray powder diffraction pattern of gained elctro-catalyst as shown in Figure 1, contrast standard map it is found that prepared electro-catalysis
Agent chemical composition is cobalt acid zinc (ZnCo2O4) and nickel cobalt sulfide (CoNi2S4).
The transmission electron microscope photo of gained elctro-catalyst from the catalyst known to macrograph as shown in Fig. 2, have
Special nucleocapsid clad structure, wherein internal layer is cobalt acid zinc nano wire, and external sheath is nickel cobalt sulfide nanometer sheet.Sour zinc is received
Rice noodles diameter is 100nm, and it is 120nm that nickel cobalt sulfide nanometer sheet, which coats layer height,.From high power photo as it can be seen that internal layer cobalt acid zinc is received
The lattice width of rice noodles corresponds to its (220) and (331) crystal face, and the lattice width of outer layer nickel cobalt sulfide nanometer sheet corresponds to it
(400) and (331) crystal face.
Result is it is found that the group for the elctro-catalyst being prepared becomes the cobalt acid of nickel cobalt sulfide nanometer sheet cladding in summary
Zinc nano wire.
3, performance test
The cobalt acid zinc nano wire and nickel cobalt sulfide nanometer sheet catalyst of independent component are synthesized with same procedure, as a comparison.
Respectively using each catalyst as working electrode, graphite rod is auxiliary electrode, and saturated calomel electrode is reference electrode,
It forms three-electrode system and tests catalyst Oxygen anodic evolution reactivity worth, electrolyte is 1 mol/L potassium hydroxide aqueous solution.
Structure is as shown in figure 3, a figure is composite electrocatalyst (ZnCo in Fig. 32O4@Ni-Co-S), cobalt acid zinc nano wire and nickel
Cobalt sulfide nanometer sheet independent component catalyst (ZnCo2O4With the linear sweep voltammetry curve of Ni-Co-S), work as electricity as seen from the figure
Current density is 10 mA/cm2When, prepared composite electrocatalyst overpotential only needs 300mV, and the cobalt acid zinc lower than independent component is received
Rice noodles and nickel cobalt sulfide nanometer sheet.
The Tafel curve that b figure is three groups in Fig. 3, wherein the Tafel slope of composite electrocatalyst is only 30 mV/dec, low
In cobalt acid zinc nano wire and nickel cobalt sulfide nanometer sheet.
Result is it is found that composite electrocatalyst has superior oxygen evolution reaction catalytic activity in summary.
4, the stability test of composite electrocatalyst
Further by chronoptentiometry in 10 mA/cm2Current density under measure oxygen evolution reaction needed for current potential and time pass
System illustrates that the composite electrocatalyst has as shown in figure 4, overpotential only increased 20mV by prolonged reaction in 10 hours
There is high stability.
Test result in summary, compared with existing catalyst, composite electrocatalyst provided by the present invention is in anode
There is very excellent catalytic activity and stability in oxygen evolution reaction, there is the application potential instead of noble metal catalyst.
Embodiment 2
It is essentially identical with 1 preparation method of embodiment, the difference is that by the circle number of electrochemical deposition nickel cobalt sulfide nanometer sheet
20 circles are changed to from 15 circles, acquired composite catalyst composition is essentially identical with embodiment ingredient.In 10mA/cm2Current density
Overpotential needed for lower measurement oxygen evolution reaction is 320 mV.
Embodiment 3
It is essentially identical with 1 preparation method of embodiment, the difference is that by the circle number of electrochemical deposition nickel cobalt sulfide nanometer sheet
10 circles are changed to from 15 circles, acquired composite catalyst composition is essentially identical with embodiment ingredient.In 10mA/cm2Current density
Overpotential needed for lower measurement oxygen evolution reaction is 335 mV.
Embodiment 4
It is essentially identical with 1 preparation method of embodiment, the difference is that hydrothermal reaction kettle is placed in baking oven, add at 120 DEG C
Heat maintains 10 hours, and final acquired composite catalyst composition is essentially identical with embodiment ingredient.It is close in the electric current of 10mA/cm2
Overpotential needed for the lower measurement oxygen evolution reaction of degree is 345 mV.
Embodiment 5
It is essentially identical with 1 preparation method of embodiment, the difference is that by the nickel foam with presoma is taken out, after cleaning drying
It is heat-treated 2 hours with 400 DEG C in air, obtains cobalt acid zinc nano wire, final acquired composite catalyst composition and embodiment
Ingredient is essentially identical.Overpotential needed for measuring oxygen evolution reaction under the current density of 10mA/cm2 is 352 mV.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide, which is characterized in that be by nickel cobalt sulfide nanometer sheet packet
Cover composite material made of cobalt acid zinc nano wire.
2. the compound analysis oxygen elctro-catalyst of metal oxide-sulfide according to claim 1, which is characterized in that the cobalt
The diameter of sour zinc nano wire is 60nm~120nm.
3. the compound analysis oxygen elctro-catalyst of metal oxide-sulfide according to claim 1, which is characterized in that the nickel
Cobalt sulfide nanometer sheet with a thickness of 100nm~150nm.
4. the preparation method of any compound analysis oxygen elctro-catalyst of claims 1 to 3, which is characterized in that use hydro-thermal reaction
Cobalt acid zinc nano wire is synthesized first, in conjunction with electrochemical deposition sulfide nanometer sheet, coats cobalt acid zinc with nickel cobalt sulfide nanometer sheet
Nano wire prepares the compound analysis oxygen elctro-catalyst of metal oxide-sulfide with nucleocapsid clad structure.
5. the preparation method according to claim 4, which comprises the steps of:
S1. the mixed aqueous solution for configuring zinc nitrate, cobalt nitrate, ammonium fluoride and urea, is transferred in hydro-thermal reaction container, is added
A piece of clean nickel foam heats 4~24 hours at 100~150 DEG C, obtains the nickel foam that growth has presoma, and taking-up is washed
After net drying, it is heat-treated 1.5~24 hours for 350~500 DEG C in air, obtains cobalt acid zinc nano wire；
S2. with cyclic voltammetry electrochemical deposition nickel cobalt sulfide nanometer sheet in three-electrode system: the growth that step S1 is obtained
There is the nickel foam of cobalt acid zinc nanometer sheet as working electrode, graphite rod is auxiliary electrode, and silver/silver chloride electrode is reference electrode；
Electrolyte is cobalt nitrate, nickel nitrate and thiocarbamide；Nickel foam clean dry is taken out after reaction, obtains nickel cobalt sulfide nanometer sheet cladding
Cobalt acid zinc nano wire, i.e., the described compound analysis oxygen elctro-catalyst of metal oxide-sulfide.
6. preparation method according to claim 5, which is characterized in that in mixed aqueous solution described in step S1, zinc nitrate and
The molar ratio of cobalt nitrate is 1:1~3；In the mixed aqueous solution, the molar ratio of ammonium fluoride and urea is 1:2~3.
7. preparation method according to claim 5, which is characterized in that in mixed aqueous solution described in step S1, zinc nitrate: nitre
Sour cobalt: ammonium fluoride: the molar ratio of urea is 1:1~3:2:4~6.
8. preparation method according to claim 5, which is characterized in that the electric potential scanning model of cyclic voltammetry described in step S2
It encloses for -1.2V~0.2V, scanning speed is 4~6mV/s, and scanning circle number is 10~20 circles；In the electrolyte, cobalt nitrate: nitre
Sour nickel: the molar ratio of thiocarbamide is 1:1~2:10~50.
9. the elctro-catalyst being prepared according to any the method for claim 4~8.
10. application of the compound analysis oxygen elctro-catalyst of metal oxide-sulfide described in claim 1 in terms of water electrolysis hydrogen production.
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| CN110152692A (en) * | 2019-06-24 | 2019-08-23 | 安徽师范大学 | Three-dimensional cobalt acid nickel@cobaltous selenide (II) nano needle arrays composite material and preparation method and application |
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| CN114457388A (en) * | 2022-01-25 | 2022-05-10 | 南阳师范学院 | Electrolyzed water oxygen evolution anode and preparation method thereof |
| CN114457388B (en) * | 2022-01-25 | 2024-02-13 | 南阳师范学院 | Electrolytic water oxygen evolution anode and preparation method thereof |
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