CN110237847A - Elctro-catalyst, electrode and its preparation method and application - Google Patents
Elctro-catalyst, electrode and its preparation method and application Download PDFInfo
- Publication number
- CN110237847A CN110237847A CN201910662246.8A CN201910662246A CN110237847A CN 110237847 A CN110237847 A CN 110237847A CN 201910662246 A CN201910662246 A CN 201910662246A CN 110237847 A CN110237847 A CN 110237847A
- Authority
- CN
- China
- Prior art keywords
- iron
- elctro
- catalyst
- electrode
- combined oxidation
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 229910001145 Ferrotungsten Inorganic materials 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 9
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 7
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 30
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- 239000000126 substance Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010411 electrocatalyst Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 239000007769 metal material Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 40
- 229910052760 oxygen Inorganic materials 0.000 description 28
- 239000001301 oxygen Substances 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
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- 229910021642 ultra pure water Inorganic materials 0.000 description 14
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- 238000004519 manufacturing process Methods 0.000 description 13
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
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- 239000000843 powder Substances 0.000 description 9
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910020350 Na2WO4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- 230000006872 improvement Effects 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910005507 FeWO4 Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
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- 238000001237 Raman spectrum Methods 0.000 description 2
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- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
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- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- GXBKELQWVXYOPN-UHFFFAOYSA-N iron tungsten Chemical compound [W][Fe][W] GXBKELQWVXYOPN-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention relates to a kind of elctro-catalysts, electrode and its preparation method and application, the elctro-catalyst is ferrotungsten combined oxidation system, in the combined oxidation system, iron, wolfram element molar ratio be 0.3:1~19:1, it include iron tungstate in the combined oxidation system, and one of optionally include iron oxide, tungsten oxide or FeOOH or a variety of.
Description
Technical field
The invention belongs to new energy and environmental technology field, are related to the production neck of elctro-catalyst and elctro-catalyst electrode
Domain, in particular to the preparation of a kind of the ferrotungsten combined oxidation system elctro-catalyst and its electrode of the novel non-non- cobalt system of nickel and answer
With.
Background technique
Utilize regenerated electric power source Jiang Shui, carbon dioxide (CO2) etc. small molecules be converted into hydrogen (H2), hydrocarbon etc.
Energy storage carrier is a kind of new energy development mode with broad prospect of application, by with the power technologies such as solar power generation
Coupling is, it can be achieved that " artificial photosynthesis " produce clean energy resource fuel, while ring caused by combustion of fossil fuel can be effectively relieved
The decline of border air quality and climate change problem.Electrochemical energy storage is reacted, either decomposition water H2Or reduction CO2At
CO、CH4Equal carbon group compounds, corresponding anode surface will all carry out water decomposition and produce O2Half-reaction, and it is whole for producing oxygen reaction
Crucial rate constants are reacted, the performance of electrocatalyst materials will directly affect the whole efficiency of full response.
In some fields, such as carrying out electrolysis water using electrocatalytic method is to carry out one kind of production of renewable energy resources and storage
Promising approach.Elctro-catalyst in electrocatalytic method need to discharge oxygen in reaction (OER) carry out slow dynamics into
Row accelerates, the transfer of four electronics and four protons involved in this process.In existing technology, it is catalyzed using noble metal base
Agent, such as IrOxAnd RuOx, these catalyst are all active to OER in acid and alkaline electrolyte, but the height of these materials itself
Cost limits their extensive use, and the cost performance of catalyst and efficiency be not high in practical applications, therefore opens
It sends out efficient under conditions of use, stable base metal production oxygen elctro-catalyst and has become research crucial in field of new energy applications
Hot spot.
In further research, it has been found that under alkaline condition, metal (oxygen) hydroxide containing Fe, such as
NiFeOxHyAnd CoFeOxHy, it is most effective OER catalyst.Bibliography 1 and bibliography 2 are reported respectively this kind of
In elctro-catalyst, the site Fe plays key effect, even if NiOxHyAnd CoOxHyIn micro Fe incorporation can also significantly improve OER
Therefore activity can show excellent production oxygen performance and lower production oxygen overpotential in alkaline electrolyte.But it is such still
So there are following problems: having also discovered using NiFeOxHyAnd CoFeOxHyWhen equal materials are produced, produces oxygen electric current and be easy
It is influenced by iron ion dissolution, leading to elctro-catalyst, stability is insufficient when used for a long time.
Meanwhile other research achievements are also reported in other research, for example, bibliography 2 discloses a kind of iron
The wolframic acid cobalt nanorod elctro-catalyst of ion doping, by the way that iron ion doping is optimized it to hydrogen-oxygen into wolframic acid cobalt nanorod
The suction-operated of radical ion, to improve its electro catalytic activity.But it in view of the analysis oxygen performance of cobaltous tungstate is weaker, and only relies on
Suction-operated and be also likely to be limited to the improvement degree of catalysis.
Therefore, further room for improvement is still had for the research of existing electrochemical catalyst in this field, considered
To important function of the Fe in OER new active Fe base catalysis is designed and developed by replacing Co and Ni with other metal species
Agent has huge potentiality.
Bibliography:
Bibliography 1:S.Klaus, Y.Cai, M.W.Louie, L.Trotochaud, A.T.Bell, J.Phys.Chem.C
2015,119,7243-7254；
106179392 B of bibliography 2:CN.
Summary of the invention
Problems to be solved by the invention
It is the problem of for above-mentioned this field, a kind of novel non-technical problem to be solved by the present invention lies in providing
Nickel, the iron-based combined oxidation system elctro-catalyst of non-cobalt system and preparation method thereof and the electrode based on the elctro-catalyst.In this way
Elctro-catalyst or elctro-catalyst electrode can when in use, especially when preparing oxygen by electrolysis water, corresponding production oxygen
Electrode shows the overpotential and stability when used for a long time of good production oxygen performance, improvement in alkaline electrolyte.
The solution to the problem
Inventor concentrates on studies through the invention, it is found that implementation by following technical solution is able to solve above-mentioned technology
Problem:
[1] for present invention firstly provides a kind of electrocatalyst composition, the composition is ferrotungsten combined oxidation system,
In the combined oxidation system, iron, wolfram element molar ratio be 0.3:1~19:1, include wolframic acid in the combined oxidation system
Iron, and, optionally include one of iron oxide, tungsten oxide or FeOOH or a variety of.
[2] composition according to [1], the ferrotungsten combined oxidation system are obtained by hydrothermal synthesis method；Iron, tungsten
The molar ratio of element is 1:1~5:1.
[3] in turn, the present invention also provides a kind of preparation methods of electrocatalyst composition comprising following steps by:
Source of iron substance and tungsten source substance are formed mixed system, the source of iron substance and tungsten source by the step of precursor liquid mixes
In substance, iron, wolfram element molar ratio be 0.3:1~19:1；
Hydrothermal synthesis step, the temperature by above-mentioned mixed system at 160 DEG C or more are handled.
[4] method according to [3], the source of iron substance are selected from divalent iron salt or its hydrate, and the tungsten source is selected from
Tungstates or its hydrate.
[5] method according to [3] or [4] further includes the pH that source of iron substance and tungsten source substance are formed to mixed system
Value is adjusted to the step of 4.5~7.5 range.
[6] is according to the described in any item methods in [3]~[5], and treatment temperature is 170~190 in the hydrothermal synthesis step
℃。
[7] is in addition, the present invention also provides a kind of elctro-catalyst electrode, the electrode includes:
Conductive substrates；
It is present in the elctro-catalyst on the conductive substrates at least partly surface,
The elctro-catalyst is ferrotungsten combined oxidation system, in the combined oxidation system, iron, wolfram element molar ratio be
0.3:1~19:1,
It include iron tungstate in the combined oxidation system, and, optionally include iron oxide, tungsten oxide or FeOOH
One of or it is a variety of.
[8] electrode according to [7], the conductive substrates are selected from carbon material or metal material, the metal material
Preferably gold, platinum, palladium or their alloy.
[9] electrode according to [7] or [8], the ferrotungsten combined oxidation system are obtained by hydrothermal synthesis method；Iron,
Wolfram element mole be 1:1~5:1.
[10] in addition, the present invention also provides it is a kind of will the above described in any item electrodes in [7]~[9] for electrolysis water,
Restore CO2And reduction preparation N2Purposes.
The effect of invention
Through the implementation of the above technical solution, the present invention can be realized following technical effect:
It is living that elctro-catalyst provided by the present invention and electrode based on the elctro-catalyst can show excellent catalysis
Property, in particular, elctro-catalyst of the invention shows quick OER dynamics under alkaline condition.
In addition, elctro-catalyst provided by the present invention is also able to maintain permanent stability in use when used for a long time.
Detailed description of the invention
Fig. 1: the relational graph of production the oxygen current density and current potential of different ferrotungsten molar ratio combined oxidation system electrodes.
Fig. 2: Fe prepared by embodiment 13W1Ferrotungsten combined oxidation system electrode is in 10mA/cm2Constant current density condition
Under, produce the relational graph of oxygen overpotential and time.
Fig. 3: Fe prepared by embodiment 13W1Ferrotungsten combined oxidation system electrode, by the constant-current response of different time
The relational graph of current density and current potential afterwards.
Fig. 4: four kinds of sample (Fe1W3Sample, Fe1W1Sample, Fe3W1Sample and Fe0.95W0.05Sample) structural characterization:
(a): XRD spectrum；
(b): Raman map；
(c), (d): energy dispersion X-ray spectrum (EDS) element mapping graph and transmission electron microscope (TEM) image.
Specific embodiment
Hereinafter, being described in detail for the contents of the present invention.The explanation of documented technical characteristic is based on this hair below
Bright representative embodiment, specific example and carry out, but the present invention is not limited to these embodiments, specific example.It needs
It is noted that
In this specification, the numberical range for using " numerical value A~numerical value B " to indicate refers to the range comprising endpoint value A, B.
In this specification, " non-nickel, non-cobalt " is indicated in the preparation process of elctro-catalyst of the invention, and does not use
Compound or raw material containing nickel or cobalt, or indicate, nickel or cobalt element in elctro-catalyst of the invention only with miscellaneous
Matter form exists or their content is lower than the detectable limit of common detection device or less.
It in this specification, is such as not particularly illustrated, then " % " indicates mass percentage.
In this specification, use " OER " as " producing oxygen reaction " abbreviation.
In this specification, the meaning for using " can with " to indicate includes carrying out certain processing and handling two without certain
The meaning of aspect.
In this specification, " optional " or " optionally " refer to that the event next described or situation can occur or can not send out
It is raw, and the description includes the case where that there is a situation where do not occur with the event for the event.
In this specification, mentioned " some specific/preferred embodiments ", " other specific/preferred embodiment party
Case ", " embodiment " etc. refer to described specific factor related with the embodiment (for example, feature, structure, property and/
Or characteristic) it include that and may be present in other embodiments or can not at least one embodiment described herein
It is present in other embodiments.In addition, it should be understood that the element can be combined in any suitable manner in various embodiments
In.
<first aspect>
In the first aspect of the invention, a kind of electrocatalyst composition is provided, the composition is ferrotungsten composite oxygen
Change system, in the combined oxidation system, iron, wolfram element molar ratio be 0.3:1~19:1, wrapped in the combined oxidation system
Iron tungstate is included, and, optionally include one of iron oxide, tungsten oxide or FeOOH or a variety of.
As the source of ferro element of the invention, wolfram element, there is no particular limitation, in general, can be the salt containing iron
And the salt containing tungsten.
For the salt containing iron that can be used of the present invention, in some specific embodiments, can be used containing
The inorganic salts such as hydrochloride, sulfate, the nitrate of iron, or use its acylate such as ferric acetate.It is some excellent in the present invention
In the embodiment of choosing, ferro element exists in the raw material containing iron that the present invention uses with the valence state of positive divalent.In addition, in this hair
In other bright specific embodiments, above-mentioned these can also be used to contain the hydrate of the salt of iron, such as can be two
Hydrate is to decahydrate.Preferably, the salt of the invention containing iron can be enumerated are as follows: molysite be green vitriol,
Iron dichloride tetrahydrate or six ferrous sulfate hydrate ammoniums.The above-mentioned molysite of the present invention can be used alone or use two kinds or more
Mixture.
For the salt containing tungsten that can be used of the present invention, can be used various tungstates, such as potassium tungstate, sodium tungstate or
One of ammonium tungstate is a variety of.
In the present invention, raw material can be passed through for the proportion of ferro element and wolfram element in above-mentioned combined oxidation system
Proportion is to be adjusted.In a preferred embodiment of the present invention, in the combined oxidation system, the molar ratio of iron, wolfram element
For 1:1~10:1, more preferably 1:1~8:1, further preferably 1.5:1~5:1.
Inventor's discovery, by controlling the molar ratio of iron and wolfram element in combined oxidation system of the invention, energy
Enough in the use process of elctro-catalyst, reduce in the past since the active metallic element that elctro-catalyst occurs is dissolved in solution or electricity
Liquid is solved, so that the drawbacks of electro-catalysis stability lowers.
In addition, not including the gold with catalytic activity in addition to iron and wolfram element in elctro-catalyst used in the present invention
Belong to element, on the one hand, as previously mentioned, integrally seeing if extraly there are the metallic elements such as catalytic activity Ir or Ru using some
It may cause the rising of production cost, but electro-catalysis effect electro-catalysis efficiency is not obviously improved, while at some
Under part, since the stability that the addition of these metallic elements may cause script of the present invention reduces.On the other hand, described later
Hydro-thermal method synthetic catalyst when, it is also possible to cause unnecessary trouble.
In electrocatalyst composition of the invention, in some specific embodiments, mainly using iron tungstate as master
Ingredient, meanwhile, it can also include iron oxide, tungsten oxide or hydroxyl oxygen in composition in other specific embodiment
Change the hydro-thermal reactions products such as iron.
<second aspect>
In the second aspect of the present invention, the preparation side of electrocatalyst composition in a kind of above-mentioned<first aspect>is provided
Method.In some specific embodiments, the preparation method includes: the step of precursor liquid mixes, by source of iron substance and tungsten source
Substance forms mixed system, in the source of iron substance and tungsten source substance, iron, wolfram element molar ratio be 0.3:1~19:1；And
The step of hydrothermal synthesis, the temperature by above-mentioned mixed system at 160 DEG C or more are handled.
The step of precursor liquid mixes
In the present invention, the step of mixing for precursor liquid, there is no particular limitation.In some specific embodiments,
The precursor liquid of elctro-catalyst of the present invention can be obtained by coprecipitation.
The present invention, containing iron or containing the salt of tungsten, forms mixed system using defined above, should during, can be with
It is realized by the form of aqueous solution.For the water in aqueous solution, electricity is urged from elctro-catalyst purity and reduction interfering ion
The influence angle of agent catalytic effect and stability in use considers, ultrapure water is used in specific embodiment of the present invention,
The ultrapure water refers to that resistivity reaches the water of 18M Ω ﹒ cm (25 DEG C) or more.
Above-mentioned mixed system can carry out in the arbitrary container in this field, it is preferred that can be auxiliary by agitating device
Mixing is helped, common such stirring can be mechanical stirring or magnetic agitation.
The forming method of mixed system will preferably be contained in the present invention from the point of view of improving elctro-catalyst activity
Molysite and tungsten salt are respectively formed aqueous solution, then pour into the aqueous solution containing tungsten salt containing in molysite aqueous solution, are mixed
Merge stirring.
In order to promote the progress of coprecipitation, in a preferred embodiment of the present invention, above-mentioned mixed system formed with
Afterwards, especially in Precipitation, the pH value of system can be adjusted.It can be used and add acid or alkali into mixed system
Method adjust system pH, the sour such as hydrochloric acid or sulfuric acid that can be used, the alkali that can be used can be the hydrogen-oxygen of alkali metal
Compound etc..In some specific embodiments of the present invention, the above-mentioned pH value of mixed system is adjusted to 4.5~7.5 ranges
The step of hydrothermal synthesis
The present invention carries out continuing hydrothermal synthesis method after coprecipitation finishes under above-mentioned mixed system.
In some specific embodiments of the invention, the mixture that coprecipitation can be obtained is transferred to hydro-thermal conjunction
At in device.For such hydrothermal synthesis device, there is no particular limitation, and pyroreaction kettle can be used.
After the mixture for obtaining above-mentioned coprecipitation is transferred to hydrothermal synthesis device, device is heated.This hair
In bright, from improve reaction efficiency and improve elctro-catalyst stability angle consider, the heating and temperature control 160 DEG C with
On, preferably 170 DEG C or more, it is highly preferred that heating temperature of the invention be 170 DEG C~190 DEG C, further preferably 175~
185℃.For the time of hydro-thermal reaction, in some specific embodiments the hydro-thermal reaction time can for 1 hour or more and
20 hours hereinafter, preferably 1~10 hour.When present invention finds carrying out hydrothermal synthesis under the above conditions, and under being conducive to
Iron tungstate (FeWO described in text4) formation.
Post-processing step
After above-mentioned hydrothermal synthesis step carries out, post-processing step can be carried out, is not had for these steps itself
It is special to limit, it can be using the methods of filtering, dry, grinding.
Preferably, when being dried, can 90 DEG C or more at a temperature of carry out.Also, some specific
Embodiment in, can be using carrying out the step of the drying under conditions of decompression or inert gas shielding.
For the obtained solid matter of drying process, the means such as grinding can be used and obtain elctro-catalyst powder.
Iron/wolfram element ratio in elctro-catalyst
In the present invention, in the elctro-catalyst obtained through the above steps, by the control of raw material proportioning, by final product
Middle iron/wolfram element molar ratio control is in 0.3:1~19:1, preferably 1:1~10:1, more preferably 1:1~8:1, further
Preferably 1.5:1~5:1.
In the present invention, there is the FeW composite material of different Fe/W molar ratios by using hydrothermal synthesis method synthesis.Below will
By to several sample (Fe1W3Sample, Fe1W1Sample, Fe3W1Sample and Fe0.95W0.05Sample) it is specifically described.
XRD diagram shown in Fig. 4 (a) shows Fe3W1And Fe1W1With the FeWO of wolframite structure present in sample4
Phase.When initial iron/wolfram element molar ratio is less than 1:3, there is the WO crystallized3Phase.Fe3W1And Fe1W1Sample Raman spectrum (see
Fig. 4 (b)) in 882cm-1And 686cm-1Place shows strong bands of a spectrum, this is attributed to FeWO4End W in the wolframite structure of phase
The vibration of=O and W-O-W key.It is reflected by transmission electron microscope (TEM) image and energy dispersion X-ray spectrum (EDS) element
It penetrates figure (in referring to fig. 4 (c), (d)) and shows that all elements are evenly dispersed in mixed oxide compound.High-resolution TEM
Image further demonstrates Fe3W1Polycrystalline FeWO in sample4The formation of phase.In FeWO4Typical wolframite structure in, Fe2+With
W6+Ion all with O2-Ion forms octahedral coordination, and corresponding octahedra edge [100] direction successively arranges.With molecule ruler
Degree obtains well dispersed Fe and W atom, and present invention finds this Direct Bondings between both substances to be believed to mention
The catalytic activity of high FeW mixed complex and the permanent stability for being conducive to electro catalytic activity.
It is therefore contemplated that advantageously containing wolframic acid ferrous components, FeWO in electrocatalyst composition of the invention4, this
The component content of sample is preferably 50% or more, more preferably 70% or more, further preferably 80% or more.Additionally, optionally,
The ingredients such as iron oxide, tungsten oxide and hydroxyl iron hydroxide can also be contained.
Typical method
It can be with following steps as the typical preparation method that elctro-catalyst of the present invention may be implemented:
(1) ratio for being 1:3~19:1 according to the molar ratio of two kinds of elements of ferrotungsten, the mole for fixing ferro element are
3mmol weighs molysite and tungsten salt respectively, and is dissolved in 7.5mL ultrapure water (18.2M Ω cm) respectively, uses magneton uniform stirring 10
Minute, the precursor liquid of tungsten salt is quickly poured into the solution containing molysite, obtains brown mixture within uniform stirring 0.5 hour；
(2) under stirring conditions, the NaOH solution of a certain amount of 2mol/L is added dropwise into mixed liquor obtained in step (1)
Or the H of 1mol/L2SO4Solution adjusts pH to 6；
(3) mixed liquor made from step (2) is transferred in 30mL Teflon reaction kettle, under the conditions of 180 DEG C react 1~
After 10h, cooled to room temperature with ultrapure water and washes of absolute alcohol and is centrifugated respectively, dry under the conditions of 100 DEG C
After grinding at room temperature, ferrotungsten combined oxidation system dusty material is made in 12h.
<third aspect>
The third aspect of the present invention provides a kind of electro catalytic electrode and preparation method thereof.Elctro-catalyst electricity of the invention
Pole, comprising: conductive substrates；It is present in the elctro-catalyst on the conductive substrates at least partly surface, the elctro-catalyst is
The elctro-catalyst of above-mentioned<first aspect>or<second aspect>preparation.
Conductive substrates
In the present invention, by conductive substrates to provide the carrier of elctro-catalyst, and make elctro-catalyst and the carrier it
Between form effective Ohmic contact.
For the material of conductive substrates, there is no particular limitation by the present invention, can be selected from metal material, the non-gold of electric conductivity
Belong to material.In some specific embodiments of the present invention, for metal material, can selected from gold, nickel, platinum, palladium or they
Alloy.In addition, the nonmetallic materials for conductive substrates that can be used in the present invention can be selected from graphite, other carbon materials
The carbon materials or electro-conductive glass etc. such as material.
In some specific embodiments of the present invention, conductive substrates be can be by these metals or nonmetallic materials
The substrate of the shapes such as the sheet or plate of preparation, for example, can be graphite plate/piece, FTO sheet glass (SnO2: F), glass carbon plate/piece
Or carbonaceous conductive paper etc..The specific size of sheet or plate is not particularly limited, can be adjusted according to actual needs or
Selection.
Also there is no particular limitation for surface or internal structure for above-mentioned sheet or platy substrate, for example, can have
The surface of certain roughness or surface or internal structure with porous structure.In some specific embodiments of the invention
In, the metal foam body with plate or sheet can be used for example as conductive substrates, such as nickel foam.Other one
In a little specific embodiments, conductive substrates of the invention are also possible to cellular skeleton structure, typically, can pass through metal
Or non-metallic fibers form cellular skeleton structure.The skeleton structure can be with certain thickness plate or sheet knot
Structure.It is, for example, possible to use the aggregations of braiding or non-woven carbon fiber as conductive substrates material, by processing or cutting
Cutting preparation has the isostructural conductive substrates of such as plate or sheet.
In addition, can also have multilayered structure in conductive substrates of the invention, in some specific embodiments, this
The structure of sample can be supporting layer/conductive layer double-layer structure, or can be supporting layer/adhesive layer/conductive layer three-layered node
Structure, or can be the structures such as conductive layer/supporting layer/conductive layer, conductive layer/adhesive layer/supporting layer/adhesive layer/conductive layer.It is right
In can be used for supporting layer of the invention, it is not particularly limited, it can be selected from conductive or non-conducting material.It can be enumerated as
High molecular material, glass, metal, semiconductor and composite material etc..For adhesive layer, common adhesiveness group can be used
Point, such as the bonding such as high molecular epoxy resin, phenolic resin, polyurethane resin, polyacrylic acid (ester), polyolefin, silicon rubber
Agent.For conductive layer, metal or the preparation of electrically conductive, non-metallic material described above can be used.Multilayered structure of the present invention
Conductive substrates can be prepared by way of conventional, for example, can be obtained by way of each layer is laminated, some specific
In embodiment, can also the method on supporting layer using deposition form conductive layer, such deposition method include solution from
Assembling, physical vapor deposition, magnetron sputtering, chemistry CVD etc..The considerations of for stability in use, durability and recuperability, this hair
In bright preferred embodiment, above-mentioned adhesive layer is not used in the conductive substrates of multilayered structure.In addition, in the present invention
Ito glass, TOC (Transparent can be used in the preferred embodiment of conductive substrates in to(for) multilayered structure
Conductive Oxide) glass, these conductive substrates can be commercially available.
Meanwhile surprisingly, it although these conductive substrates disclosed above can be used, further studies
It has been shown that, the metal gold substrate that the use of metallic substrates, especially gold are formed, can further improve elctro-catalyst of the invention
Activity.Therefore, the conductive layer on preferred conductive substrates or conductive substrates surface is selected from the present invention: golden disk substrate, gold
Piece substrate or gold thin film substrate.
In some specific embodiments of the present invention, golden membranous layer can be formed on arbitrary substrate by sputtering method,
For the thickness of the golden membranous layer, there is no particular limitation, such as can be 100~2000nm.Optionally the golden film surface is carried out
Roughening treatment.
In other some specific embodiments, gold and other metal (such as silver and nickel) sputtering methods can be used,
Alloy film layer is formed on substrate, then by etch, other above-mentioned alloys is dissolved and are removed, porous gold thin film is formed.
Electrocatalyst layers forming method
For the forming method of electrocatalyst layers, there is no particular limitation.In some specific embodiments of the invention
In, allow existing either physically or chemically to be formed using various.Deposition method, which can be enumerated, to be had: solution self assembly, gas phase/liquid
Mutually the methods of deposition, ink dispersion method, spray coating method, physical vapor deposition, magnetron sputtering, chemistry CVD are deposited.
In some preferred embodiments of the present invention, elctro-catalyst can be formed in conduction by the method for dispersion liquid
Property substrate surface.From the point of view of improving dispersibility, the present invention disperses elctro-catalyst in alcohols solvent, it is preferable that point
It dissipates in isopropanol.Also, for the considerations of improving dispersion effect, contain ultrapure water and dispersing aid in dispersion liquid.Preferably,
These dispersing aiies can be fluorine-containing dispersing agent (such as Nafion).In some specific embodiments of the present invention, dispersion liquid
In, the dosage (volume) of alcohols solvent and ultrapure water is than being 1:1~49:1, preferably 20:1~45:1.
In some specific embodiments, the elctro-catalyst dispersant liquid drop of iron content tungsten oxide is added to the conduction of gold formation
Property substrate surface, it is different according to the surface areas of the conductive substrates and use the dispersion liquids of different volumes, such as can be 5~80
μ L etc..
It optionally, can be using dry, deaeration after forming electrocatalyst layers in conductive substrates by the above method
Etc. processes post-processed.
<fourth aspect>
In the fourth aspect of the present invention, provide a kind of by elctro-catalyst provided by the present invention or elctro-catalyst electrode
For electrolysis water, reduction CO2And reduction preparation N2Purposes.
For the concrete scenes of these purposes, there is no particular limitation, can be the preparation of clean energy resource, is also possible to water
It pollutes, the processing or purification of atmosphere pollution.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1Fe3W1The preparation of sample
(1) 1.167g (NH is weighed4)2Fe(SO4)2·6H2O and 0.330g Na2WO4·2H2O is dissolved in 7.5mL respectively
In 18.2M Ω cm ultrapure water, using magneton uniform stirring 10min, by Na2WO4·2H2O solution is quickly poured into containing the molten of molysite
Liquid continues after stirring 0.5h, the NaOH solution of a certain amount of 2mol/L or the H of 1mol/L is added dropwise into mixture solution2SO4Solution
Adjust pH to 6.
(2) step (1) mixture solution is transferred in 30mL Teflon reaction kettle, is packaged in stainless steel lining, 180
After reacting 5h under the conditions of DEG C, cooled to room temperature, respectively with ultrapure water and washes of absolute alcohol and in 8000 turns/min condition
Lower centrifuge separation 5min, centrifugate dry 12h under the conditions of 100 DEG C, after grinding, is made Fe3W1Powder sample.
(3) Fe prepared in step (2) is weighed3W1Powder sample 2.5mg, is separately added into the isopropanol of 970 μ L, and 20 μ L are super
The Nafion solution of pure water and 10 μ L 5% is made 1mL and contains Fe3W1The particle dispersion of sample after being ultrasonically treated 0.5h, measures
It is 1 × 1cm that 40 μ L dispersant liquid drops, which are added to area,2, thickness 100nm Au film substrate on.After dispersion liquid is dry, melting is used
Indium welds aluminum conductor and substrate, and with epoxy resin AB glue encapsulated electrode, obtains Fe3W1Produce oxygen electrode.
By Fe3W1Electrode is put into three-electrode electro Chemical device, selects Hg/HgO electrode for reference electrode, platinum electrode conduct
To electrode, for 1mol/L KOH solution as reaction electrolyte, it is the pure O of 5sccm that flow is used before testing2It is bubbled into solution
20min is continually fed into O in test2, cyclic voltammetry voltage range of choice is 0-0.75VHg/HgO, test result such as Fig. 1 institute
Show, the electrode of preparation is more than 1.50VRHEAfter start generate produce oxygen electric current, in 10mA/cm2Current density condition under, produce oxygen
Overpotential is 0.40V.Stability test result is shown in Fig. 2, Fe3W1Electrode is in 10mA/cm2It, can be steady under conditions of constant current density
Surely 200h is run.After stability test 50,100,150,200h replacement KOH electrolyte, Fe3W1The cyclic voltammetric performance of electrode is shown in
Fig. 3 passes through the stability test of 200h, Fe as the result is shown3W1Electrode is in 10mA/cm2Under overpotential be down to 0.38V.
2 Fe of embodiment1W1The preparation of sample
(1) 1.176g (NH is weighed4)2Fe(SO4)2·6H2O and 0.990g Na2WO4·2H2O is dissolved in 7.5mL respectively
In 18.2M Ω cm ultrapure water, using magneton uniform stirring 10min, by Na2WO4Solution is quickly poured into the solution containing molysite, continues
After stirring 0.5h, the NaOH solution of a certain amount of 2mol/L or the H of 1mol/L are added dropwise into mixture solution2SO4Solution adjust pH to
6。
(2) step (1) mixture solution is transferred in 30mL Teflon reaction kettle, is packaged in stainless steel lining, 180
After reacting 5h under the conditions of DEG C, cooled to room temperature, respectively with ultrapure water and washes of absolute alcohol and in 8000 turns/min condition
Lower centrifuge separation 5min, centrifugate dry 12h under the conditions of 100 DEG C, after grinding, is made Fe1W1Powder sample.
(3) Fe prepared in step (2) is weighed1W1Powder sample 2.5mg, is separately added into the isopropanol of 970 μ L, and 20 μ L are super
The Nafion solution of pure water and 10 μ L 5% is made 1mL and contains Fe1W1The particle dispersion of sample after being ultrasonically treated 0.5h, measures
It is 1 × 1cm that 40 μ L dispersant liquid drops, which are added to area,2, thickness 100nm Au film substrate on.After dispersion liquid is dry, melting is used
Indium welds aluminum conductor and substrate, and with epoxy resin AB glue encapsulated electrode, obtains Fe1W1Produce oxygen electrode.
By Fe1W1Electrode is put into three-electrode electro Chemical device, selects Hg/HgO electrode for reference electrode, platinum electrode conduct
To electrode, for 1mol/L KOH solution as reaction electrolyte, it is the pure O of 5sccm that flow is used before testing2It is bubbled into solution
20min is continually fed into O in test2, cyclic voltammetry voltage range of choice is 0-0.75VHg/HgO, test result such as Fig. 1 institute
Show, the Fe of preparation1W1Electrode is more than 1.50VRHEAfter start generate produce oxygen electric current, in 10mA/cm2Current density condition under,
Production oxygen overpotential is 0.42V.
1 Fe of comparative example2O3The preparation of sample
(1) 1.176g (NH is weighed4)2Fe(SO4)2·6H2O is dissolved in 15mL 18.2M Ω cm ultrapure water, equal using magneton
After even stirring 0.5h, the NaOH solution of a certain amount of 2mol/L or the H of 1mol/L are added dropwise into solution2SO4Solution adjusts pH to 7.
(2) step (1) solution is transferred in 30mL Teflon reaction kettle, is packaged in stainless steel lining, in 180 DEG C of conditions
After lower reaction 5h, cooled to room temperature is centrifuged with ultrapure water and washes of absolute alcohol and under the conditions of 8000 turns/min respectively
5min is separated, after grinding, Fe is made in centrifugate dry 12h under the conditions of 100 DEG C2O3Powder sample.
(3) Fe prepared in step (2) is weighed2O3Powder sample 2.5mg, is separately added into the isopropanol of 970 μ L, and 20 μ L are super
The Nafion solution of pure water and 10 μ L 5% is made 1mL and contains Fe2O3The particle dispersion of sample after being ultrasonically treated 0.5h, measures
It is 1 × 1cm that 40 μ L dispersant liquid drops, which are added to area,2, thickness 100nm Au film substrate on.After dispersion liquid is dry, melting is used
Indium welds aluminum conductor and substrate, and with epoxy resin AB glue encapsulated electrode, obtains Fe2O3Produce oxygen electrode.
Obtained Fe2O3It produces oxygen electrode to be put into three-electrode electro Chemical device, selects Hg/HgO electrode for reference electrode, platinum
Electrode is as to electrode, and for 1mol/L KOH solution as reaction electrolyte, it is the pure O of 5sccm that flow is used before testing2Into solution
It is bubbled 20min, is continually fed into O in test2, cyclic voltammetry voltage range of choice is 0-0.8VHg/HgO, test result such as Fig. 1
It is shown, Fe2O3Electrode is more than 1.55VRHEAfter start generate current-responsive, in 1.70VRHECurrent density be lower than 5mA/cm2。
2 WO of comparative example3The preparation of sample
(1) 1.979g Na is weighed2WO4·2H2O is dissolved in 15mL 18.2M Ω cm ultrapure water, uses magneton uniform stirring
After 0.5h, a certain amount of dense HCl solution is added dropwise into solution and adjusts pH to 1.6.
(2) step (1) solution is transferred in 30mL Teflon reaction kettle, is packaged in stainless steel lining, in 180 DEG C of conditions
After lower reaction 5h, cooled to room temperature is centrifuged with ultrapure water and washes of absolute alcohol and under the conditions of 8000 turns/min respectively
5min is separated, after grinding, WO is made in centrifugate dry 12h under the conditions of 100 DEG C3Powder sample.
(3) WO prepared in step (2) is weighed3Powder sample 2.5mg, is separately added into the isopropanol of 970 μ L, and 20 μ L are ultrapure
The Nafion solution of water and 10 μ L 5% is made 1mL and contains WO3The particle dispersion of sample after being ultrasonically treated 0.5h, measures 40 μ L
It is 1 × 1cm that dispersant liquid drop, which is added to area,2, thickness 100nm Au film substrate on.It, will using molten indium after dispersion liquid is dry
Aluminum conductor and substrate are welded, and with epoxy resin AB glue encapsulated electrode, obtain WO3Electrode.
Obtained WO3Electrode is put into three-electrode electro Chemical device, selects Hg/HgO electrode for reference electrode, and platinum electrode is made
For to electrode, for 1mol/L KOH solution as reaction electrolyte, it is the pure O of 5sccm that flow is used before testing2It is bubbled into solution
20min is continually fed into O in test2, cyclic voltammetry voltage range of choice is 0-0.8VHg/HgO, test result such as Fig. 1 institute
Show, WO3Electrode is more than 1.60VRHEJust start to generate current-responsive afterwards, in 1.70VRHEUnder current density be lower than 1mA/cm2。
In conclusion the present invention compared with iron-based, tungsten base electrode, shows higher production oxygen efficiency, in 10mA/cm2's
Under current density condition, initial production oxygen overpotential is lower than 0.45V, and after 200h constant current test, overpotential is further decreased
To 0.38V, very high production oxygen activity and stability are shown.Raising for stability, inventor have found that this can be attributed to
When being operated using elctro-catalyst of the invention, with the passage for using the time, turning for object phase has occurred in elctro-catalyst
Become.The feature of FeOOH phase can be further proved by Raman spectrum after stability test.It is therefore intended that iron-tungsten mixing oxygen
Compound experienced from crystallization FeWO4To the phase transformation of the oxyhydroxide species of shortrange order.
It should be noted that although describing technical solution of the present invention, those skilled in the art's energy with specific example
Enough to understand, the present invention answers without being limited thereto.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.The selection of term used herein, purport
In principle, the practical application or to the technological improvement in market for best explaining each embodiment, or make the art its
Its those of ordinary skill can understand each embodiment disclosed herein.
Industrial availability
Elctro-catalyst and elctro-catalyst electrode provided by the present invention and preparation method thereof can be applied industrially.
Claims (10)
1. a kind of electrocatalyst composition, which is characterized in that the composition is ferrotungsten combined oxidation system, the combined oxidation
In system, iron, wolfram element molar ratio be 0.3:1~19:1, include iron tungstate in the combined oxidation system, and, optionally
Ground includes one of iron oxide, tungsten oxide or FeOOH or a variety of.
2. composition according to claim 1, which is characterized in that the ferrotungsten combined oxidation system passes through hydrothermal synthesis method
It obtains；Iron, wolfram element molar ratio be 1:1~5:1.
3. a kind of preparation method of electrocatalyst composition, which comprises the steps of:
Source of iron substance and tungsten source substance are formed mixed system, the source of iron substance and tungsten source substance by the step of precursor liquid mixes
In, iron, wolfram element molar ratio be 0.3:1~19:1；
Hydrothermal synthesis step, the temperature by above-mentioned mixed system at 160 DEG C or more are handled.
4. according to the method described in claim 3, it is characterized in that, the source of iron substance be selected from divalent iron salt or its hydrate,
The tungsten source is selected from tungstates or its hydrate.
5. the method according to claim 3 or 4, which is characterized in that further include source of iron substance is formed with tungsten source substance it is mixed
The step of pH value of zoarium system is adjusted to 4.5~7.5 range.
6. according to the described in any item methods of claim 3~5, which is characterized in that treatment temperature in the hydrothermal synthesis step
It is 170~190 DEG C.
7. a kind of elctro-catalyst electrode, which is characterized in that the electrode includes:
Conductive substrates；
It is present in the elctro-catalyst on the conductive substrates at least partly surface,
The elctro-catalyst is ferrotungsten combined oxidation system, in the combined oxidation system, iron, wolfram element molar ratio be 0.3:
1~19:1,
It include iron tungstate in the combined oxidation system, and, it optionally includes in iron oxide, tungsten oxide or FeOOH
It is one or more.
8. electrode according to claim 7, which is characterized in that the conductive substrates are selected from carbon material or metal material,
The metal material is preferably gold, platinum, palladium or their alloy.
9. electrode according to claim 7 or 8, which is characterized in that the ferrotungsten combined oxidation system passes through hydrothermal synthesis
Method obtains；Iron, wolfram element mole be 1:1~5:1.
10. a kind of be used for electrolysis water, reduction CO for the described in any item electrodes of claim 7~92And reduction preparation N2Use
On the way.
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