CN110237847B - Electrocatalyst, electrode, and preparation method and application thereof - Google Patents
Electrocatalyst, electrode, and preparation method and application thereof Download PDFInfo
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- CN110237847B CN110237847B CN201910662246.8A CN201910662246A CN110237847B CN 110237847 B CN110237847 B CN 110237847B CN 201910662246 A CN201910662246 A CN 201910662246A CN 110237847 B CN110237847 B CN 110237847B
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- iron
- electrocatalyst
- electrode
- tungsten
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 10
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 7
- 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 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 6
- JHOPGIQVBWUSNH-UHFFFAOYSA-N iron tungsten Chemical group [Fe].[Fe].[W] JHOPGIQVBWUSNH-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000758 substrate Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007769 metal material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910005507 FeWO4 Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 30
- 239000010410 layer Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 239000006185 dispersion Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
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- 150000003839 salts Chemical class 0.000 description 13
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- GXBKELQWVXYOPN-UHFFFAOYSA-N iron tungsten Chemical compound [W][Fe][W] GXBKELQWVXYOPN-UHFFFAOYSA-N 0.000 description 11
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- 238000000975 co-precipitation Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
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- 239000011521 glass Substances 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
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- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 239000010935 stainless steel Substances 0.000 description 4
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- 150000003657 tungsten Chemical class 0.000 description 4
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- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 229910002451 CoOx Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 150000004683 dihydrates Chemical class 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
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- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group 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
- SVHYQQLGPHVQFY-UHFFFAOYSA-N iron;oxotungsten Chemical compound [Fe].[W]=O SVHYQQLGPHVQFY-UHFFFAOYSA-N 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 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
- 239000011343 solid material Substances 0.000 description 1
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
-
- B01J35/33—
-
- 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
Abstract
The invention relates to an electrocatalyst, an electrode, a preparation method and application thereof, wherein the electrocatalyst is an iron-tungsten composite oxidation system, the molar ratio of iron to tungsten in the composite oxidation system is 0.3: 1-19: 1, the composite oxidation system comprises iron tungstate, and optionally comprises one or more of iron oxide, tungsten oxide or iron oxyhydroxide.
Description
Technical Field
The invention belongs to the technical field of new energy and environmental protection, relates to the production field of an electrocatalyst and an electrocatalyst electrode, and particularly relates to a novel non-nickel and non-cobalt system electrocatalyst of an iron-tungsten composite oxidation system and preparation and application of an electrode thereof.
Background
Using regenerated power source to supply water and carbon dioxide (CO)2) Conversion of small molecules to hydrogen (H)2) The energy storage carriers such as hydrocarbon and the like are a new energy development mode with wide application prospect, can realize 'artificial photosynthesis' to produce clean energy fuel by coupling with electric power technologies such as solar power generation and the like, and can effectively relieve the problems of environmental air quality reduction and climate change caused by fossil fuel combustion. For electrochemical energy storage reactions, either water splitting to produce H2Or reduction of CO2To CO and CH4The carbon-based compounds corresponding to the anode surface are all subjected to water decomposition to produce O2Half reactions, and the oxygen production reaction are the key rate control steps of the overall reaction, and the performance of the electrocatalyst material will directly affect the overall efficiency of the overall reaction.
In some fields, for example, electrolysis of water using electrocatalysis is a promising approach for renewable energy production and storage. The electrocatalysts in electrocatalysis require acceleration of the slow kinetics of Oxygen Evolution Reactions (OERs), which involve the transfer of four electrons and four protons. In the prior art, noble metal-based catalysis is usedAgents, e.g. IrOxAnd RuOxThe catalysts have activity to OER in acid and alkaline electrolytes, but the wide application of the catalysts is limited by the high cost of the materials, and the cost performance and the electric energy utilization efficiency of the catalysts in practical application are not high, so that the development of the non-noble metal oxygen generation electrocatalyst which is efficient and stable under the use condition becomes a key research hotspot in the field of new energy application.
In further studies, Fe-containing metal (oxy) hydroxides, such as NiFeO, were also found under alkaline conditionsxHyAnd CoFeOxHyAre the most effective OER catalysts. Reference 1 and reference 2 report that in this type of electrocatalyst, the Fe site plays a critical role, even though NiOxHyAnd CoOxHyThe doping of a small amount of Fe in the electrolyte can also obviously improve the OER activity, so that the electrolyte can show excellent oxygen generation performance and lower oxygen generation overpotential in the alkaline electrolyte. However, the following problems still remain: it has also been found that the use of NiFeOxHyAnd CoFeOxHyWhen the materials are produced, the oxygen generation current is easily influenced by iron ion dissolution, so that the stability of the electrocatalyst is insufficient when the electrocatalyst is used for a long time.
Meanwhile, other research results have also been reported in other studies, for example, reference 2 discloses an iron ion-doped cobalt tungstate nanorod electrocatalyst which improves its electrocatalytic activity by optimizing its adsorption to hydroxyl ions by doping iron ions into cobalt tungstate nanorods. However, it is considered that cobalt tungstate is poor in oxygen evolution performance and may have a limited degree of improvement in catalysis depending only on adsorption.
Therefore, there is still room for further improvement in the art for the research of existing electrochemical catalysts, and there is a great potential to design and develop new active Fe-based catalysts by replacing Co and Ni with other metal species in consideration of the important role of Fe in OER.
Reference documents:
reference 1: s.klaus, y.cai, m.w.louie, l.Trotochauud, a.t.bell, j.phys.chem.c 2015,119, 7243-;
reference 2: CN 106179392B.
Disclosure of Invention
Problems to be solved by the invention
In view of the problems in the prior art, the technical problem to be solved by the present invention is to provide a novel iron-based composite oxidation system electrocatalyst without nickel and cobalt, a preparation method thereof, and an electrode based on the electrocatalyst. Such an electrocatalyst or electrocatalyst electrode is capable of exhibiting good oxygen generating performance in alkaline electrolytes, improved overpotential and long term use stability when in use, particularly when oxygen is produced by electrolysis of water.
Means for solving the problems
Through intensive research by the inventors of the present invention, it was found that the above technical problems can be solved by implementing the following technical solutions:
[1] the invention firstly provides an electrocatalyst composition which is an iron-tungsten composite oxidation system, wherein the molar ratio of iron to tungsten elements in the composite oxidation system is 0.3: 1-19: 1, the composite oxidation system comprises iron tungstate and optionally one or more of iron oxide, tungsten oxide or iron oxyhydroxide.
[2] The composition according to [1], wherein the iron-tungsten composite oxide system is obtained by a hydrothermal synthesis method; the molar ratio of the iron element to the tungsten element is 1: 1-5: 1.
[3] Furthermore, the present invention also provides a method for preparing an electrocatalyst composition, comprising the steps of:
mixing the precursor solution, namely forming a mixed system by using an iron source substance and a tungsten source substance, wherein the molar ratio of iron to tungsten in the iron source substance to the tungsten source substance is 0.3: 1-19: 1;
a hydrothermal synthesis step, wherein the mixed system is treated at the temperature of more than 160 ℃.
[4] The method according to [3], wherein the iron source substance is selected from a divalent iron salt or a hydrate thereof, and the tungsten source is selected from a tungstate salt or a hydrate thereof.
[5] The method according to [3] or [4], further comprising a step of adjusting the pH value of a mixed system formed by the iron source substance and the tungsten source substance to a range of 4.5 to 7.5.
[6] The method according to any one of [3] to [5], wherein the treatment temperature in the hydrothermal synthesis step is 170 to 190 ℃.
[7] In addition, the present invention provides an electrocatalyst electrode comprising:
a conductive substrate;
an electrocatalyst present on at least a portion of a surface of the electrically conductive substrate,
the electrocatalyst is an iron-tungsten composite oxidation system, the molar ratio of iron to tungsten in the composite oxidation system is 0.3: 1-19: 1,
the composite oxidation system includes iron tungstate, and optionally one or more of iron oxide, tungsten oxide, or iron oxyhydroxide.
[8] The electrode according to [7], wherein the conductive substrate is selected from a carbon material or a metal material, and the metal material is preferably gold, platinum, palladium or an alloy thereof.
[9] The electrode according to [7] or [8], wherein the iron-tungsten composite oxide system is obtained by a hydrothermal synthesis method; the mol ratio of the iron element to the tungsten element is 1: 1-5: 1.
[10]In addition, the invention also provides a method for synthesizing the above [7]]～[9]Any one of the electrodes is used for electrolyzing water and reducing CO2And reduction preparation of N2The use of (1).
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the invention can realize the following technical effects:
the electrocatalyst and the electrode based on the electrocatalyst provided by the invention can show excellent catalytic activity, and particularly, the electrocatalyst shows rapid OER kinetics under alkaline conditions.
In addition, the electrocatalyst provided by the invention can keep long-term use stability when used for a long time.
Drawings
FIG. 1: the relationship graph of the oxygen generation current density and the potential of the electrodes of the composite oxidation system with different iron-tungsten molar ratios.
FIG. 2: fe prepared in example 13W1The electrode of the iron-tungsten composite oxidation system is at 10mA/cm2Under the condition of constant current density, the oxygen generation overpotential is plotted against time.
FIG. 3: fe prepared in example 13W1The relationship graph of current density and potential of the iron-tungsten composite oxidation system electrode after constant current reaction at different time.
FIG. 4: four samples (Fe)1W3Sample, Fe1W1Sample, Fe3W1Sample and Fe0.95W0.05Sample) structural characterization:
(a) the method comprises the following steps An XRD spectrum;
(b) the method comprises the following steps A Raman spectrum;
(c) and (d): energy dispersive X-ray spectroscopy (EDS) elemental maps and Transmission Electron Microscope (TEM) images.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the term "non-nickel and non-cobalt" means that a compound or a raw material containing nickel or cobalt is not used in the preparation process of the electrocatalyst according to the present invention, or that the nickel or cobalt element is present only as impurities in the electrocatalyst according to the present invention or the content thereof is below the detection limit of a usual detection apparatus.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, "OER" is used as an abbreviation for "oxygen generation reaction".
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
In a first aspect of the invention, an electrocatalyst composition is provided, wherein the composition is an iron-tungsten composite oxidation system, the molar ratio of iron to tungsten elements in the composite oxidation system is 0.3: 1-19: 1, the composite oxidation system comprises iron tungstate, and optionally comprises one or more of iron oxide, tungsten oxide or iron oxyhydroxide.
The source of the iron element and the tungsten element in the present invention is not particularly limited, and generally, salts containing iron and salts containing tungsten are available.
As the iron-containing salts which can be used in the present invention, inorganic salts such as iron-containing hydrochloride, sulfate and nitrate, or organic acid salts such as iron acetate may be used in some specific embodiments. In some preferred embodiments of the present invention, the iron element of the iron-containing feedstock used in the present invention is present in a positive divalent valence state. In another specific embodiment of the present invention, hydrates of these iron-containing salts, for example, dihydrate to decahydrate, may also be used. Preferably, the iron-containing salts of the present invention can be listed as: the ferric salt is ferrous sulfate heptahydrate, ferrous chloride tetrahydrate or ferrous ammonium sulfate hexahydrate. The above iron salts of the present invention may be used singly or in admixture of two or more kinds.
For the tungsten-containing salt that can be used in the present invention, various tungstates, such as one or more of potassium tungstate, sodium tungstate, or ammonium tungstate, can be used.
In the present invention, the ratio of the iron element to the tungsten element in the composite oxidation system can be adjusted by the ratio of the raw materials. In a preferred embodiment of the present invention, in the complex oxidation system, the molar ratio of the iron element to the tungsten element is 1:1 to 10:1, more preferably 1:1 to 8:1, and still more preferably 1.5: 1-5: 1.
The inventor of the present invention has found that by controlling the molar ratio of the iron element to the tungsten element in the composite oxidation system of the present invention, the disadvantage that the stability of electrocatalysis is reduced because active metal elements appearing in the electrocatalysts are dissolved in a solution or an electrolyte in the past can be reduced in the use process of the electrocatalysts.
In addition, the electrocatalyst used in the present invention does not contain metal elements having catalytic activity other than iron and tungsten elements, on one hand, as mentioned above, if some metal elements having catalytic activity, such as Ir or Ru, are additionally used, the production cost may be increased as a whole, but the electrocatalytic efficiency of the electrocatalytic effect is not significantly improved, and under some conditions, the original stability of the present invention may be reduced due to the addition of these metal elements. On the other hand, when the catalyst is synthesized by a hydrothermal method described later, unnecessary troubles may be caused.
In some embodiments, the electrocatalyst compositions of the invention comprise predominantly iron tungstate as the primary component, while in other embodiments the composition may also comprise hydrothermal reaction products such as iron oxide, tungsten oxide, or iron oxyhydroxide.
< second aspect >
In a second aspect of the present invention, there is provided a method for preparing the electrocatalyst composition according to the < first aspect > above. In some specific embodiments, the method of making comprises: mixing the precursor solution, namely forming a mixed system by using an iron source substance and a tungsten source substance, wherein the molar ratio of iron to tungsten in the iron source substance to the tungsten source substance is 0.3: 1-19: 1; and a step of hydrothermal synthesis, in which the mixed system is treated at a temperature of 160 ℃ or higher.
Step of mixing precursor liquid
In the present invention, the step of mixing the precursor liquid is not particularly limited. In some embodiments, the precursor solution of the electrocatalyst according to the invention may be obtained by means of a co-precipitation process.
The invention uses the iron-containing or tungsten-containing salts defined above to form mixed systems, which can be achieved by means of aqueous solutions. For water in an aqueous solution, ultrapure water, which means water having a resistivity of 18M Ω £ cm (25 ℃) or more, is used in a specific embodiment of the present invention from the viewpoint of electrocatalyst purity and reduction of the influence of interfering ions on the catalytic effect of the electrocatalyst and use stability.
The above-mentioned mixing system may be carried out in any vessel in the art, and preferably, the mixing may be assisted by a stirring device, and such stirring may be mechanical stirring or magnetic stirring in general.
In the method of forming the mixed system, it is preferable in the present invention that the iron-containing salt and the tungsten-containing salt are separately formed into aqueous solutions, and then the aqueous solution containing the tungsten salt is poured into the aqueous solution containing the iron salt, mixed and stirred, from the viewpoint of enhancing the activity of the electrocatalyst.
In order to facilitate the coprecipitation method, in a preferred embodiment of the present invention, the pH of the system may be adjusted after the above-mentioned mixed system is formed, particularly, at the time of precipitation. The pH of the system can be adjusted by adding an acid or a base to the mixed system, and the acid used may be, for example, hydrochloric acid or sulfuric acid, and the base used may be, for example, a hydroxide of an alkali metal. In some embodiments of the present invention, the pH of the mixed system is adjusted to a range of 4.5 to 7.5
Step of hydrothermal synthesis
After the coprecipitation method is carried out under the mixed system, the hydrothermal synthesis method is continuously carried out.
In some embodiments of the invention, the mixture obtained by the co-precipitation process may be transferred to a hydrothermal synthesis unit. The hydrothermal synthesis apparatus is not particularly limited, and a high-temperature reaction vessel may be used.
After transferring the mixture obtained by the coprecipitation method to a hydrothermal synthesis device, the device is heated. In the present invention, the heating temperature is controlled to 160 ℃ or higher, preferably 170 ℃ or higher, more preferably 170 to 190 ℃, and even more preferably 175 to 185 ℃, from the viewpoint of improving the reaction efficiency and improving the stability of the electrocatalyst. Regarding the hydrothermal reaction time, in some specific embodiments, the hydrothermal reaction time may be 1 hour or more and 20 hours or less, preferably 1 to 10 hours. The present inventors have found that when hydrothermal synthesis is carried out under the above-mentioned conditions, iron tungstate (FeWO) described below is advantageous4) Is performed.
Post-treatment step
After the completion of the hydrothermal synthesis step, a post-treatment step may be carried out, and these steps themselves are not particularly limited, and methods such as filtration, drying, grinding and the like may be employed.
Preferably, the drying treatment may be performed at a temperature of 90 ℃ or more. Also, in some embodiments, the drying step may be performed under reduced pressure or under inert gas.
The dried solid material can be ground to obtain an electrocatalyst powder.
Iron/tungsten element ratio in electrocatalysts
In the electrocatalyst obtained in the above step, the molar ratio of the iron element to the tungsten element in the final product is controlled to be 0.3:1 to 19:1, preferably 1:1 to 10:1, more preferably 1:1 to 8:1, and even more preferably 1.5:1 to 5:1 by controlling the raw material ratio.
In the present invention, FeW composite materials having different Fe/W molar ratios are synthesized by using a hydrothermal synthesis method. In the following, several samples (Fe) were run through1W3Sample, Fe1W1Sample, Fe3W1Sample and Fe0.95W0.05Sample) is specifically described.
The XRD pattern shown in FIG. 4(a) shows Fe3W1And Fe1W1FeWO with wolframite structure present in the sample4And (4) phase(s). WO in which crystallization occurs when the initial iron/tungsten element molar ratio is less than 1:33And (4) phase(s). Fe3W1And Fe1W1Raman spectrum of the sample (see FIG. 4(b)) at 882cm-1And 686cm-1Shows a strong band due to FeWO4The terminal W ═ O and W — O — W bond vibrations in the wolframite structure of the phase. It was shown by Transmission Electron Microscope (TEM) images and energy dispersive X-ray spectroscopy (EDS) elemental maps (see (c), (d) in fig. 4) that all elements were uniformly dispersed in the mixed oxide composite. High resolution TEM images further confirmed Fe3W1Polycrystalline FeWO in samples4And (4) forming a phase. In FeWO4In a typical wolframite structure, Fe2+And W6+Ions are all with O2-The ions form an octahedral coordination and the corresponding octahedral edge [100 ]]The directions are arranged layer by layer. The present inventors have found that such direct bonding between the two species is believed to enhance the catalytic activity of the FeW hybrid complex and to contribute to the long-term stability of the electrocatalytic activity.
Thus, it is considered to be advantageous for the electrocatalyst compositions of the invention to contain an iron tungstate component, FeWO4The content of such components is preferably 50% or more, more preferably 70% or more, and still more preferably 80% or more. In addition, optionally, iron oxide and oxygen may be containedTungsten oxide, iron oxyhydroxide, and the like.
Exemplary methods
As a typical preparation method by which the electrocatalyst according to the invention can be realized, the following steps are possible:
(1) fixing the molar weight of iron element to be 3mmol according to the molar ratio of the two elements of iron and tungsten to be 1: 3-19: 1, respectively weighing iron salt and tungsten salt, respectively dissolving the iron salt and the tungsten salt in 7.5mL of ultrapure water (18.2M omega cm), uniformly stirring for 10 minutes by using magnetons, quickly pouring precursor solution containing the tungsten salt into solution containing the iron salt, and uniformly stirring for 0.5 hour to obtain a brown mixture;
(2) dropwise adding a certain amount of 2mol/L NaOH solution or 1mol/L H into the mixed solution obtained in the step (1) under the condition of stirring2SO4Adjusting the pH value of the solution to 6;
(3) and (3) transferring the mixed solution prepared in the step (2) into a 30mL Teflon reaction kettle, reacting for 1-10 h at 180 ℃, naturally cooling to room temperature, respectively cleaning with ultrapure water and absolute ethyl alcohol, centrifugally separating, drying for 12h at 100 ℃, and grinding at room temperature to obtain the iron-tungsten composite oxidation system powder material.
< third aspect >
In a third aspect of the invention, an electrocatalytic electrode and a method of making the same are provided. The electrocatalyst electrode of the invention comprises: a conductive substrate; an electrocatalyst present on at least a part of a surface of the electrically conductive substrate, the electrocatalyst being an electrocatalyst prepared according to the above < first aspect > or < second aspect >.
Conductive substrate
In the present invention, the support for the electrocatalyst is provided by an electrically conductive substrate and an effective ohmic contact is made between the electrocatalyst and the support.
The material of the conductive substrate is not particularly limited in the present invention, and may be selected from a metal material and a conductive non-metal material. In some specific embodiments of the present invention, for the metallic material, gold, nickel, platinum, palladium or an alloy thereof may be selected. The non-metallic material for the conductive substrate that can be used in the present invention may be selected from carbon materials such as graphite and other carbon materials, conductive glass, and the like.
In some embodiments of the present invention, the conductive substrate may be a substrate in the shape of a sheet or a plate made of these metallic or non-metallic materials, for example, a graphite plate/sheet, an FTO glass sheet (SnO)2F), a glassy carbon plate/sheet or carbon conductive paper, etc. The specific size of the sheet or plate is not particularly limited, and may be adjusted or selected according to actual needs.
The surface or internal structure of the sheet-like or plate-like substrate is also not particularly limited, and for example, a surface having a certain roughness or a surface or internal structure having a porous structure may be used. In some specific embodiments of the present invention, for example, a metal foam body having a plate shape or a sheet shape, such as nickel foam, may be used as the conductive substrate. In other embodiments, the conductive substrate of the present invention may also be a porous skeletal structure, typically formed by metallic or non-metallic fibers. The skeletal structure may be a plate-like or sheet-like structure having a thickness. For example, a conductive substrate having a structure such as a plate-like or sheet-like shape can be prepared by processing or cutting using an aggregate of woven or non-woven carbon fibers as a conductive substrate material.
In addition, the conductive substrate of the present invention may have a multilayer structure, and in some specific embodiments, such a structure may be a double-layer structure of a support layer/a conductive layer, or may be a triple-layer structure of a support layer/an adhesive layer/a conductive layer, or may be a conductive layer/a support layer/a conductive layer, a conductive layer/an adhesive layer/a support layer/an adhesive layer/a conductive layer, or the like. The support layer that can be used in the present invention is not particularly limited and may be selected from conductive or non-conductive materials. Examples thereof include polymer materials, glass, metals, semiconductors, and composite materials. As the adhesive layer, a general adhesive component, for example, an adhesive such as a high molecular epoxy resin, a phenol resin, a urethane resin, polyacrylic acid (ester), polyolefin, silicone rubber, or the like can be used. For the conductive layer, the metal or conductive non-metal material described above may be used for preparation. The conductive substrate of the multilayer structure of the present invention can be prepared in a conventional manner, for example, by stacking the layers, and in some specific embodiments, the conductive layer can be formed on the support layer by using a deposition method, such as solution self-assembly, physical evaporation, magnetron sputtering, chemical CVD, and the like. In a preferred embodiment of the present invention, the above-described adhesive layer is not used in the conductive substrate of the multilayer structure in view of stability in use, durability, and recyclability. In addition, ITO glass, toc (transparent Conductive oxide) glass may be used for the Conductive substrate of the multilayer structure in some preferred embodiments of the present invention, and these Conductive substrates may be commercially available.
Also, surprisingly, although the electrically conductive substrates disclosed above may be used, further studies have shown that the use of metal substrates, particularly metal gold substrates formed of gold, can further enhance the activity of the electrocatalysts of the invention. Therefore, the conductive substrate or the conductive layer on the surface of the conductive substrate preferred in the present invention is selected from: a gold disk substrate, a gold sheet substrate, or a gold thin film substrate.
In some embodiments of the present invention, the gold film layer may be formed on any substrate by a sputtering method, and the thickness of the gold film layer is not particularly limited, and may be, for example, 100 to 2000 nm. Optionally, the surface of the gold film is roughened.
In other embodiments, a porous gold film may be formed by sputtering gold and other metals (e.g., silver and nickel) to form an alloy film on a substrate, and then removing the other alloys by etching.
Method for forming electrocatalyst layer
The method for forming the electrocatalyst layer is not particularly limited. In some specific embodiments of the invention, formation is permitted using various existing physical or chemical methods. Deposition methods can be enumerated as follows: solution self-assembly, gas/liquid phase deposition, ink dispersion, spraying, physical evaporation, magnetron sputtering, chemical CVD and other methods.
In some preferred embodiments of the present invention, the electrocatalyst may be formed on the surface of the electrically conductive substrate by the method of dispersion. The present invention disperses the electrocatalyst in an alcohol solvent, preferably, isopropanol, from the viewpoint of improving dispersibility. In addition, the dispersion liquid contains ultrapure water and a dispersion aid in order to improve the dispersion effect. Preferably, these dispersing aids may be fluorine-containing dispersants (e.g., Nafion). In some specific embodiments of the present invention, the ratio of the amount (volume) of the alcohol solvent to the amount of the ultrapure water in the dispersion is 1:1 to 49:1, preferably 20:1 to 45: 1.
In some specific embodiments, the electrocatalyst dispersion containing iron-tungsten oxide is dropped on the surface of the conductive substrate formed of gold, and different volumes of the dispersion are used depending on the surface area of the conductive substrate, and may be, for example, 5 to 80 μ L or the like.
Optionally, after forming the electrocatalyst layer on the electrically conductive substrate by the above-described method, post-treatment may be performed using a process such as drying and defoaming.
< fourth aspect >
In a fourth aspect of the invention, there is provided an electrocatalyst or an electrocatalyst electrode provided by the invention for use in the electrolysis of water and reduction of CO2And reduction preparation of N2The use of (1).
The specific scenes of these applications are not particularly limited, and the applications may be the production of clean energy, or the treatment or purification of water pollution or air pollution.
Examples
The invention is further described with reference to the figures and examples.
Example 1Fe3W1Preparation of samples
(1) Weigh 1.167g (NH)4)2Fe(SO4)2·6H2O and 0.330g Na2WO4·2H2O, dissolved in 7 respectively.5mL of 18.2 M.OMEGA.cm ultrapure water was uniformly stirred with a magneton for 10min, and Na was added2WO4·2H2Quickly pouring the O solution into the solution containing the ferric salt, continuously stirring for 0.5H, and dropwise adding a certain amount of 2mol/L NaOH solution or 1mol/L H into the mixture solution2SO4The solution was adjusted to pH 6.
(2) Transferring the mixture solution obtained in the step (1) into a 30mL Teflon reaction kettle, packaging the mixture in a stainless steel lining, reacting for 5h at 180 ℃, naturally cooling to room temperature, respectively washing with ultrapure water and absolute ethyl alcohol, centrifuging for 5min at 8000 rpm, drying the centrifuged matter at 100 ℃ for 12h, and grinding to obtain Fe3W1Powder samples.
(3) Weighing Fe prepared in step (2)3W12.5mg of the powder sample was added 970. mu.L of isopropyl alcohol, 20. mu.L of ultrapure water and 10. mu.L of 5% Nafion solution, respectively, to prepare 1mL of a solution containing Fe3W1The particle dispersion of the sample was sonicated for 0.5h, and 40. mu.L of the dispersion was measured and dropped onto a 1X 1cm area2And an Au film substrate with the thickness of 100 nm. After the dispersion liquid is dried, welding an aluminum wire and a substrate by using molten indium, and packaging an electrode by using epoxy resin AB glue to obtain Fe3W1An oxygen generating electrode.
Mixing Fe3W1The electrode is placed in a three-electrode electrochemical device, an Hg/HgO electrode is selected as a reference electrode, a platinum electrode is selected as a counter electrode, a 1mol/L KOH solution is used as a reaction electrolyte, and pure O with the flow of 5sccm is used before testing2Bubbling in the solution for 20min, and continuously introducing O during the test2The selection range of the cyclic voltammetry test voltage is 0-0.75VHg/HgOThe test results are shown in FIG. 1, and the prepared electrode is at a voltage exceeding 1.50VRHEThen, the oxygen generating current is generated at 10mA/cm2The oxygen generation overpotential under the current density condition of (1) is 0.40V. The stability test results are shown in FIG. 2, Fe3W1The electrode is at 10mA/cm2Under the condition of constant current density, the device can stably run for 200 h. Stability test 50, 100, 150, 200h after KOH electrolyte replacement, Fe3W1The cyclic voltammetric behavior of the electrode is shown in FIG. 3, which shows stability measurements over 200hTest of Fe3W1The electrode is at 10mA/cm2The overpotential below was reduced to 0.38V.
Example 2 Fe1W1Preparation of samples
(1) Weigh 1.176g (NH)4)2Fe(SO4)2·6H2O and 0.990g Na2WO4·2H2O, dissolved in 7.5mL of 18.2M omega cm ultrapure water respectively, stirred uniformly for 10min with a magneton, and Na2WO4The solution is quickly poured into the solution containing ferric salt, and after the solution is continuously stirred for 0.5H, a certain amount of 2mol/L NaOH solution or 1mol/L H solution is dripped into the mixture solution2SO4The solution was adjusted to pH 6.
(2) Transferring the mixture solution obtained in the step (1) into a 30mL Teflon reaction kettle, packaging the mixture in a stainless steel lining, reacting for 5h at 180 ℃, naturally cooling to room temperature, respectively washing with ultrapure water and absolute ethyl alcohol, centrifuging for 5min at 8000 rpm, drying the centrifuged matter at 100 ℃ for 12h, and grinding to obtain Fe1W1Powder samples.
(3) Weighing Fe prepared in step (2)1W12.5mg of the powder sample was added 970. mu.L of isopropyl alcohol, 20. mu.L of ultrapure water and 10. mu.L of 5% Nafion solution, respectively, to prepare 1mL of a solution containing Fe1W1The particle dispersion of the sample was sonicated for 0.5h, and 40. mu.L of the dispersion was measured and dropped onto a 1X 1cm area2And an Au film substrate with the thickness of 100 nm. After the dispersion liquid is dried, welding an aluminum wire and a substrate by using molten indium, and packaging an electrode by using epoxy resin AB glue to obtain Fe1W1An oxygen generating electrode.
Mixing Fe1W1The electrode is placed in a three-electrode electrochemical device, an Hg/HgO electrode is selected as a reference electrode, a platinum electrode is selected as a counter electrode, a 1mol/L KOH solution is used as a reaction electrolyte, and pure O with the flow of 5sccm is used before testing2Bubbling in the solution for 20min, and continuously introducing O during the test2The selection range of the cyclic voltammetry test voltage is 0-0.75VHg/HgOAnd the test results are shown in FIG. 1, Fe prepared1W1Electrodes at over 1.50VRHEThen oxygen production is startedCurrent at 10mA/cm2The oxygen generation overpotential under the current density condition of (2) is 0.42V.
Comparative example 1Fe2O3Preparation of samples
(1) Weigh 1.176g (NH)4)2Fe(SO4)2·6H2O, dissolving in 15mL of 18.2M omega cm ultrapure water, uniformly stirring for 0.5H by using a magneton, and dropwise adding a certain amount of 2mol/L NaOH solution or 1mol/L H into the solution2SO4The solution was adjusted to pH 7.
(2) Transferring the solution obtained in the step (1) into a 30mL Teflon reaction kettle, packaging the solution in a stainless steel lining, reacting for 5h at 180 ℃, naturally cooling to room temperature, respectively cleaning with ultrapure water and absolute ethyl alcohol, centrifugally separating for 5min at 8000 rpm, drying the centrifugally separated substance at 100 ℃ for 12h, grinding to obtain Fe2O3Powder samples.
(3) Weighing Fe prepared in step (2)2O32.5mg of the powder sample was added 970. mu.L of isopropyl alcohol, 20. mu.L of ultrapure water and 10. mu.L of 5% Nafion solution, respectively, to prepare 1mL of a solution containing Fe2O3The particle dispersion of the sample was sonicated for 0.5h, and 40. mu.L of the dispersion was measured and dropped onto a 1X 1cm area2And an Au film substrate with the thickness of 100 nm. After the dispersion liquid is dried, welding an aluminum wire and a substrate by using molten indium, and packaging an electrode by using epoxy resin AB glue to obtain Fe2O3An oxygen generating electrode.
Obtained Fe2O3Placing the oxygen generating electrode into a three-electrode electrochemical device, selecting an Hg/HgO electrode as a reference electrode, a platinum electrode as a counter electrode, 1mol/L KOH solution as a reaction electrolyte, and using pure O with the flow of 5sccm before testing2Bubbling in the solution for 20min, and continuously introducing O during the test2The selection range of the cyclic voltammetry test voltage is 0-0.8VHg/HgOThe test results are shown in FIG. 1, Fe2O3Electrode over 1.55VRHEThen, the current response is started to generate at 1.70VRHECurrent density of less than 5mA/cm2。
Comparative example 2 WO3Preparation of samples
(1) 1.979g of Na were weighed2WO4·2H2O, dissolving in 15mL of 18.2M omega cm ultrapure water, uniformly stirring for 0.5h by using a magneton, and dropwise adding a certain amount of concentrated HCl solution into the solution to adjust the pH to 1.6.
(2) Transferring the solution obtained in the step (1) into a 30mL Teflon reaction kettle, packaging the solution in a stainless steel lining, reacting for 5h at 180 ℃, naturally cooling to room temperature, respectively cleaning with ultrapure water and absolute ethyl alcohol, centrifugally separating for 5min at 8000 rpm, drying the centrifugally separated substance at 100 ℃ for 12h, and grinding to obtain WO3Powder samples.
(3) Weighing the WO prepared in step (2)32.5mg of the powder sample was added 970. mu.L of isopropyl alcohol, 20. mu.L of ultrapure water and 10. mu.L of 5% Nafion solution, respectively, to prepare 1mL of a WO-containing solution3The particle dispersion of the sample was sonicated for 0.5h, and 40. mu.L of the dispersion was measured and dropped onto a 1X 1cm area2And an Au film substrate with the thickness of 100 nm. After the dispersion liquid is dried, welding an aluminum wire with a substrate by using molten indium, and packaging an electrode by using epoxy resin AB glue to obtain WO3And an electrode.
Obtained WO3The electrode is placed in a three-electrode electrochemical device, an Hg/HgO electrode is selected as a reference electrode, a platinum electrode is selected as a counter electrode, a 1mol/L KOH solution is used as a reaction electrolyte, and pure O with the flow of 5sccm is used before testing2Bubbling in the solution for 20min, and continuously introducing O during the test2The selection range of the cyclic voltammetry test voltage is 0-0.8VHg/HgOThe test results are shown in FIG. 1, WO3Electrodes at over 1.60VRHEThe current response is started to generate at 1.70VRHECurrent density lower than 1mA/cm2。
In conclusion, compared with iron-based and tungsten-based electrodes, the invention has higher oxygen production efficiency at 10mA/cm2Under the condition of current density, the initial oxygen generation overpotential is lower than 0.45V, and after a constant current test for 200h, the overpotential is further reduced to 0.38V, so that high oxygen generation activity and stability are shown. With respect to the improvement in stability, the inventors have found that this can be attributed to the fact that, when operating with the electrocatalyst according to the invention, over time of use,a phase transition occurs in the electrocatalyst. The FeOOH phase can be further characterized by raman spectroscopy after stability testing. Thus, it was shown that the iron-tungsten mixed oxide underwent FeWO crystallization4Phase transition to short range ordered oxyhydroxide species.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The electrocatalyst, the electrocatalyst electrode and the preparation method thereof provided by the invention can be applied in industry.
Claims (5)
1. An electrocatalyst electrode for an oxygen-generating reaction, the electrode comprising:
a conductive substrate;
an electrocatalyst composition present on at least a portion of a surface of the electrically conductive substrate,
the electrocatalyst composition is an iron-tungsten composite oxidation system, the molar ratio of iron to tungsten in the composite oxidation system is 1: 1-5: 1,
the composite oxidation system comprises iron tungstate and iron oxyhydroxide and one or more of iron oxide or tungsten oxide, and the content of the iron tungstate is more than 50 mass percent of the electrocatalyst composition,
the iron tungstate is FeWO4。
2. The electrode of claim 1, wherein the conductive substrate is selected from a carbon material or a metallic material.
3. The electrode of claim 2, wherein the metallic material is gold, platinum, palladium, or an alloy thereof.
4. The electrode according to any one of claims 1 to 3, wherein the iron-tungsten composite oxide system is obtained by hydrothermal synthesis.
5. Use of the electrode according to any one of claims 1 to 4 for electrolysis of water and reduction of CO2And reduction preparation of N2The use of (1).
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