CN109569594B - Titanate-supported noble metal-based oxygen evolution electrocatalyst and preparation method thereof - Google Patents
Titanate-supported noble metal-based oxygen evolution electrocatalyst and preparation method thereof Download PDFInfo
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- CN109569594B CN109569594B CN201811451186.7A CN201811451186A CN109569594B CN 109569594 B CN109569594 B CN 109569594B CN 201811451186 A CN201811451186 A CN 201811451186A CN 109569594 B CN109569594 B CN 109569594B
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- titanate
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- oxygen evolution
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 64
- 239000001301 oxygen Substances 0.000 title claims abstract description 64
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940005991 chloric acid Drugs 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000002244 precipitate Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 27
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 19
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical group O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 16
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002113 barium titanate Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 21
- 150000002500 ions Chemical class 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 47
- 238000003756 stirring Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 15
- 229910052741 iridium Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 13
- 238000013112 stability test Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000011258 core-shell material Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 iridium ions Chemical class 0.000 description 1
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- DJSKLKQRHSKRDZ-UHFFFAOYSA-N zinc dioxido(oxo)titanium Chemical compound [Zn+2].[O-][Ti]([O-])=O DJSKLKQRHSKRDZ-UHFFFAOYSA-N 0.000 description 1
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- B01J35/33—
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of electrocatalysts, and particularly relates to a titanate-supported noble metal-based oxygen evolution electrocatalyst and a preparation method thereof. According to the invention, metal chloric acid and titanate solution are mixed, because the metal chloric acid has acidity, and under the acidic condition, a metal-oxygen structure on the surface of titanate reacts with acid to generate metal positive ions to be dissolved, so that titanate with a perovskite structure with crystal lattice vacancies on the surface is left, and a noble metal oxide is synthesized on the surface of the titanate, so that the titanate-supported noble metal oxygen evolution electrocatalyst is obtained; the preparation method is simple, high in safety, low in equipment requirement and suitable for large-scale production; the obtained oxygen evolution electrocatalyst has good stability, a plurality of reaction sites and high catalytic activity.
Description
Technical Field
The invention belongs to the field of electrocatalysts, and particularly relates to a titanate-supported noble metal-based oxygen evolution electrocatalyst and a preparation method thereof.
Background
The energy conversion technology plays an important role in the consumption and storage of renewable energy, wherein the Solid polymer water electrolysis (SPE) technology has the advantages of high efficiency, small volume, fast start and stop, long service life and the like, and is gradually accepted and initially commercialized at home and abroad.
However, since the solid polymer water electrolysis technology requires the use of noble metals as its catalysts, the cost of the galvanic pile is higher than that of the currently popular alkaline electrolysis, so that the scale of application is limited. On the hydrogen evolution side, it is now possible to use carbon-supported platinum catalysts, which achieve better performance at lower noble metal loadings. The hydrogen evolution reaction also involves only 2 electrons and the overpotential of the electrocatalyst is relatively low. For 4-electron reaction in which oxygen is precipitated, the overpotential of the electrocatalyst is relatively high, and in order to achieve better performance, a catalyst with a high noble metal (iridium/ruthenium) loading needs to be used. However, since the consumption of a catalyst using only a noble metal is large and the cost is too high, a supported noble metal catalyst is generally prepared by adding a noble metal as an active phase to a carrier. A common support is TiO2、Al2O3、AC、SnO2And MOF, etc., such as Sundaparian, etc. (Sundaparian, Ralinghong, Shijijun, Chengliang, Liulili, Xuqu. IrO having a core-shell structure2Research on water electrolysis oxygen evolution catalyst for @ Ti [ J]Chinese ceramic, 2017, 53 (07): 36-40.) with H2IrCl6·nH2O and titanium powder are used as main raw materials, and an iridium-coated titanium (Ir @ Ti) catalyst is prepared by adopting a sodium borohydride reduction method. IrO is prepared by heating Ir @ Ti catalyst at different temperatures2Wrapped Ti (IrO)2@ Ti) catalyst. Research shows that IrO prepared by the method2@ Ti catalyst, nanoscale IrO2Distributed on the surface of Ti particles to form a wrapped catalytic layer with a core-shell structure. IrO treated at 500 deg.C2The @ Ti catalyst has the highest oxygen evolution activity. According to the molar ratio of Ir to Ti of 1: 2, 1: 6, 1: 110 configured IrO2@ Ti catalyst with IrO2The content of IrO is increased2Envelope-type structure, IrO2The catalytic layer is coated on the catalyst layer, so that the oxygen evolution potential can be effectively reduced. Wherein 1: 2, the oxygen evolution performance of the catalyst is optimal, and the current of the electrolyzed water is 0.24A cm at 25 ℃ under normal pressure-2The electrolytic voltage at this time was 3V. Chinese patent application CN108546962A discloses a preparation method of a porous carbon doped iridium electrolyzed water oxygen evolution catalyst with high specific surface area, which comprises the steps of dipping iridium ions into an organic framework MOF-5 material by using a dipping method to obtain a precursor and preparing the porous carbon doped iridium oxygen evolution catalyst with high specific surface area from the precursor. However, the preparation method has various steps, needs more organic solvents and has higher cost. However, these studies still have the problems of low catalyst activity, complex preparation method, large amount of organic solvent, and the like. The technicians in the field are always dedicated to searching a supported noble metal oxygen evolution catalyst with simple preparation method, low cost and good catalytic performance, and no report of combining titanate and noble metal base as an oxygen evolution electrocatalyst is provided at present.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the oxygen evolution catalyst is prepared without titanate-supported noble metal oxide in the prior art, so that the titanate-supported noble metal-based oxygen evolution electrocatalyst with simple preparation method, low cost and good catalyst activity and the preparation method thereof are provided.
Therefore, the technical scheme of the invention is as follows:
the titanate-supported noble metal-based oxygen evolution electrocatalyst is characterized by comprising titanate, titanate with lattice vacancy and noble metal oxide; the titanate is selected from one of strontium titanate, barium titanate, magnesium titanate, calcium titanate, iron titanate, copper titanate, nickel titanate, cobalt titanate, yttrium titanate, zinc titanate, manganese titanate, molybdenum titanate and silver titanate.
Further, the noble metal oxide is iridium oxide or ruthenium oxide.
Further, the titanate is one of strontium titanate, barium titanate and calcium titanate.
Further, the titanate is strontium titanate.
Further, the titanate having lattice vacancy is prepared by reacting titanate with H +.
Further, the mass ratio of the titanate to the noble metal oxide is 10-99: 1-90.
furthermore, the mass ratio of the titanate to the noble metal oxide is 50-99: 1-50.
further, the oxygen evolution electrocatalyst comprises a titanate core body and a composite layer coated on the titanate, wherein the composite layer comprises titanate with lattice defects and noble metal oxide.
Further, the composite layer includes a titanate layer having lattice sites and a noble metal oxide layer; or the like, or, alternatively,
the composite layer includes a titanate layer having lattice defects, a noble metal oxide layer, and a mixed layer formed of a mixture of titanate having lattice defects and noble metal oxide; or the like, or, alternatively,
the composite layer includes a mixed layer formed of a mixture of a titanate having lattice defects and a noble metal oxide.
The invention also provides a preparation method of the titanate supported noble metal based oxygen evolution electrocatalyst, which is characterized by comprising the following steps:
(1) mixing the nano titanate solution with metal chloric acid and sodium hydroxide respectively to form a mixed solution;
(2) centrifuging the mixed solution obtained in the step (1), and taking a precipitate;
(3) and (3) calcining the precipitate obtained in the step (2) to obtain the oxygen evolution electrocatalyst.
Further, in the step (1), after the nano titanate solution is mixed with metal chloric acid, sodium hydroxide is added to form a mixed solution with the pH value of 5-11.
Further, in the step (1), after the nano titanate solution is mixed with sodium hydroxide, metal chloric acid is added to form a mixed solution, and the pH value is adjusted to be less than 7.
Further, in the step (1), after the nano titanate solution is mixed with sodium hydroxide, metal chloric acid is added to form a mixed solution, and the pH value is adjusted to be less than 7; the pH is adjusted to 5-11 by further addition of an acidic or basic solution.
Further, the acidic solution is hydrochloric acid, sulfuric acid or nitric acid.
Further, the metal chloric acid is chloro-iridic acid or chloro-ruthenic acid.
Further, in the step (1), the molar ratio of the nano titanate to the metal chloric acid is 1: 0.1-10.
further, in the step (1), the mixing time of the nano titanate solution and the metal chloric acid is 5-20 min.
Further, in the step (1), the concentration of the nano titanate solution is 0.01-1 mol/L.
Further, in the step (1), the concentration of the sodium hydroxide is 0.1-5 mol/L.
Further, in the step (2), a process of rinsing the obtained precipitate multiple times is also included.
Further, in the step (3), the calcination temperature is 300-800 ℃, and the calcination time is 1-4 h.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of a titanate-supported noble metal-based oxygen evolution electrocatalyst, wherein metal chloric acid has acidity, and a metal-oxygen structure on the surface of titanate reacts with acid to generate metal positive ions to be dissolved under the acidic condition, so that titanate with a perovskite structure with crystal lattice vacancies on the surface is left, and iridium oxide/ruthenium oxide is synthesized on the surface of the substance, so that the titanate-iridium oxide/ruthenium oxide core-shell structure electrocatalyst with high performance and multiple active sites and with vacancies formed by metal precipitation on the surface is obtained; the preparation method is simple, high in safety, low in equipment requirement and suitable for large-scale production.
2. The invention provides a preparation method of titanate-supported noble metal-based oxygen evolution electrocatalyst, which comprises the steps of mixing a nano titanate solution with metal chloric acid and sodium hydroxide respectively to form a mixed solution, centrifuging, taking precipitate, and calcining; firstly, mixing titanate solution with metal chloric acid, then adding sodium hydroxide to form relatively thick titanate layer with lattice vacancy on titanate surface. Firstly, mixing the nano titanate solution with sodium hydroxide, then adding metal chloric acid, and finally achieving the process step that the PH is less than 7, so that a relatively thin titanate layer with lattice vacancy on the surface of titanate can be formed. If the solution in the process step is always in an alkaline or neutral environment, a titanate layer with lattice defects on the surface cannot be obtained, and only ordinary titanate can be obtained.
3. The invention provides a titanate-supported noble metal-based oxygen evolution electrocatalyst which has the advantage of high reaction activity, the common titanium oxide carrier has poor conductivity, and metal doping can affect crystal lattices to form a perovskite structure, increase the reaction sites of the catalyst, improve the performance of the catalyst and reduce the loading amount of noble metals.
Drawings
FIG. 1 XRD spectrum of oxygen evolution electrocatalyst prepared in example 1;
FIG. 2 shows the electronic structure of strontium titanate and the change of strontium dissolved on the surface;
FIG. 3 is an SEM (a: 5000X) (b: 50000X) photograph of a strontium titanate-supported iridium oxide core-shell electrocatalyst;
figure 4 is a comparison of oxygen evolution activity of different catalysts.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The molecular formula of the chloroiridic acid and chlororuthenic acid used in the examples is Cl6H2Ir·6H2O，Cl6H2Ru·6H2O; are purchased from carbofuran. The grain size of the nanometer titanate is 20-40nm, and the grain size of the nanometer titanium dioxide is 20-40 nm.
The overpotential test method comprises the following steps: the overpotential test method comprises the following steps: the voltammetry curve was measured using an electrochemical workstation, and the value of the electrolysis voltage at the corresponding current density was subtracted by the value of the voltage required for the reaction kinetics (1.229V). The catalyst loading amount on the anode side was 2mg/cm2。
Stability test conditions: the catalyst loading amount on the anode side was 2.5mg/cm2A Nafion 115 membrane (thickness 127 μm) was used as a solid electrolyte separator in a water electrolytic cell, and Pt/C (40 wt% Pt) available from Johnson Matthey corporation was used as a cathode hydrogen evolution catalyst. The effective area of the catalyst is about 1cm2。
Example 1
Preparation of strontium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.5g of chloroiridic acid, stirring for 10min, and adding 2mol/L sodium hydroxide solution until the pH value is 9; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; the precipitate was calcined at 550 ℃ for 2h to give 0.46g of oxygen evolution electrocatalyst.
FIG. 1 is an XRD spectrum of the prepared oxygen evolution electrocatalyst, and it can be seen from the diagram that the peak positions of SrO are embodied in two, i.e. the Sr-O position planes in the surface and the crystal are different; FIG. 2 shows the electronic structure of strontium titanate and the change of the surface strontium after dissolution, which forms Sr with lattice vacancy1－xTiO3－y(ii) a FIG. 3 SEM (a: 5000X) (b: 50000X) photograph of the oxygen evolution electrocatalyst of this example; from the 50000x photograph, it can be seen that the catalyst is of a good core-shell structure. The ellipsoidal larger particles are strontium titanate with a diameter of 100-300 nm, which is the core of the core-shell catalyst. The fine particles on the surface are iridium oxide group coated on the surface of the core as a shellIts diameter is 20-40 nm. These two components are uniformly distributed in the photograph, forming a pore (5000x photograph) structure, which is the most typical core-shell electrocatalyst herein.
The catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.23V, and after the stability test for 1h, the current attenuation rate is 4%.
Example 2
Preparation of strontium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst. The catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.31V, and after the stability test for 1h, the current attenuation rate is 5.2%.
Example 3
Preparation of strontium titanate supported ruthenium-based oxygen evolution electrocatalyst
Weighing 0.21g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.5g of chlororuthenic acid, stirring for 10min, and adding 2mol/L sodium hydroxide solution until the pH value is 9; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; the precipitate was calcined at 550 ℃ for 2h to give 0.42g of oxygen evolution electrocatalyst. The catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.25V, and after the stability test for 1h, the current attenuation rate is 4.5%.
Example 4
Preparation of strontium titanate supported ruthenium-based oxygen evolution electrocatalyst
Weighing 0.21g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 5g of chlororuthenic acid, stirring for 10min, and adding 2mol/L sodium hydroxide solution until the pH value is 10; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 800 ℃ for 1h to obtain the oxygen evolution electrocatalyst. The catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.23V, and after the stability test for 1h, the attenuation rate is 4.8%.
Example 5
Preparation of strontium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 2.3g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 10mL of 2mol/L sodium hydroxide solution, and uniformly mixing for 10 min; adding 0.5g of chloroiridic acid, and stirring for 5 min; titrating by using 2mol/L hydrochloric acid until the pH value is 5; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 400 ℃ for 3h to obtain the oxygen evolution electrocatalyst. The catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.33V, and after the stability test for 1h, the attenuation rate is 5.0%.
Example 6
Preparation of strontium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 1.5g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 5mL of 4mol/L sodium hydroxide solution, and uniformly mixing for 10 min; adding 0.5g of chloroiridic acid, and stirring for 15 min; titrate with 4mol/L hydrochloric acid until pH is 5.5; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 600 ℃ for 1.5h to obtain the oxygen evolution electrocatalyst. The test shows that the catalyst has an overpotential of 0.29V at a current density of 10mA/cm2, and the decay rate of 3.9 percent after the stability test for 1 h.
Example 7
Preparation of strontium titanate supported ruthenium-based oxygen evolution electrocatalyst
Weighing 10g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 15mL of 1mol/L sodium hydroxide solution, uniformly mixing for 10min, adding 2g of chlororuthenic acid, stirring for 10min, and titrating by using 4mol/L hydrochloric acid until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 450 ℃ for 2.5h to obtain the oxygen evolution electrocatalyst. The catalyst is tested to have the overpotential of 0.28V under the current density of 10mA/cm2, and the decay rate is 5.4% after the stability test for 1 h.
Example 8
Preparation of barium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano barium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst.
Example 9
Preparation of zinc titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano zinc titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst.
Example 10
Preparation of calcium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano calcium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst.
Example 11
Preparation of yttrium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano yttrium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 6; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst.
Comparative example 1
Iridium oxide electrocatalyst supported on titanium oxide:
weighing 0.23g of nano titanium dioxide (particle size: 20nm, specific surface area: 30m/g) powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.5g of chloroiridic acid, stirring for 10min, and adding 2mol/L sodium hydroxide solution until the pH value is 9; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 550 ℃ for 2h to obtain the iridium oxide electrocatalyst supported by titanium oxide. The test shows that the catalyst has an overpotential of 0.42V under the current density of 10mA/cm2, and the decay rate of 10.4% after the stability test for 1 h.
Comparative example 2
Gold plated titanium oxide supported iridium oxide electrocatalyst:
weighing 0.23g of gold-plated titanium dioxide (gold is 1% attached to titanium dioxide) powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.5g of chloroiridic acid, stirring for 10min, and adding 2mol/L sodium hydroxide solution until the pH value is 9; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 550 ℃ for 2h to obtain the iridium oxide electrocatalyst supported by gold-plated titanium oxide. The test shows that the catalyst has an overpotential of 0.40V under the current density of 10mA/cm2, and the decay rate of 8.6 percent after the stability test for 1 h.
Comparative example 3
Mixing 0.23g of nano strontium titanate powder and 0.267g of iridium hydroxide, and calcining at 550 ℃ for 2 hours to obtain an oxygen evolution electrocatalyst; the catalyst was tested at 10mA/cm2Under the current density, the overpotential is 0.51V, and after the stability test for 1h, the current attenuation rate is 19%.
Comparative example 4
Preparation of yttrium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano yttrium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 0.1g of chloroiridic acid, stirring for 5min, and adding 0.1mol/L sodium hydroxide solution until the pH value is 2; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 300 ℃ for 4h to obtain the oxygen evolution electrocatalyst. The catalyst was tested at 10mA/cm2The overpotential is 0.38V under the current density, and the current attenuation rate is tested after 1h of stability testThe content was found to be 7.1%.
Comparative example 5
Preparation of strontium titanate supported iridium-based oxygen evolution electrocatalyst
Weighing 0.23g of nano strontium titanate powder, adding 40mL of deionized water, stirring for 30min to form a suspension, adding 20mL of 1mol/L sodium hydroxide solution, uniformly mixing for 10min, adding 0.5g of chloroiridic acid, stirring for 10min, and titrating by using 4mol/L hydrochloric acid until the pH value is 10; centrifuging at 10000rpm for 1h, taking the precipitate, rinsing for multiple times, centrifuging and removing ions in the precipitate; and calcining the precipitate at 450 ℃ for 2.5h to obtain the oxygen evolution electrocatalyst. The test shows that the catalyst has an overpotential of 0.55V under the current density of 10mA/cm2, and the decay rate of 15.7 percent after the stability test for 1 h.
Experimental example 1
Catalyst Activity test
The catalyst loading amount on the anode side was 2mg/cm2A Nafion 115 membrane (thickness 127 μm) was used as a solid electrolyte separator in a water electrolytic cell, and Pt/C (40 wt% Pt) available from Johnson Matthey corporation was used as a cathode hydrogen evolution catalyst. The effective area of the catalyst is about 1cm2. The oxygen evolution activity (LCV) of the different catalysts is shown in FIG. 1, and it can be seen from FIG. 4 that the current density of the strontium titanate supported iridium oxide electrocatalyst exceeds 10mA/cm at 1.4Vsce2The activity of the iridium oxide electrocatalyst supported on gold-plated titanium oxide was about 10 times (1 mA/cm)2) An activity 20 times or more that of the iridium oxide electrocatalyst supported on titanium oxide<0.5mA/cm2). Of the three non-noble metal dispersed noble metal electrocatalysts, the strontium titanate supported iridium oxide catalyst performed best.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. The titanate-supported noble metal-based oxygen evolution electrocatalyst is characterized by comprising titanate, titanate with lattice vacancy and noble metal oxide; the titanate is selected from one of strontium titanate, barium titanate, magnesium titanate, calcium titanate, yttrium titanate and zinc titanate; the noble metal oxide is iridium oxide or ruthenium oxide;
the titanate with lattice defect is composed of titanate and H+The reaction is carried out to obtain;
the preparation method of the titanate supported noble metal based oxygen evolution electrocatalyst comprises the following steps of:
(1) mixing the nano titanate solution with metal chloric acid, and then adding sodium hydroxide to form a mixed solution with the pH value of 5-11;
or mixing the nano titanate solution with sodium hydroxide, adding metal chloric acid to form a mixed solution, and adjusting the pH value to be less than 7;
(2) centrifuging the mixed solution obtained in the step (1), and taking a precipitate;
(3) and (3) calcining the precipitate obtained in the step (2) to obtain the oxygen evolution electrocatalyst.
2. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 1, characterized in that the titanate is strontium titanate.
3. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 1, characterized in that the mass ratio of titanate to noble metal oxide is 10-99: 1-90.
4. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 3, comprising titanate core bodies and titanate-coated composite layers comprising titanates having lattice vacancies and noble metal oxides.
5. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 4, wherein said composite layer comprises a titanate layer having lattice vacancies and a noble metal oxide layer.
6. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 4, wherein said composite layer comprises a titanate layer having lattice vacancies, a noble metal oxide layer, and a mixed layer formed from a mixture of titanates and noble metal oxides having lattice vacancies.
7. The titanate-supported noble metal-based oxygen evolution electrocatalyst according to claim 4, wherein said composite layer comprises a mixed layer formed from a mixture of titanates and noble metal oxides with lattice vacancies.
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