CN109569593B - Oxygen evolution electrocatalyst of strontium-doped noble metal oxide and preparation method thereof - Google Patents
Oxygen evolution electrocatalyst of strontium-doped noble metal oxide and preparation method thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 65
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 65
- 239000001301 oxygen Substances 0.000 title claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 33
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims abstract description 27
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940005991 chloric acid Drugs 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 56
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 26
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 18
- 238000011068 loading method Methods 0.000 description 15
- 229910000457 iridium oxide Inorganic materials 0.000 description 13
- 238000013112 stability test Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 150000002926 oxygen Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen 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
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical compound [Ir]=O YJZATOSJMRIRIW-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
- 239000000919 ceramic Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 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
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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 an oxygen evolution electrocatalyst of a strontium-doped noble metal oxide and a preparation method thereof. According to the invention, by utilizing the condition that the solubility of strontium hydroxide changes along with the temperature, a high-temperature strontium hydroxide solution reacts with metal chloric acid, then the temperature is reduced to separate out a strontium hydroxide precipitate on the outer layer of a noble metal hydroxide, and the precipitate is calcined at high temperature to obtain the oxygen evolution electrocatalyst of a strontium-doped noble metal oxide; the method is simple, has low requirement on equipment, and 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 an oxygen evolution electrocatalyst of a strontium-doped noble metal oxide 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. Prepared by heating Ir @ Ti catalyst at different temperaturesIrO2Wrapped 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. IrO is prepared according to the molar ratio of Ir to Ti of 1: 2, 1: 6 and 1: 102@ 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 continuously dedicated to searching a supported noble metal oxygen evolution catalyst with simple preparation method, low cost and good catalytic performance, and at present, the combination of strontium (Sr) and noble metal oxide as an oxygen evolution electrocatalyst is not reported.
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 the strontium-doped noble metal oxide in the prior art, thereby providing the oxygen evolution electrocatalyst of the strontium-doped noble metal oxide and the preparation method thereof, wherein the preparation method is simple, the cost is low, and the catalyst activity is good.
Therefore, the technical scheme of the invention is as follows:
a preparation method of an oxygen evolution electrocatalyst of a strontium-doped noble metal oxide comprises the following steps:
(1) mixing metal chloric acid with strontium hydroxide solution at 70-90 ℃;
(2) cooling the mixed solution obtained in the step (1) to 0-30 ℃, centrifuging, 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), the molar ratio of strontium hydroxide to metal chloric acid is not less than 3: 1.
further, in the step (1), the metal chloric acid is chloro-iridic acid or chloro-ruthenic acid.
Further, in the step (1), the concentration of the metal chloric acid is 0.02-2 mol/L.
Further, in the step (1), the concentration of strontium hydroxide is 0.15-1.7 mol/L.
Further, metal chloric acid and metal oxide nano-particles are mixed to form a suspension, and then the suspension is mixed with a strontium hydroxide solution at 70-90 ℃.
Further, in the step (1), the metal oxide is one of titanium oxide, tin oxide and zirconium oxide.
Further, in the step (1), the molar ratio of metal chloric acid to metal oxide is 1: 0.1-10.
further, in the step (3), the calcination temperature is 400-.
An oxygen evolution electrocatalyst of a strontium doped noble metal oxide prepared according to the above method.
Further, the oxygen evolution electrocatalyst includes a noble metal oxide and strontium oxide having crystal lattice vacancies.
Further, the oxygen evolution electrocatalyst is of a core-shell structure and comprises a core body and strontium oxide coated on the core body and having crystal lattice vacancies, wherein the core body is a noble metal oxide; or the core body is a mixture formed by noble metal oxide and metal oxide; or the core body is a composite structure formed by encapsulating metal oxide by noble metal oxide;
further, the noble metal oxide is iridium oxide or ruthenium oxide; the metal oxide is one of titanium oxide, tin oxide and zirconium oxide.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of an oxygen evolution electrocatalyst of a strontium-doped noble metal oxide, which is characterized in that strontium is precipitated by utilizing the change of the solubility of strontium hydroxide along with the temperature to synthesize the strontium-doped oxygen evolution electrocatalyst.
2. The invention provides an oxygen evolution electrocatalyst prepared by strontium-doped noble metal oxide, wherein non-noble metal strontium (Sr) is doped into a noble metal catalyst, so that the influence on crystal lattices can be generated, the reaction sites of the catalyst are increased, the performance of the catalyst is improved, and the loading amount of noble metal is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of an oxygen evolution electrocatalyst prepared in examples 1-8 of the present invention;
FIG. 2 is a schematic diagram of the structure of an oxygen evolution electrocatalyst prepared in examples 1-8 of the present invention;
FIG. 3 XRD profile of the oxygen evolution electrocatalyst prepared in example 1;
FIG. 4 SEM image of oxygen evolution electrocatalyst prepared in example 1;
figure 5 XRD signature of the oxygen evolution electrocatalyst prepared in example 9.
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 particle size of the metal oxides, i.e., titanium oxide, tin oxide and zirconium oxide, in the examples and comparative examples was 30 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 stability test method comprises the following steps: fixing the electrolysis voltage for a period of time, and testing the attenuation value of the current density; or at a fixed current density for a period of time.
Example 1
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridate; preparing 21.85mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the above two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining at 550 deg.C for 2 hr to obtain 0.55g of SrO and IrO2The molar ratio is 1: 2 strontium-doped iridium oxide oxygen evolution electrocatalyst.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential of the catalyst is 0.28V, and the current density is 100mA/cm2The overpotential of the catalyst is 0.66V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays by 5%. FIG. 1 is a schematic diagram of the structure of an oxygen evolution electrocatalyst prepared according to examples 1-8, in which the core is a noble metal oxide and the shell is strontium oxide with crystal lattice vacancies; FIG. 3 is an XRD characteristic spectrum of the oxygen evolution electrocatalyst prepared in this example; fig. 4 is an SEM image of the oxygen evolution electrocatalyst prepared in this example.
Example 2
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridate; preparing 28.45mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the above two solutions, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining at 550 deg.C for 2 hr to obtain 0.86g of SrO and IrO2The molar ratio is 2: 1 strontium-doped iridium oxide oxygen evolution electrocatalyst.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.33V, and the current density was 100mA/cm2The overpotential of the catalyst is 0.74V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays by 5.5%.
Example 3
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
20mL of 0.02mol/L chloroiridate is prepared; preparing 8mL of 0.15mol/L strontium hydroxide solution at 90 ℃; mixing the two, cooling to 30 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 400 ℃ for 4 hours to obtain the strontium-doped iridium oxide oxygen evolution electrocatalyst.
Example 4
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
20mL of 2mol/L chloroiridate is prepared; 100mL of 1.7mol/L strontium hydroxide solution at 70 ℃ is prepared; mixing the two, cooling to 0 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 600 ℃ for 1.5h to obtain the strontium-doped iridium oxide oxygen evolution electrocatalyst.
Example 5
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 0.1mol/L chlororuthenate; preparing 21.85mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining the precipitate at 550 deg.C for 2 hr to obtain SrO and RuO2The molar ratio is 1: 2 strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential of the catalyst is 0.28V, and the current density is 100mA/cm2The overpotential of the catalyst is 0.64V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 6.0%.
Example 6
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 0.1mol/L chlororuthenate; preparing 28.45mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining the precipitate at 550 deg.C for 2 hr to obtain SrO and RuO2The molar ratio is 2: 1 strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.31V and the current density was 100mA/cm2The overpotential of the catalyst is 0.68V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 5.8%.
Example 7
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 1mol/L chlororuthenate; preparing 80mL of 1.0mol/L strontium hydroxide solution at 85 ℃; mixing the two, cooling to 20 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 800 ℃ for 1h to obtain the strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
Example 8
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 0.5mol/L chlororuthenate; 25mL of 1.2mol/L strontium hydroxide solution at 85 ℃; mixing the two, cooling to 20 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 800 ℃ for 1h to obtain the strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
Example 9
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridic acid, and adding 0.002mol of titanium oxide nano particles to form a suspension; preparing 28.45mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the above two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining the precipitate at 550 deg.C for 2 hr to obtain IrO2、SrO、TiO2The molar ratio is 1: 0.5: 1 strontium-doped iridium oxide oxygen evolution electrocatalyst.
The preparation loading is 3mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential of the catalyst is 0.35V, and the current density is 100mA/cm2The overpotential of the catalyst is 0.75V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density attenuation is 4.5 percent; FIG. 2 is a schematic diagram showing the structures of oxygen evolution electrocatalysts prepared in examples 9 to 12, wherein the core is a composite structure formed by encapsulating a metal oxide with a noble metal oxide, and the shell is strontium oxide having crystal lattice vacancies. Fig. 5 is an XRD characteristic spectrum of the oxygen evolution electrocatalyst prepared in this example.
Example 10
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridic acid, and adding 0.01mol of titanium oxide nanoparticles to form a suspension; preparing 28.45mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the above two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, calcining the precipitate at 550 deg.C for 2 hr to obtain IrO2、SrO、TiO2The molar ratio is 1: 0.5: 5 strontium-doped iridium oxide oxygen evolution electrocatalyst.
Example 11
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 0.02mol/L chlororuthenate, and adding 0.004mol of tin oxide nano-particles to form a suspension; preparing 15mL of 0.15mol/L strontium hydroxide solution at 90 ℃; mixing the two, cooling to 30 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 400 ℃ for 4 hours to obtain the strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
The preparation loading is 3mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.33V, and the current density was 100mA/cm2The overpotential of the catalyst is 0.74V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 5.6%.
Example 12
Preparation of oxygen evolution electrocatalyst of strontium-doped ruthenium oxide
Preparing 20mL of 2mol/L chlororuthenate, and adding 0.004mol of zirconium oxide nano particles to form a suspension; preparing 80mL of 1.7mol/L strontium hydroxide solution at 70 ℃; mixing the two, cooling to 0 ℃, centrifuging at 10000rpm, taking the precipitate, and calcining the precipitate at 600 ℃ for 1.5h to obtain the strontium-doped ruthenium oxide oxygen evolution electrocatalyst.
Comparative example 1
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridate; preparing 21.85mL of 0.6mol/L strontium hydroxide solution at 60 ℃; mixing the two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, and calcining the precipitate at 550 deg.C for 2 hr.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential is 0.39V and the current density is 100mA/cm2When the catalyst is used, the overpotential of the catalyst is 0.81V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 7.1%.
Comparative example 2
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridate; preparing 21.85mL of 0.6mol/L strontium hydroxide solution at 100 ℃; mixing the two, cooling to 20 deg.C, centrifuging at 10000rpm, collecting precipitate, and calcining the precipitate at 550 deg.C for 2 hr.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential is 0.38V and the current density is 100mA/cm2The overpotential of the catalyst is 0.84V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 8%.
Comparative example 3
Preparation of oxygen evolution electrocatalyst of strontium doped iridium oxide
Preparing 20mL of 0.1mol/L chloroiridate; preparing 21.85mL of 0.6mol/L strontium hydroxide solution at 80 ℃; mixing the two, cooling to 40 deg.C, centrifuging at 10000rpm, collecting precipitate, and calcining the precipitate at 550 deg.C for 2 hr.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.40V, and the current density was 100mA/cm2The overpotential of the catalyst is 0.83V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 9%.
Comparative example 4
1mol of iridium hydroxide and 0.5mol of strontium hydroxide were mixed and then calcined at 550 ℃ for 2 hours.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.42V, and the current density was 100mA/cm2The overpotential of the catalyst is 0.98V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 11%.
Comparative example 5
Preparing 20mL of 0.1mol/L chloroiridate; preparing 21mL of 0.2mol/L sodium hydroxide solution at 80 ℃; mixing the two solutions, adding 0.01mol titanium oxide nanoparticles (diameter 30nm) to form suspension, cooling to 40 deg.C, centrifuging at 10000rpm, collecting precipitate, and calcining at 550 deg.C for 2 hr. An iridium oxide electrocatalyst supported only by titanium oxide was obtained.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2When the catalyst is used, the overpotential of the catalyst is 0.48V, and the current density is 100mA/cm2When the catalyst is used, the overpotential of the catalyst is 1.08V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays by 10%. The iridium oxide electrocatalyst supported on titanium oxide has poorer performance than the iridium oxide catalyst supported on strontium oxide or strontium oxide + titanium oxide.
Comparative example 6
Preparing 20mL of 0.1mol/L chlororuthenate; preparing 21mL of 0.2mol/L sodium hydroxide solution at 80 ℃; mixing the two solutions, adding 0.01mol titanium oxide nanoparticles (diameter 30nm) to form suspension, cooling to 40 deg.C, centrifuging at 10000rpm, collecting precipitate, and calcining at 550 deg.C for 2 hr. A ruthenium oxide electrocatalyst supported only by titanium oxide was obtained.
The preparation loading is 2.5mg/cm2The oxygen evolution electrode of (1) was tested at a current density of 10mA/cm2The overpotential of the catalyst was 0.44V, and the current density was 100mA/cm2When the catalyst is used, the overpotential of the catalyst is 1.01V; at 100mA/cm2Under the test condition of the current density, after 2.5 hours of stability test, the current density decays to 12%. The titanium oxide-supported ruthenium oxide electrocatalyst has poorer performance than the strontium oxide or strontium oxide + titanium oxide-supported ruthenium oxide catalyst.
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 (3)
1. A preparation method of an oxygen evolution electrocatalyst of a strontium-doped noble metal oxide is characterized by comprising the following steps:
(1) firstly, mixing metal chloric acid and metal oxide nano particles to form a suspension, and then mixing the suspension with a strontium hydroxide solution at 70-90 ℃;
(2) cooling the mixed solution obtained in the step (1) to 0-30 ℃, centrifuging, and taking a precipitate;
(3) calcining the precipitate obtained in the step (2) to obtain the oxygen evolution electrocatalyst;
in the step (1), the metal chloric acid is chloro-iridic acid or chloro-ruthenic acid, the addition concentration of the metal chloric acid is 0.02-2 mol/L, the metal oxide is one of titanium oxide, tin oxide and zirconium oxide, the addition concentration of strontium hydroxide is 0.15-1.7 mol/L, and the molar ratio of the strontium hydroxide to the metal chloric acid in the mixed solution is more than or equal to 3: 1, and the molar ratio of metal chloric acid to metal oxide is 1: 0.1 to 10;
in the step (3), the calcination temperature is 400-1200 ℃, and the calcination time is 1-4 h.
2. An oxygen evolution electrocatalyst of strontium doped noble metal oxide prepared according to the preparation method of claim 1.
3. The oxygen evolution electrocatalyst according to claim 2, comprising noble metal oxides and strontium oxide with crystal lattice vacancies.
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