CN109569593A - A kind of analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals and preparation method thereof - Google Patents
A kind of analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals and preparation method thereof Download PDFInfo
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- CN109569593A CN109569593A CN201811450919.5A CN201811450919A CN109569593A CN 109569593 A CN109569593 A CN 109569593A CN 201811450919 A CN201811450919 A CN 201811450919A CN 109569593 A CN109569593 A CN 109569593A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 74
- 239000001301 oxygen Substances 0.000 title claims abstract description 74
- 238000004458 analytical method Methods 0.000 title claims abstract description 67
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 45
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 32
- 239000010970 precious metal Substances 0.000 title claims abstract description 21
- 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 26
- 230000001376 precipitating effect Effects 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 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
- 238000001354 calcination Methods 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000005119 centrifugation Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-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
- -1 chlorine iridium Acid Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 16
- 238000011068 loading method Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 14
- 238000013112 stability test Methods 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 10
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000002474 experimental 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 239000010953 base metal Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material 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
- 238000003786 synthesis reaction 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to elctro-catalyst fields, and in particular to a kind of analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals and preparation method thereof.The present invention utilizes strontium hydroxide solubility with temperature situation of change, high temperature strontium hydroxide solution is reacted with metal chloric acid, again by cooling so that the outer layer precipitation strontium hydroxide precipitating of noble metal hydroxide, will precipitate high-temperature calcination, obtain the analysis oxygen elctro-catalyst of the metal oxide containing precious metals of strontium doping；The method of the present invention is simple, low for equipment requirements, and the analysis oxygen elctro-catalyst stability of acquisition is good, and reaction site is more, and catalytic activity is high.
Description
Technical field
The invention belongs to elctro-catalyst fields, and in particular to a kind of analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals and
Preparation method.
Background technique
Energy Conversion Technology is dissolved in renewable energy to play a significant role with storage, wherein solid polymer water electrolysis
It is more that (Solid polymer water electrolysis, SPE) technology has that high-efficient, small in size, start and stop are fast, the service life is long etc.
Kind advantage, gradually to be received both at home and abroad and being tentatively commercialized.
However since solid polymer water electrolysis technology needs to use noble metal as its catalyst, pile cost is more current
Universal lye electrolysis is higher, so limiting its application scale.Side is precipitated in hydrogen, can be used at present carbon-supported
Platinum catalyst reaches better performance under lower noble metal loadings.Hydrogen evolution reaction also only relates to 2 electricity
The overpotential of son, elctro-catalyst is relatively low.And be 4 electron reactions for oxygen evolution, the overpotential of elctro-catalyst is relatively
Height needs the catalyst using high noble metal (iridium/ruthenium) loading to reach preferable performance.However your gold is used merely
Belong to big as the consumption of catalyst, cost is excessively high, therefore generally can be added to carrier for noble metal as activity, and load is made
Type noble metal catalyst.Common carrier has TiO2、Al2O3、AC、SnO2With MOF etc., such as (Sun Liangliang, the Luo Ling such as Sun Liang is good
Rainbow, Shi Jijun, Cheng Liang, Liu Lili, Xu Xu have core-shell structure IrO2In research [J] of the electrolysis water oxygen-separating catalyst of@Ti
State's ceramics, 2017,53 (07): 36-40.) with H2IrCl6·nH2O and titanium valve are primary raw material, using sodium borohydride reduction
Prepare iridium package titanium (Ir@Ti) catalyst.By heating at different temperatures to Ir@Ti catalyst, IrO is prepared2
Wrap up Ti (IrO2@Ti) catalyst.Research shows that: the IrO of this method preparation2@Ti catalyst, nanoscale IrO2It is distributed in Ti
Grain surface, forms the coated catalytic layer with core-shell structure.The IrO handled at 500 DEG C2@Ti catalyst has highest
Oxygen evolution activity.Molar ratio according to Ir: Ti is the IrO of 1: 2,1: 6,1: 10 configurations2@Ti catalyst, with IrO2The increasing of content
Height forms IrO2Sheath configuration, IrO2Catalytic Layer, which is coated on, can be effectively reduced oxygen evolution potential.The wherein catalyst of 1:2
Oxygen best performance is analysed, under normal pressure, at 25 DEG C, electrolysis water electric current is 0.24Acm-2When decomposition voltage be 3V.Chinese patent
Application CN108546962A discloses a kind of preparation method of the electrolysis water oxygen-separating catalyst of high specific surface area porous carbon doped iridium,
Iridium ion is impregnated into using infusion process and obtains presoma in organic frame MOF-5 material and thus to prepare high-specific surface area more
Hole carbon doped iridium oxygen-separating catalyst, the preparation process improve corrosion resistance of the anode of electrolytic water catalyst in acidic electrolysis bath
With the stability of catalyst.But the step of this preparation method, is various, and needs more organic solvent, higher cost.
However, these researchs the problems such as that there are still catalyst activities is low, and preparation method is complicated, and consumption of organic solvent is big.This field skill
Art personnel have been devoted to find the carried noble metal analysis oxygen catalysis that a kind of preparation method is simple, at low cost, catalytic performance is good
Agent, and there is no the reports that strontium (Sr) and metal oxide containing precious metals are combined as to analysis oxygen elctro-catalyst at present.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming in the prior art does not have strontium doping metal oxide containing precious metals
The defect of oxygen-separating catalyst is prepared, to provide a kind of preparation method simple, at low cost, good catalyst activity the expensive gold of strontium doping
Belong to the analysis oxygen elctro-catalyst and preparation method thereof of oxide.
For this purpose, technical scheme is as follows:
A kind of preparation method of the analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals, comprising the following steps:
(1) metal chloric acid is mixed with 70-90 DEG C of strontium hydroxide solution；
(2) mixed solution that step (1) obtains is cooled to 0-30 DEG C, centrifugation takes precipitating；
(3) the precipitating calcining obtained step (2) is to get analysis oxygen elctro-catalyst.
Further, in the step (1), molar ratio >=3:1 of strontium hydroxide and metal chloric acid.
Further, in the step (1), metal chloric acid is chloro-iridic acid or ruthenium hydrochloride.
Further, in the step (1), the concentration of metal chloric acid is 0.02-2mol/L.
Further, in the step (1), the concentration of strontium hydroxide is 0.15-1.7mol/L.
Further, the nano particle of metal chloric acid and metal oxide is first mixed to form suspension, then with 70-90
DEG C strontium hydroxide solution mixing.
Further, in the step (1), metal oxide is one of titanium oxide, tin oxide and zirconium oxide.
Further, in the step (1), metal chloric acid and metal oxide molar ratio are 1:0.1-10.
Further, in the step (3), calcination temperature is 400-1200 DEG C, calcination time 1-4h.
A kind of analysis oxygen elctro-catalyst for the strontium doping metal oxide containing precious metals being prepared according to the above method.
Further, the analysis oxygen elctro-catalyst includes metal oxide containing precious metals and the strontium oxide strontia for having lattice vacancy.
Further, the analysis oxygen elctro-catalyst is core-shell structure, and including nucleome and be coated on nucleome have lattice vacancy
Strontium oxide strontia, the nucleome be metal oxide containing precious metals；Or to be that metal oxide containing precious metals and metal oxide are formed mixed for the nucleome
It is fit；Or the nucleome is the composite construction that metal oxide containing precious metals encapsulated metal oxide is formed；
Further, the metal oxide containing precious metals are yttrium oxide or ruthenium-oxide；The metal oxide is titanium oxide, oxidation
One of tin and zirconium oxide.
Technical solution of the present invention has the advantages that
1, the present invention provides a kind of preparation method of the analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals, utilizes hydroxide
Strontium is precipitated in the variation of strontium solubility with temperature, and the analysis oxygen elctro-catalyst of synthesis doping strontium, preparation method is simple, without any organic solvent
Addition, high safety is low for equipment requirements, be suitble to large-scale production.
2, the present invention provides a kind of strontium doping metal oxide containing precious metals preparation analysis oxygen elctro-catalyst, and base metal strontium (Sr) is mixed
Enter in noble metal catalyst, lattice can be had an impact, increase catalyst reaction site, improve catalyst performance, reduces expensive
Metal loading.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the analysis oxygen elctro-catalyst that 1-8 of the embodiment of the present invention is prepared；
Fig. 2 is the structural schematic diagram for the analysis oxygen elctro-catalyst that 1-8 of the embodiment of the present invention is prepared；
The XRD characteristic spectrum for the analysis oxygen elctro-catalyst that Fig. 3 embodiment 1 is prepared；
The SEM figure for the analysis oxygen elctro-catalyst that Fig. 4 embodiment 1 is prepared；
The XRD characteristic spectrum for the analysis oxygen elctro-catalyst that Fig. 5 embodiment 9 is prepared.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
The partial size of metal oxide, that is, titanium oxide, tin oxide and zirconium oxide is 30nm in embodiment and comparative example.
Overpotential test method: overpotential test method: VA characteristic curve is measured using electrochemical workstation, in correspondence
Current density under decomposition voltage value, subtract the numerical value of voltage needed for kinetics (1.229V).
Stability test method: continued electrolysis for a period of time, tests the decaying of current density under fixed a certain decomposition voltage
Value；Or continued electrolysis is for a period of time under fixed a certain current density.
Embodiment 1
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.1mol/L；80 DEG C of configuration, the strontium hydroxide solution 21.85mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h, obtain 0.55g, SrO, IrO2
The strontium doping yttrium oxide that molar ratio is 1:2 analyses oxygen elctro-catalyst.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.28V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.66V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 5%.Fig. 1 is embodiment 1-
The structural schematic diagram of the 8 analysis oxygen elctro-catalysts being prepared, nucleome is metal oxide containing precious metals, and shell is the oxidation for having lattice vacancy
Strontium；Fig. 3 is the XRD feature spectrogram for the analysis oxygen elctro-catalyst that the present embodiment is prepared；Fig. 4 is the analysis that the present embodiment is prepared
The SEM of oxygen elctro-catalyst schemes.
Embodiment 2
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.1mol/L；80 DEG C of configuration, the strontium hydroxide solution 28.45mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h, obtain 0.86g, SrO, IrO2
The strontium doping yttrium oxide that molar ratio is 2:1 analyses oxygen elctro-catalyst.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.33V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.74V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 5.5%.
Embodiment 3
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.02mol/L；90 DEG C of configuration, the strontium hydroxide solution 8mL of 0.15mol/L；By the two
30 DEG C are cooled to after mixing, 10000rpm centrifugation takes precipitating, will be deposited in 400 DEG C of calcining 4h to get strontium doping yttrium oxide and analyses oxygen
Elctro-catalyst.
Embodiment 4
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 2mol/L；70 DEG C of configuration, the strontium hydroxide solution 100mL of 1.7mol/L；The two is mixed
0 DEG C is cooled to after conjunction, 10000rpm centrifugation takes precipitating, will be deposited in 600 DEG C of calcining 1.5h to get strontium doping yttrium oxide and analyses oxygen
Elctro-catalyst.
Embodiment 5
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
Configure the ruthenium hydrochloride 20mL of 0.1mol/L；80 DEG C of configuration, the strontium hydroxide solution 21.85mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h, obtain SrO, RuO2Molar ratio
Oxygen elctro-catalyst is analysed for the strontium doping ruthenium-oxide of 1:2.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.28V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.64V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 6.0%.
Embodiment 6
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
Configure the ruthenium hydrochloride 20mL of 0.1mol/L；80 DEG C of configuration, the strontium hydroxide solution 28.45mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h, obtain SrO, RuO2Molar ratio
Oxygen elctro-catalyst is analysed for the strontium doping ruthenium-oxide of 2:1.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.31V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.68V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 5.8%.
Embodiment 7
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
Configure the ruthenium hydrochloride 20mL of 1mol/L；85 DEG C of configuration, the strontium hydroxide solution 80mL of 1.0mol/L；The two is mixed
After be cooled to 20 DEG C, 10000rpm centrifugation takes precipitating, will be deposited in 800 DEG C of calcining 1h and analyses oxygen electricity to get strontium doping ruthenium-oxide and urges
Agent.
Embodiment 8
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
Configure the ruthenium hydrochloride 20mL of 0.5mol/L；85 DEG C of configuration, the strontium hydroxide solution 25mL of 1.2mol/L；The two is mixed
20 DEG C are cooled to after conjunction, 10000rpm centrifugation takes precipitating, will be deposited in 800 DEG C of calcining 1h to get strontium doping ruthenium-oxide analysis oxygen electricity
Catalyst.
Embodiment 9
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
The chloro-iridic acid 20mL for configuring 0.1mol/L, the Titanium dioxide nanoparticle that 0.002mol is added form suspension；Configuration
80 DEG C, the strontium hydroxide solution 28.45mL of 0.6mol/L；20 DEG C are cooled to after the two is mixed, 10000rpm centrifugation, it is heavy to take
It forms sediment, 550 DEG C of calcining 2h will be deposited in get IrO2、SrO、TiO2The strontium doping yttrium oxide that molar ratio is 1:0.5:1 is analysed oxygen electricity and is urged
Agent.
Preparing loading is 3mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalyst
Overpotential be 0.35V, current density be 100mA/cm2When, the overpotential of the catalyst is 0.75V；In 100mA/cm2Electricity
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 4.5%；Fig. 2 is embodiment 9-
The structural schematic diagram of the 12 analysis oxygen elctro-catalysts being prepared, nucleome is answering for metal oxide containing precious metals encapsulated metal oxide formation
Structure is closed, shell is the strontium oxide strontia for having lattice vacancy.Fig. 5 is the XRD feature for the analysis oxygen elctro-catalyst that the present embodiment is prepared
Spectrogram.
Embodiment 10
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
The chloro-iridic acid 20mL for configuring 0.1mol/L, the Titanium dioxide nanoparticle that 0.01mol is added form suspension；Configuration 80
DEG C, the strontium hydroxide solution 28.45mL of 0.6mol/L；20 DEG C are cooled to after the two is mixed, 10000rpm centrifugation takes precipitating,
550 DEG C of calcining 2h will be deposited in get IrO2、SrO、TiO2The strontium doping yttrium oxide that molar ratio is 1:0.5:5 analyses oxygen electro-catalysis
Agent.
Embodiment 11
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
The ruthenium hydrochloride 20mL for configuring 0.02mol/L, the tin oxide nanoparticles that 0.004mol is added form suspension；Configuration
90 DEG C, the strontium hydroxide solution 15mL of 0.15mol/L；30 DEG C are cooled to after the two is mixed, 10000rpm centrifugation takes precipitating,
400 DEG C of calcining 4h will be deposited in and analyse oxygen elctro-catalyst to get strontium doping ruthenium-oxide.
Preparing loading is 3mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalyst
Overpotential be 0.33V, current density be 100mA/cm2When, the overpotential of the catalyst is 0.74V；In 100mA/cm2Electricity
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 5.6%.
Embodiment 12
The preparation of the analysis oxygen elctro-catalyst of strontium doping ruthenium-oxide
The ruthenium hydrochloride 20mL for configuring 2mol/L, the Zirconium oxide nano grain that 0.004mol is added form suspension；Configuration 70
DEG C, the strontium hydroxide solution 80mL of 1.7mol/L；0 DEG C is cooled to after the two is mixed, 10000rpm centrifugation takes precipitating, will sink
It forms sediment and analyses oxygen elctro-catalyst in 600 DEG C of calcining 1.5h to get strontium doping ruthenium-oxide.
Comparative example 1
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.1mol/L；60 DEG C of configuration, the strontium hydroxide solution 21.85mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.39V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.81V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 7.1%.
Comparative example 2
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.1mol/L；100 DEG C of configuration, the strontium hydroxide solution 21.85mL of 0.6mol/L；By two
20 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.38V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.84V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 8%.
Comparative example 3
The preparation of the analysis oxygen elctro-catalyst of strontium doping yttrium oxide
Configure the chloro-iridic acid 20mL of 0.1mol/L；80 DEG C of configuration, the strontium hydroxide solution 21.85mL of 0.6mol/L；By two
40 DEG C are cooled to after person's mixing, 10000rpm centrifugation takes precipitating, will be deposited in 550 DEG C of calcining 2h.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.40V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.83V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 9%.
Comparative example 4
After 1mol hydroxide iridium and 0.5mol strontium hydroxide are mixed, in 550 DEG C of calcining 2h.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.42V, is 100mA/cm in current density2When, the overpotential of the catalyst is 0.98V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 11%.
Comparative example 5
Configure the chloro-iridic acid 20mL of 0.1mol/L；80 DEG C of configuration, the sodium hydroxide solution 21mL of 0.2mol/L；The two is mixed
After conjunction, the Titanium dioxide nanoparticle (diameter 30nm) that 0.01mol is added forms suspension, is cooled to 40 DEG C, and 10000rpm is centrifuged,
Precipitating is taken, 550 DEG C of calcining 2h will be deposited in.Obtain the yttrium oxide elctro-catalyst that only titanium oxide supports.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.48V, is 100mA/cm in current density2When, the overpotential of the catalyst is 1.08V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 10%.What titanium oxide supported
Yttrium oxide elctro-catalyst performance is poor compared with the oxidation iridium catalyst that strontium oxide strontia or strontium oxide strontia+titanium oxide support.
Comparative example 6
Configure the ruthenium hydrochloride 20mL of 0.1mol/L；80 DEG C of configuration, the sodium hydroxide solution 21mL of 0.2mol/L；The two is mixed
After conjunction, the Titanium dioxide nanoparticle (diameter 30nm) that 0.01mol is added forms suspension, is cooled to 40 DEG C, and 10000rpm is centrifuged,
Precipitating is taken, 550 DEG C of calcining 2h will be deposited in.Obtain the oxidation ruthenium electro-catalyst that only titanium oxide supports.
Preparing loading is 2.5mg/cm2Analysis oxygen electrode, by test, current density be 10mA/cm2When, the catalysis
The overpotential of agent is 0.44V, is 100mA/cm in current density2When, the overpotential of the catalyst is 1.01V；In 100mA/cm2
Under the test condition of current density, after 2.5 hours stability tests, current density decays to 12%.What titanium oxide supported
It is poor compared with the ruthenium oxide catalysts that strontium oxide strontia or strontium oxide strontia+titanium oxide support to aoxidize ruthenium electro-catalyst performance.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of preparation method of the analysis oxygen elctro-catalyst of strontium doping metal oxide containing precious metals, which comprises the following steps:
(1) metal chloric acid is mixed with 70-90 DEG C of strontium hydroxide solution；
(2) mixed solution that step (1) obtains is cooled to 0-30 DEG C, centrifugation takes precipitating；
(3) the precipitating calcining obtained step (2) is to get analysis oxygen elctro-catalyst.
2. preparation method according to claim 1, which is characterized in that in the step (1), strontium hydroxide and metal chloric acid
Molar ratio >=3:1.
3. preparation method according to claim 1 or 2, which is characterized in that in the step (1), metal chloric acid is chlorine iridium
Acid or ruthenium hydrochloride.
4. preparation method according to claim 1-3, which is characterized in that in the step (1), first by metal
The nano particle of chloric acid and metal oxide is mixed to form suspension, then mixes with 70-90 DEG C of strontium hydroxide solution.
5. the preparation method according to claim 4, which is characterized in that the metal oxide is titanium oxide, tin oxide
One of with zirconium oxide.
6. preparation method according to claim 1-5, which is characterized in that in the step (1), metal chloric acid
It is 1:0.1-10 with metal oxide molar ratio.
7. preparation method according to claim 1-6, which is characterized in that in the step (3), calcination temperature
It is 400-1200 DEG C, calcination time 1-4h.
8. a kind of strontium doping metal oxide containing precious metals that preparation method according to claim 1-7 is prepared
Analyse oxygen elctro-catalyst.
9. analysis oxygen elctro-catalyst according to claim 8, which is characterized in that including metal oxide containing precious metals and have lattice vacancy
Strontium oxide strontia.
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