CN116590735A - Oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies and preparation process thereof - Google Patents
Oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies and preparation process thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000001301 oxygen Substances 0.000 title claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 81
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 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
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000001307 helium Substances 0.000 claims abstract description 3
- 229910052734 helium Inorganic materials 0.000 claims abstract description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical group [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007806 chemical reaction intermediate Substances 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000457 iridium oxide Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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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)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies and a preparation process thereof, wherein the preparation process comprises the following steps: s1, drying metal oxide; s2, mixing the precursor solution of the soluble metal salt, the metal oxide in the S1 and the aqueous solution of the reducing agent, and depositing the metal nano particles on the surface of the metal oxide by using a solvothermal reduction method; filtering to obtain precipitate after full reaction, and drying; s3, placing the precipitate of the S2 into a resistance furnace with protective atmosphere for heat treatment, wherein the temperature of the heat treatment is 400-600 ℃, the protective atmosphere is inert gas, and the inert gas is nitrogen, helium or argon. The oxygen evolution electrocatalyst prepared by the preparation process has excellent electrocatalytic activity and durability, advanced process and controllable cost, and has wide market application prospect.
Description
Technical Field
The invention relates to the field of electrocatalysts, in particular to an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies and a preparation process thereof.
Background
Proton exchange membrane electrolyzed water is considered to be the most promising electrolyzed water system in the future due to higher current density, energy efficiency and higher hydrogen purity. However, the acidic corrosion environment used by the proton exchange membrane, the oxidation environment required by the oxygen evolution reaction and the four-electron process involved in the oxygen evolution reaction present serious challenges for the development of oxygen evolution electrocatalysts. Development of efficient and stable, cost-friendly oxygen evolution electrocatalyst is one of the bottlenecks of large-scale utilization of the current proton exchange membrane water electrolysis technology. In a strong acid environment suitable for a proton exchange membrane, noble metal iridium oxide is considered as a first catalyst for proton exchange membrane water electrolysis technology commercial use, and the improvement of the utilization rate of iridium element and the improvement of interfacial mass transfer of an electrocatalyst are important problems at present.
An effective strategy to increase overall catalytic activity is to increase the activation sites and their intrinsic activity. Modulating the surface atomic composition, electronic structure and microstructure of the electrocatalyst helps to form highly active catalytic sites and promote the conversion process of the electrocatalytic reaction intermediates. One of the effective strategies to achieve this goal is to prepare a composite catalyst with heterogeneous interfaces, such as an Ir alloy material doped with Cu, ni, co, sn, etc.; for example, ir is supported on a specific metal oxide surface, e.g. IrO 2 、RuO 2 、Fe 2 O 3 And NiCo 2 O 4 Etc. Synergistic catalysis between heterogeneous interfaces not only contributes to H 2 The adsorption process of O on the Ir surface also reduces the desorption energy of the reaction intermediate and effectively improves the electrocatalytic activity and stability. Another strategy is to reconstruct the oxygen-rich vacancy surfaces, the lattice oxygen being activated by increasing the non-stoichiometric ratio of IrOx and participating in the electrocatalytic oxygen evolution process, such as the formation of rich oxygen vacancies in transition metal hydroxides, oxides and perovskite compounds, leading to an effective enhancement of electrocatalytic activity.
It should be noted that the information disclosed in this background section is only for the purpose of increasing the understanding of the general background of the invention for the purpose of understanding the background of the invention that the inventors have created their conception and should not be construed as an admission or any form of suggestion that this information constitutes prior art already known to those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide an oxygen evolution electrocatalyst having heterogeneous interfaces and oxygen-enriched vacancies, and a preparation process thereof, wherein the oxygen evolution electrocatalyst prepared by the preparation process has excellent electrocatalytic activity and durability.
The adopted technical scheme is as follows:
a preparation process of an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies comprises the following steps:
s1, drying metal oxide;
s2, mixing the precursor solution of the soluble metal salt, the metal oxide in the S1 and the aqueous solution of the reducing agent, and depositing the metal nano particles on the surface of the metal oxide by using a solvothermal reduction method; filtering to obtain precipitate after full reaction, and drying;
s3, placing the precipitate of the S2 into a resistance furnace with protective atmosphere for heat treatment, wherein the temperature of the heat treatment is 400-600 ℃, the protective atmosphere is inert gas, and the inert gas is nitrogen, helium or argon.
Further, in S1, the metal oxide is RuO 2 、IrO 2 Or MnO 2 。
Further, in S2, the reducing agent includes one or more of sodium borohydride, formic acid, formaldehyde, and ethylene glycol.
Further, in S2, the concentration of the aqueous solution of the reducing agent is 10-100mmol/L.
Further, in S2, the aqueous reducing agent solution is added dropwise to mix.
Further, in S3, the time of the heat treatment is 1-5 hours.
Further, in S2, the metal oxide is IrO2, and the precursor solution of the soluble metal salt is a chloroiridium solution, a ruthenium chloride solution, or a chloroplatinic acid solution.
Further, in S2, the precursor solution of the soluble metal salt and the metal oxide are mixed first, and then the pH is adjusted to 7-8; next, the mixture was heated and stirred at 60-80℃for 5-6 hours, and then an aqueous reducing agent solution was added dropwise.
An oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies is prepared by the preparation process described in the technical scheme.
Further, the oxygen evolution electrocatalyst is Ru-RuO 2 、Ir-IrO 2 Or Mn-MnO 2 。
Compared with the prior art, the invention can realize the following effects:
the invention provides a preparation process of a novel oxygen evolution electrocatalyst with heterogeneous interfaces and rich oxygen vacancies, which takes a precursor solution of soluble metal salt as a precursor, deposits noble metal nano particles on the surface of metal oxide in a reducing agent aqueous solution thermal reduction mode, and sinters the noble metal nano particles in an inert atmosphere, thereby promoting oxygen species competition between the noble metal nano particles and the metal oxide, forming heterogeneous interfaces and manufacturing rich oxygen defect vacancies, effectively promoting the rapid generation and decomposition of oxygen evolution reaction intermediates, and remarkably improving oxygen evolution electrocatalysis activity and durability. The method has simple process and obvious effect, and is expected to be applied to the commercial production of oxygen evolution electrocatalyst.
That is, the metal nano particles are deposited on the surface of the metal oxide through a simple and controllable preparation process, and the subsequent heat treatment in inert atmosphere promotes the generation of rich heterogeneous interfaces of tight combination between the metal particles and the metal oxide, and simultaneously, a large number of oxygen-enriched vacancy defects are formed, so that the adsorption and desorption processes of the electrocatalytic reaction intermediate product are greatly improved.
The oxygen evolution electrocatalyst prepared by the preparation process has excellent electrocatalytic activity and durability, advanced process and controllable cost, and has wide market application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only embodiments of the present invention, and that other embodiments of the drawings may be obtained without inventive effort to a person skilled in the art.
FIG. 1 is a schematic diagram showing the effect of the preparation process of the oxygen evolution electrocatalyst with rich heterogeneous interfaces and oxygen-enriched vacancies of example 1.
FIG. 2 is a TEM high resolution photograph of an oxygen evolution electrocatalyst with enriched heterogeneous interfaces and oxygen-enriched vacancies treated by the preparation process provided in example 1.
Fig. 3 is XPS spectra before and after the treatment of the preparation process of example 1.
Fig. 4 is a graph showing the comparison of the content of each metal species and the corresponding oxide before and after the treatment in the preparation process of example 1.
FIG. 5 is a graph comparing electrochemical activity of oxygen evolution electrocatalyst with enriched heterogeneous interfaces and oxygen-enriched vacancies treated by the preparation process of example 1 with untreated oxide.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
M in the following examples is mol/L; mM is mmol/L.
Example 1
A preparation process of an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies comprises the following steps:
s1, firstly, preparing a metal oxide carrier. Drying the metal oxide for later use; this example will be made of IrO 2 And (3) drying for later use (or commercial iridium oxide).
S2, then goldBelongs to the deposition of metal nano particles on the surface of oxide. Mixing a precursor solution of soluble metal salt, the metal oxide in S1 and a sodium borohydride aqueous solution, and depositing metal nano particles on the surface of the metal oxide by using a solvothermal reduction method; filtering to obtain precipitate after full reaction, and drying; in this example 90mg of homemade IrO was used 2 (or commercial iridium oxide) and 7.8mL (10 mM, 50% excess) of chloroiridate in methanol are mixed and then the pH is adjusted to slightly above 7, such as pH7.1. Next, the mixture was heated and stirred at 60℃for 5 hours, and then 80mM sodium borohydride aqueous solution was added dropwise. After one hour, the mixture solution was centrifuged, washed, filtered, and the precipitate was taken and dried overnight at 80 ℃.
S3, finally, carrying out inert atmosphere heat treatment on the surface of the electrocatalyst. And (3) placing the precipitate of the S2 into a resistance furnace in an argon atmosphere for heat treatment, wherein the temperature of the heat treatment is 400-600 ℃. In this example, the obtained powder was calcined at 500℃for 1 hour under Ar atmosphere to obtain Ir-IrO 2 A catalyst.
FIG. 1 is a schematic diagram showing the effect of the preparation process of the oxygen evolution electrocatalyst with rich heterogeneous interfaces and oxygen-enriched vacancies of example 1.
The initial state of the step S1 is shown in fig. 1 a. The process effect achieved in step S2 is shown in fig. 1 b. The process effect achieved in step S3 is shown in fig. 1 c. Wherein reference numeral 1 denotes a metal oxide matrix, in this embodiment IrO 2 The label 2 represents the deposited metal nanoparticle, ir in this example, and the label 3 represents the oxygen vacancies formed after the inert atmosphere heat treatment.
FIG. 2 is a TEM high resolution photograph of an oxygen evolution electrocatalyst with enriched heterogeneous interfaces and oxygen-enriched vacancies treated by the preparation process provided in example 1. Wherein the label 4 represents metal nanoparticles, in this example Ir, and the label 5 represents metal oxide particles, in this example IrO 2 。
Fig. 3 is XPS spectra before and after the treatment of the preparation process of example 1. Wherein fig. 3a is an XPS profile comparison of Ir and fig. 3b is an XPS profile comparison of O.
Fig. 4 is a comparison of the content of each metal species with the corresponding oxide before and after the treatment in the preparation process of example 1.
FIG. 5 is a comparison of electrochemical activity of oxygen evolution electrocatalyst with enriched heterogeneous interfaces and oxygen-enriched vacancies treated by the preparation process of example 1 versus untreated oxide.
Experimental methods were conducted with reference to conventional experimental methods in the art, and the above experimental results indicate that the oxygen evolution electrocatalyst prepared by the process has excellent electrocatalytic activity and unexpected durability.
In fig. 1, the preparation process of the invention is to introduce metal nano particles on the surface of noble metal oxide, and make the metal nano particles abstract partial oxygen on the surface of oxide by means of inert atmosphere sintering, so as to form abundant oxygen vacancy defects and heterogeneous surfaces. In fig. 3 to 4, in XPS analysis, the oxygen vacancy content of the oxygen evolution electrocatalyst constructed in this way was significantly increased, the ratio of defective oxygen to metal oxygen was significantly increased to 3.41, and a rich heterostructure surface was observed in TEM testing (see fig. 2). In FIG. 5, electrochemical experiments show that the electrocatalyst rich in oxygen vacancies and heterogeneous interfaces exhibits excellent electrocatalytic oxygen evolution performance at 10mAcm -2 The overpotential at current density of (2) is only 329mV, its mass activity at 1.6Vvs. RHE (reversible hydrogen electrode) is higher than 1851AgIrO 2 -1 Is significantly better than the oxygen evolution catalyst before the treatment.
The technology is expected to be applied to the commercial utilization of oxygen evolution electrocatalyst in proton exchange membrane electrolyzed water system.
Ru-RuO can be prepared according to example 1 2 Catalyst, mn-MnO 2 The catalyst forms example 2 and example 3, and will not be described in detail.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation process of the oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies is characterized by comprising the following steps:
s1, drying metal oxide;
s2, mixing the precursor solution of the soluble metal salt, the metal oxide in the S1 and the aqueous solution of the reducing agent, and depositing the metal nano particles on the surface of the metal oxide by using a solvothermal reduction method; filtering to obtain precipitate after full reaction, and drying;
s3, placing the precipitate of the S2 into a resistance furnace with protective atmosphere for heat treatment, wherein the temperature of the heat treatment is 400-600 ℃, the protective atmosphere is inert gas, and the inert gas is nitrogen, helium or argon.
2. The process for preparing oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1, wherein in S1 the metal oxide is RuO 2 、IrO 2 Or MnO 2 。
3. The process for preparing oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1, wherein in S2 the reducing agent comprises one or more of sodium borohydride, formic acid, formaldehyde, ethylene glycol.
4. The process for preparing an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1 wherein the concentration of the aqueous reducing agent in S2 is from 10 to 100mmol/L.
5. The process for preparing an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1 wherein in S2 the aqueous reducing agent solution is added dropwise and mixed.
6. The process for preparing an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1 wherein the time of the heat treatment in S3 is from 1 to 5 hours.
7. According to claim 1The preparation process of the oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies is characterized in that in S2, the metal oxide is IrO 2 The precursor solution of the soluble metal salt is chloroiridium acid solution, ruthenium chloride solution or chloroplatinic acid solution.
8. The process for preparing an oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies according to claim 1 wherein in S2 the precursor solution of the soluble metal salt, the metal oxide are mixed first and then the pH is adjusted to 7-8; next, the mixture was heated and stirred at 60-80℃for 5-6 hours, and then an aqueous reducing agent solution was added dropwise.
9. Oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies, characterized in that it is obtained by the preparation process according to claims 1 to 8.
10. The oxygen evolution electrocatalyst with heterogeneous interfaces and oxygen-enriched vacancies of claim 9, wherein the oxygen evolution electrocatalyst is Ru-RuO 2 、Ir-IrO 2 Or Mn-MnO 2 。
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2023
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