CN116732569A - Ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies, and preparation method and application thereof - Google Patents
Ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies, and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 111
- 239000001301 oxygen Substances 0.000 title claims abstract description 111
- 239000006104 solid solution Substances 0.000 title claims abstract description 74
- KRSZDIGCQWBYNU-UHFFFAOYSA-N [Mn].[Ru] Chemical compound [Mn].[Ru] KRSZDIGCQWBYNU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002070 nanowire Substances 0.000 title claims abstract description 67
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 49
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 40
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 7
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 7
- 239000011565 manganese chloride Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
-
- 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 discloses a preparation method of ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies, which comprises the following steps: under the ice water bath condition, adding manganese chloride, tetramethyl ammonium hydroxide and hydrogen peroxide into water, and stirring and mixing to obtain a mixed solution; dialyzing the supernatant to neutrality by centrifugation to obtain metastable manganese dioxide; and uniformly mixing ruthenium chloride, cobalt chloride, hydrochloric acid and the metastable manganese dioxide to obtain a reaction solution, and performing hydrothermal reaction to obtain the ruthenium-manganese nanowire solid solution containing oxygen vacancies. The invention also discloses the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst prepared by the preparation method and an anode for the electrolytic water oxygen evolution reaction. The ruthenium-manganese nanowire solid solution has higher activity, and the activity and stability of the ruthenium-manganese nanowire solid solution are further improved by adding cobalt chloride in a hydrothermal reaction.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies, a preparation method and application thereof.
Background
The hydrogen with heat value and low pollution is the most ideal renewable energy source, and the electrochemical water decomposition hydrogen production by using renewable power is a promising hydrogen production method. However, in electrochemical water splitting, the kinetics of the oxygen evolution reaction are relatively slow, as the generation of oxygen molecules is accompanied by a process of four electron transfer, resulting in a higher overpotential. Compared with alkaline water, the acidic water decomposition using the proton exchange membrane electrolytic cell has the advantages of higher ionic conductivity, high voltage efficiency, faster system response and the like. However, limited structural stability and activity have hindered the practical use of electrocatalysts in acidic electrolytes. Therefore, the development of oxygen evolution materials that are durable and active under severe acidic conditions is of great importance for the wide application of proton exchange membrane electrolyzer electrolysis technology.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst, wherein the prepared ruthenium-manganese nanowire solid solution has higher activity, and the activity and stability of the catalyst are further improved by adding cobalt chloride in a hydrothermal reaction.
The invention also aims to provide the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies prepared by the preparation method.
It is still another object of the present invention to provide the use of the ruthenium manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies described above.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies comprises the following steps:
(1) Under the ice water bath condition, adding manganese chloride, tetramethyl ammonium hydroxide and hydrogen peroxide into water, and stirring and mixing to obtain a mixed solution; dialyzing the supernatant to neutrality by centrifugation to obtain metastable manganese dioxide;
(2) Uniformly mixing ruthenium chloride, cobalt chloride, hydrochloric acid and the metastable manganese dioxide to obtain a reaction solution, and performing hydrothermal reaction to obtain a ruthenium-manganese nanowire solid solution containing oxygen vacancies;
wherein the molar ratio of ruthenium chloride, cobalt chloride and metastable manganese dioxide is (0.05-0.33): (0.05-0.22): 1.
preferably, in the step (1), the molar ratio of manganese chloride to tetramethyl ammonium hydroxide is 1:5-6.
Preferably, the mass concentration of the hydrogen peroxide is 25-35%, and the addition amount is 5-7% of the mixed solution.
Preferably, the stirring speed is 800-1000r/min, and the stirring time is 8-24 hours.
Preferably, the temperature of the hydrothermal reaction is 140-200 ℃ and the time is 0.5-3 hours.
Preferably, the pH value of the reaction solution is 1-2.
The oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst is prepared by a preparation method of the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst, and has a linear structure composed of nano particles.
The application of the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies is used for preparing an anode for electrolytic water oxygen evolution reaction.
Preferably, the anode for the electrolytic water oxygen precipitation reaction comprises an electrode matrix and a ruthenium-manganese nanowire solid solution acidic oxygen precipitation electrocatalyst containing oxygen vacancies, wherein the ruthenium-manganese nanowire solid solution acidic oxygen precipitation electrocatalyst is coated on the surface of the electrode matrix.
Preferably, the electrode substrate is a glassy carbon electrode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the preparation method of the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst, a metastable-state lamellar manganese dioxide precursor is prepared, then hydrothermal is carried out in one step, and the metastable-state lamellar manganese dioxide reacts with manganese chloride and cobalt chloride in a reaction to carry out structural evolution, so that the oxygen vacancy-rich ruthenium-manganese nanowire solid solution can be obtained. The ruthenium-manganese solid solution is converted from metastable lamellar manganese dioxide through a solid-solution-solid route, the nucleation of the ruthenium-manganese solid solution in the hydrothermal reaction process can be promoted by the existence of ruthenium chloride, then the newly formed atomic nucleus is used as the center of subsequent growth of the ruthenium-manganese solid solution, and the metastable lamellar manganese dioxide and Mn in the solution under the acidic hydrothermal condition 4+ In a dynamic stateBalance state: mnO (MnO) 2 +4H + →Mn 4+ +2H 2 O. Nucleation and growth of ruthenium-manganese solid solutions deplete Mn in the reaction solution 4+ The ions then further promote dissolution of the metastable layered manganese dioxide until they are completely dissolved and converted to ruthenium manganese solid solutions. The cobalt chloride is subjected to hydrothermal reaction in the presence of cobalt chloride, so that cobalt oxide can be doped into a solid solution crystal structure, and the cobalt oxide is dissolved into the solution during the cooling process of a reaction system due to the instability of the cobalt oxide under the acidic environment condition, so that the ruthenium-manganese nanowire solid solution rich in oxygen vacancies is obtained. The method can directly manufacture oxygen defects in one step, does not need to carry out other steps, has low requirements on production equipment, easily obtained raw materials, is beneficial to large-scale production, reduces the consumption of noble metals, reduces the production cost, and has high activity and long service life in the acid oxygen precipitation reaction by taking the obtained ruthenium-manganese nanowire solid solution rich in oxygen vacancies as a catalyst, and high stability even under different current densities.
(2) The anode of electrolytic water oxygen precipitation reaction prepared by the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancy of the invention has the current density reaching 10mA/cm in the acidic oxygen precipitation reaction 2 At an overpotential of only 200mV, and can be set at 10mA/cm 2 Is operated continuously for more than 600 hours.
Drawings
FIG. 1 is a scanning electron microscope image of metastable sheet manganese dioxide prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of the ruthenium-manganese nanowire solid solution electrocatalyst enriched in oxygen vacancies obtained in example 1 and example 2 of the present invention;
FIGS. 3 (a) and (b) are scanning electron microscope images of the oxygen vacancy-rich ruthenium-manganese nanowire solid solution electrocatalysts obtained in example 1 and example 2, respectively, of the present invention;
FIGS. 4 (a) and (b) are respective transmission electron microscopic images (transmission electron microscopic electron acceleration voltage: 100 kV) of the oxygen vacancy-rich ruthenium-manganese nanowire solid solution electrocatalysts obtained in example 1 and example 2 of the present invention;
FIGS. 5 (a) and (b) are an X-ray photoelectron spectrum O element 1s orbital plot and a full spectrum plot, respectively, of the oxygen vacancy-rich ruthenium-manganese nanowire solid solution electrocatalyst obtained in example 1 and example 2 of the present invention;
FIG. 6 is an electron paramagnetic resonance diagram of the ruthenium-manganese nanowire solid solution electrocatalyst enriched in oxygen vacancies obtained in example 1 and example 2 of the present invention.
FIG. 7 is a graph of linear sweep voltammetry measurements of oxygen vacancy-enriched ruthenium manganese nanowire solid solution electrocatalysts obtained in examples 1-5 of the invention;
FIG. 8 shows the oxygen vacancy-rich ruthenium-manganese nanowire solid solution electrocatalyst obtained in example 1 and example 2 of the present invention at 10mA/cm 2 Constant current test patterns at current density;
FIG. 9 shows the oxygen vacancy-enriched ruthenium-manganese nanowire solid solution electrocatalyst obtained in example 1 of the present invention at 10mA/cm 2 、20mA/cm 2 、30mA/cm 2 、40mA/cm 2 、50mA/cm 2 Constant current test patterns at current densities of (3).
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The source of all the raw materials is not particularly limited and is commercially available.
Example 1
The preparation method of the ruthenium-manganese nanowire solid solution rich in oxygen vacancies comprises the following specific steps:
1) The tetramethylammonium hydroxide solution with the content of 0.67mol/L is prepared by deionized water, 36mL is added, and then 4.0mL of hydrogen peroxide with the mass fraction of 30% is added for uniform mixing.
2) A manganese chloride hydrate solution with a content of 0.3mol/L and 20mL was prepared with deionized water.
3) The solution prepared in step 1) was added rapidly to the manganese chloride solution within 15 seconds and vigorously stirred in an ice-water bath at 800r/min for 12 hours.
4) Centrifuging the mixed solution in the step 3) by using a centrifugal machine at the rotating speed of 8000r/min for 3min, taking the centrifuged upper mixed solution, dialyzing to neutrality in deionized water to obtain uniformly dispersed metastable-state lamellar manganese dioxide, and a scanning electron microscope chart of which is shown in figure 1.
5) Taking out 0.230mmol of the metastable-state lamellar manganese dioxide material obtained in the step 4), mixing with 0.050mmol of ruthenium chloride and 0.0375mmol of cobalt chloride in 34.5mL of deionized water, and finally adding 0.5mL of concentrated hydrochloric acid to adjust the pH value to 1-2.
6) And 5) placing the mixed solution obtained in the step 5) into a hydrothermal reaction kettle, heating to 180 ℃ and reacting for 3 hours. And (3) cleaning the product to obtain the ruthenium-manganese nanowire solid solution rich in oxygen vacancies.
Example 2
The preparation method of the ruthenium-manganese nanowire solid solution material rich in oxygen vacancies comprises the following steps:
steps 1) -4) are the same as in example 1;
5) Taking out 0.230mmol of the metastable-state lamellar manganese dioxide material obtained in the step 4), mixing with 0.050mmol of ruthenium chloride in 34.5mL of deionized water, and finally adding 0.5mL of concentrated hydrochloric acid;
step 6) is the same as in example 1.
Example 3
The preparation method of the ruthenium-manganese nanowire solid solution material rich in oxygen vacancies comprises the following steps:
steps 1) -4) are the same as in example 1;
5) Taking out 0.230mmol of the metastable lamellar manganese dioxide material obtained in the step (4), mixing with 0.050mmol of ruthenium chloride and 0.0125mmol of cobalt chloride in 34.5mL of deionized water, and finally adding 0.5mL of concentrated hydrochloric acid;
step 6) is the same as in example 1.
Example 4
The preparation method of the ruthenium-manganese nanowire solid solution material rich in oxygen vacancies comprises the following steps:
steps 1) -4) are the same as in example 1;
5) Taking out 0.230mmol of the metastable sheet manganese dioxide material obtained in the step (4), mixing with 0.050mmol of ruthenium chloride and 0.025mmol of cobalt chloride in 34.5mL of deionized water, and finally adding 0.5mL of concentrated hydrochloric acid;
step 6) is the same as in example 1.
Example 5
The preparation method of the ruthenium-manganese nanowire solid solution material rich in oxygen vacancies comprises the following steps:
steps 1) -4) are the same as in example 1;
5) Taking out 0.230mmol of the metastable lamellar manganese dioxide material obtained in the step (4), mixing with 0.050mmol of ruthenium chloride and 0.050mmol of cobalt chloride in 34.5mL of deionized water, and finally adding 0.5mL of concentrated hydrochloric acid;
step 6) is the same as in example 1.
Analysis of the products
The ruthenium-manganese nanowire solid solution electrocatalysts rich in oxygen vacancies obtained in example 1 and example 2 were analyzed by X-ray diffraction to obtain X-ray diffraction patterns thereof, which were consistent with solid solution properties, as shown in fig. 2.
The ruthenium-manganese nanowire solid solution electrocatalysts rich in oxygen vacancies obtained in example 1 and example 2 were analyzed by using a scanning electron microscope to obtain a scanning electron microscope image thereof, and the catalysts were in a line shape as shown in fig. 3.
The ruthenium-manganese nanowire solid solution electrocatalysts rich in oxygen vacancies obtained in example 1 and example 2 were analyzed using a transmission electron microscope to obtain transmission electron microscope micrographs thereof, and the catalysts exhibited a linear structure composed of small nanoparticles, as shown in fig. 4.
Analysis of the ruthenium-manganese nanowire solid solution electrocatalysts enriched in oxygen vacancies obtained in example 1 and example 2 by X-ray photoelectron spectroscopy gave XPS plots of the O element 1s orbitals, which found a distinct characteristic peak of oxygen vacancies at a binding energy of 531.9eV, indicating that the catalysts were enriched in oxygen vacancies, as shown in fig. 5 (a). Example 1 is a ruthenium-manganese nanowire solid solution electrocatalyst rich in oxygen vacancies, which is obtained by adding cobalt chloride into a reaction system, and the characteristic peak area ratio of the corresponding oxygen vacancies is obviously increased compared with the catalyst synthesized in example 2, so that more oxygen vacancies exist, which indicates that cobalt chloride can promote the formation of oxygen vacancy defects in the ruthenium-manganese nanowire solid solution. As shown in fig. 5 (b), no characteristic peak of Co element was found in the full spectrum of the X-ray photoelectron spectrum of the oxygen-vacancy-rich ruthenium-manganese nanowire solid solution electrocatalyst obtained in example 1, indicating that Co element was not incorporated into the oxygen-vacancy-rich ruthenium-manganese nanowire solid solution electrocatalyst.
The ruthenium-manganese nanowire solid solution electrocatalysts enriched in oxygen vacancies obtained in example 1 and example 2 were analyzed using electron paramagnetic resonance to obtain EPR plots showing that when g=2.003, the electrons captured a significant oxygen vacancy signal, as shown in fig. 6, indicating that the catalysts are enriched in oxygen vacancies. Example 2 the catalyst synthesized without the addition of cobalt chloride had a particularly low signal strength of oxygen vacancies, and when cobalt chloride was added to the reaction system, the ESR signal strength of the oxygen vacancy-rich ruthenium-manganese nanowire solid solution electrocatalyst obtained in example 1 increased significantly, indicating that cobalt chloride can promote the formation of oxygen vacancy defects in the ruthenium-manganese nanowire solid solution.
Evaluation of catalyst Performance
4mg of ruthenium manganese nanowire solid solution powder rich in oxygen vacancies was added to 1mL of the mixed solution (containing 750. Mu.L of isopropanol, 250. Mu.L of deionized water and 10. Mu.L of 5wt% Nafion) and sonicated uniformly as a catalyst slurry. After 10. Mu.L of the catalyst slurry was dropped on a glassy carbon electrode having a diameter of 5mm and naturally dried, the catalyst slurry was used as an anode for the electrolytic water oxygen precipitation reaction.
Test conditions: using a three electrode test method, a catalyst coated glassy carbon electrode was used as the working electrode, 0.5. 0.5M H 2 SO 4 Hg/HgSO as electrolyte 4 As a reference electrode, a carbon rod was used as a counter electrode, CHI760E was used as a test instrument, and the test was performed at normal temperature and pressure.
Linear sweep voltammetry test: the scan rate was 5mV/s. Linear sweep voltammetry test patterns of examples 1-5 were obtained as shown in FIG. 7. The result shows that after cobalt chloride is added into the reaction system to generate more oxygen vacancies, the catalytic performance is obviously improved, the performance is gradually improved along with the increase of the cobalt chloride, the ruthenium-manganese nanowire solid solution electrocatalyst rich in oxygen vacancies obtained in the embodiment 1 achieves the optimal catalytic performance, and the catalytic performance is reduced due to the excessive addition of the cobalt chloride. To achieve optimal catalytic performance, it is necessary to adjust the amount of cobalt chloride added, i.e., the oxygen vacancy level of the catalyst.
Constant current test: the oxygen vacancy-rich ruthenium manganese nanowire solid solution electrocatalysts obtained in example 1 and example 2 were at 10mA/cm 2 As shown in fig. 8, the results show that the catalyst of example 1 with cobalt chloride added to generate more oxygen vacancies has greatly improved stability compared with the catalyst synthesized in example 2, which indicates that the addition of cobalt chloride to generate more oxygen vacancies in the reaction is beneficial to improving the stability of ruthenium-manganese nanowire solid solution. The oxygen vacancy-rich ruthenium manganese nanowire solid solution electrocatalyst obtained in example 1 was at 10mA/cm 2 、20mA/cm 2 、30mA/cm 2 、40mA/cm 2 、50mA/cm 2 Constant current test chart at current density of (2) as shown in fig. 9.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.
Claims (10)
1. The preparation method of the ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst containing oxygen vacancies is characterized by comprising the following steps:
(1) Under the ice water bath condition, adding manganese chloride, tetramethyl ammonium hydroxide and hydrogen peroxide into water, and stirring and mixing to obtain a mixed solution; dialyzing the supernatant to neutrality by centrifugation to obtain metastable manganese dioxide;
(2) Uniformly mixing ruthenium chloride, cobalt chloride, hydrochloric acid and the metastable manganese dioxide to obtain a reaction solution, and performing hydrothermal reaction to obtain a ruthenium-manganese nanowire solid solution containing oxygen vacancies;
wherein the molar ratio of ruthenium chloride, cobalt chloride and metastable manganese dioxide is (0.05-0.33): (0.05-0.22): 1.
2. the method for preparing the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 1, wherein the molar ratio of manganese chloride to tetramethyl ammonium hydroxide in step (1) is 1:5-6.
3. The method for preparing the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 1, wherein the mass concentration of the hydrogen peroxide is 25-35%, and the addition amount is 5-7% of the mixed solution.
4. The method for preparing the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 1, wherein the stirring speed is 800-1000r/min, and the stirring time is 8-24 hours.
5. The method for preparing the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 140 ℃ to 200 ℃ for 0.5 to 3 hours.
6. The method for preparing an oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 1, wherein the pH value of the reaction solution is 1 to 2.
7. An oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst prepared by the method for preparing the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to any one of claims 1 to 6, characterized by exhibiting a linear structure composed of nanoparticles.
8. The use of the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 7 for preparing an anode for an electrolytic water oxygen evolution reaction.
9. The use of the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 8, wherein the anode for the electrolytic water oxygen evolution reaction comprises an electrode substrate and the oxygen vacancy-containing ruthenium-manganese nanowire solid solution acidic oxygen evolution electrocatalyst coated on the surface of the electrode substrate.
10. The use of an oxygen vacancy containing ruthenium manganese nanowire solid solution acidic oxygen evolution electrocatalyst according to claim 9, wherein the electrode substrate is a glassy carbon electrode.
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