CN111450851B - Preparation method of sulfur-doped cobalt-based nano oxygen evolution electrocatalyst - Google Patents
Preparation method of sulfur-doped cobalt-based nano oxygen evolution electrocatalyst Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 31
- 239000010941 cobalt Substances 0.000 title claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 60
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 15
- 239000011593 sulfur Substances 0.000 abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- -1 sulfur ions Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/61—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of electrocatalytic materials, and particularly relates to a preparation method of a sulfur-doped cobalt-based nano oxygen evolution electrocatalyst. The electrocatalyst is a composite material formed by doping cobaltosic oxide nano cubic blocks with cobalt-based sulfide; the method comprises the following steps: firstly, synthesizing cobalt-based hydroxide by adopting a hydrothermal reaction, calcining to obtain a cobaltosic oxide material with a nano cube structure, and then performing the hydrothermal reaction with the previously prepared cobaltosic oxide by taking thioacetamide as a sulfur source to prepare the oxygen evolution electrocatalyst. The electrocatalyst of the invention provides more active sites due to the special nano cube structure and chemical composition, increases the electrochemical active area and has higher oxygen evolution activity and stability; the preparation method is simple and convenient, the steps are simple, the operation is easy, the appearance of the sample is easy to regulate and control, the raw materials are rich, the price is low, the large-scale synthesis and popularization and use are facilitated, and a good foundation is laid for the development and the industrial application of new energy.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a preparation method of a sulfur-doped cobalt-based nano oxygen evolution electrocatalyst.
Background
Energy is an important material basis for human survival and development, and is a hot spot of international, economic, military and external traffic attention today. The current energy crisis and environmental pollution have become increasingly severe, and the development of renewable clean energy has become the focus of attention for various nationists. Hydrogen energy is recognized as an ideal energy carrier with the most potential in the future by virtue of the characteristics of cleanliness and high efficiency. The hydrogen production by water electrolysis is favored by researchers because of simple process principle. The electrolysis voltage is an important criterion for evaluating the energy consumption of the electrolyzed water, because of the high overpotential and the large ohmic voltage drop, and the voltage required for the actual electrolysis of the water is often much higher than theoretically. The key to improving the energy conversion efficiency and the performance of the electrolytic water system is to reduce the reaction resistance or overpotential. Therefore, there is a need to find anode catalysts with low overpotential to accelerate the oxygen evolution electrode reaction rate to improve the energy conversion efficiency. At present, the best catalyst for the hydrogen and oxygen reduction reaction of the electrolysis water is still Pt-based noble metal, and RuO 2 、IrO 2 And the like are considered to be the best performing OER electrocatalysts. However, these noble metals have limited reserves in the crust, are expensive and have poor stability, and are unfavorable for mass production for electrocatalytic reactions. Therefore, the catalyst which is cheap, efficient, durable and environment-friendly can be controlled to be one of the current research hotspots.
Disclosure of Invention
The present invention aims to overcome the disadvantages of the prior art and to solve the above problems. The invention provides a preparation method of the oxygen evolution electrocatalyst with certain catalytic activity, simple preparation process and low and rich raw material price.
In order to achieve the above object, the present invention comprises the following specific steps:
the invention is prepared from cobalt nitrate hexahydrate, sodium hydroxide, thioacetamide and ethanol, and comprises the following specific steps:
(1) Respectively dispersing cobalt nitrate hexahydrate and sodium hydroxide in water for ultrasonic treatment to obtain an aqueous solution of sodium hydroxide and an aqueous solution of cobalt nitrate;
(2) Then dripping the aqueous solution of sodium hydroxide into the aqueous solution of cobalt nitrate at a constant speed, and stirring to obtain a mixed solution;
(3) Carrying out hydrothermal reaction on the mixed solution in the step (2), centrifuging, washing and drying after the reaction to obtain precursor powder;
(4) Calcining the precursor powder in the step (3) in a muffle furnace to obtain cobaltosic oxide powder; respectively dispersing cobaltosic oxide powder and thioacetamide in absolute ethyl alcohol for ultrasonic treatment to obtain an ethanol solution of the cobaltosic oxide and an ethanol solution of the thioacetamide; then mixing the ethanol solution of cobaltosic oxide and the ethanol solution of thioacetamide to obtain a mixed solution; stirring and then carrying out hydrothermal reaction; and centrifuging, washing, freeze-drying and drying the precipitate obtained after the reaction to obtain the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst.
Preferably, in step (1), the ratio of the amount of cobalt nitrate hexahydrate to water is 0.388g:1mL.
Preferably, in the step (1), the usage ratio of sodium hydroxide to water is 0.04g:1mL.
Preferably, in the step (2), when the mixture is added dropwise, the dosage ratio of sodium hydroxide in the aqueous solution of sodium hydroxide to cobalt nitrate in the aqueous solution of cobalt nitrate is 0.04g:0.388g; the stirring time is 30-40 min.
Preferably, in the step (3), the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 5h.
Preferably, in the step (4), the dosage ratio of the cobaltosic oxide powder to the absolute ethanol is 1.5mg:1mL;
preferably, in the step (4), the dosage ratio of the thioacetamide to the water is 1.2 to 14.4mg:1mL;
preferably, in the step (4), when the ethanol solution of cobaltosic oxide and the ethanol solution of thioacetamide are mixed, the dosage ratio of the cobaltosic oxide in the ethanol solution of cobaltosic oxide to the thioacetamide in the ethanol solution of thioacetamide is 1.5mg: 1.2-14.4 mg.
Preferably, in the step (4), the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 12 hours.
The beneficial effects of the invention are as follows:
(1) The invention adopts an anion regulation strategy, adjusts the electronic structure of an active site through the doping of sulfur ions, increases the exposure of a catalytic active site, accelerates the transmission rate of electrons, reduces delta G related to the adsorption and desorption of the OER intermediate on the surface of the catalyst, and improves the overall performance of the OER catalyst. Due to the special nano cube structure and chemical composition, compared with a cobaltosic oxide monomer catalyst, the material exposes more active sites, and the electrochemical active area is increased; compared with other transition metal electrocatalysts, the material has higher oxygen evolution activity and stability, and only needs over-potential as low as 292mV to reach 10mA cm in 1M KOH -2 Is used for the current density of the battery. The preparation method is simple and convenient, the steps are simple, the operation is easy, and the appearance of the sample is easy to regulate and control; is beneficial to large-scale preparation in industrial production and has considerable industrialized application potential.
(2) The invention has proved a simple and cost-effective strategy to prepare the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst, and can easily realize the regulation and control of the microstructure and morphology of the material by controlling the reaction conditions, thereby improving the performance of the catalyst.
Drawings
FIG. 1 is a scanning electron microscope picture of a tricobalt tetraoxide monomer prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the electrocatalytic material prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of the tricobalt tetraoxide monomer prepared in example 1 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the electrocatalytic material prepared in examples 1-4 of this invention.
FIG. 5 is a linear sweep voltammogram of the oxygen evolution reaction of electrocatalytic materials of varying doping levels of sulfur prepared in examples 1-4 of this invention.
Detailed Description
In order to make the present invention better understood by those skilled in the art, the following description of the technical solutions of the embodiments of the present invention will be made in detail, with reference to the accompanying drawings of the embodiments of the present invention, which are only some of the embodiments of the present invention, but not limiting. All other embodiments based on the following are intended to fall within the scope of the present invention.
Example 1:
(1) Carrying out solvothermal reaction;
respectively dissolving 11.64g of cobalt nitrate hexahydrate and 0.4g of sodium hydroxide in 30mL of water and 10mL of water, and stirring for 10min to obtain an aqueous solution of sodium hydroxide and an aqueous solution of cobalt nitrate; then dropwise adding sodium hydroxide solution into the cobalt nitrate solution under stirring, stirring for 30min, transferring the solution into a 50mL polytetrafluoroethylene-lined stainless steel reaction kettle, and then placing the reaction kettle into a 180 ℃ constant temperature oven for heat preservation for 5h; and (3) naturally cooling to room temperature, taking out, centrifuging by using a high-speed rotary centrifuge, washing the precipitate with deionized water for three times and ethanol for two times, and placing the precipitate in a vacuum drying oven at 60 ℃ for 24 hours. And (3) fully grinding the dried sample, spreading the sample in a crucible, placing the crucible in a muffle furnace, heating to 500 ℃ at a speed of 2 ℃/min, and calcining for 3 hours to obtain the cobaltosic oxide powder with the nano cubic structure.
(2) Vulcanizing reaction;
96mg of thioacetamide is taken as a sulfur source and is dissolved in 20mL of absolute ethyl alcohol to obtain an ethanol solution of the thioacetamide; dispersing 60mg of cobaltosic oxide powder into 40mL of ethanol and carrying out ultrasonic treatment for 30min, then adding an ethanol solution of thioacetamide, stirring, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 100mL after 30min, and placing the reaction kettle into a constant-temperature oven with a temperature of 140 ℃ for 12h; and (3) naturally cooling the catalyst to room temperature, taking out the catalyst, centrifuging the catalyst by using a high-speed rotary centrifuge, washing the precipitate with deionized water for three times and ethanol for two times, freeze-drying the precipitate for 24 hours, and taking out the precipitate to obtain the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst.
Characterization analysis:
scanning electron microscope photographs of the obtained cobaltosic oxide monomer catalyst and the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst are shown in fig. 1 and 2. From the scan results shown in FIG. 1, it can be seen that the cubic structure of tricobalt tetraoxide has been successfully prepared, and that the cubic structure is uniform in size and has a side length of about 200nm. From the scanning result shown in fig. 2, the morphology of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst material is changed, and sulfide is in a nano flower-shaped structure, so that the specific surface area of the electrocatalyst can be greatly increased, and more active sites are provided.
As can be seen from the analysis of the X-ray diffraction spectrum chart 3 of the cobaltosic oxide monomer catalyst, the prepared cobaltosic oxide is in a cubic phase and completely coincides with a standard card (JCPLS No. 50-0653) of the cobaltosic oxide, which means that the cobaltosic oxide can be synthesized by a one-step hydrothermal method, and no impurity peak is detected, thus indicating that the purity of the prepared cobaltosic oxide is higher; the X-ray diffraction pattern 4 of the sulfur-doped cobalt-based nano-oxygen evolution electrocatalyst shows some noise, which may be due to the complex multicomponent composition in the sulfide product. Diffraction peaks can be identified by mixtures of two cobalt sulfide phases, respectively CoS 1.097 And Co 3 S 4 。
Performance test:
sulfur-doped cobalt-based nano oxygen evolution electrocatalysts with different sulfur doping contents are prepared by the same method for comparison.
All performance tests were performed on a CHI 760E electrochemical workstation equipped with a typical three-electrode system, with oxygen evolution performance testing of the electrocatalyst material in 1mol/L potassium hydroxide solution electrolyte. Wherein, a platinum wire electrode is used as a counter electrode, an Ag/Agcl electrode is used as a reference electrode, 4mg of the prepared electrocatalyst powder is weighed and added into a mixed solution of 980ul of isopropanol and 20ul of nafion solution, and after ultrasonic treatment is carried out for 30min, a microscale sample injection needle is used for dripping 10ul to 3mm of glassy carbon electrode, and the mixture is dried to be used as a working electrode. At a scan rate of 5mV/s. As shown in FIG. 5, when the current density is 10mA/cm 2 The overpotential of the prepared sulfur-doped cobalt-based nano oxygen evolution electrocatalyst is reduced to 292mV, and the overpotential of the cobaltosic oxide monomer catalyst is 425mV, which shows that the oxygen evolution performance of the catalyst is obviously improved. As described in the above results, a sulfur was successfully produced by the methodThe doped cobalt-based nano oxygen evolution electrocatalyst has excellent catalytic activity for oxygen evolution reaction.
Example 2:
the preparation method of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst is basically the same as that of example 1, except that: in the vulcanizing step, 24mg of thioacetamide is taken as a sulfur source and is dissolved in 20mL of absolute ethyl alcohol to obtain an ethanol solution of the thioacetamide, and the rest steps are the same; further characterization analysis and performance testing were performed, and example 2 was able to achieve the objectives of the invention.
Example 3:
the preparation method of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst is basically the same as that of example 1, except that: in the vulcanization step, 192mg of thioacetamide is taken as a sulfur source and is dissolved in 20mL of absolute ethyl alcohol, and the rest steps are the same; further characterization analysis and performance testing were performed, and example 3 was able to achieve the objectives of the invention.
Example 4:
the preparation method of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst is basically the same as that of example 1, except that: 288mg of thioacetamide is taken as a sulfur source in the vulcanization step, and is dissolved in 20mL of absolute ethyl alcohol, and the rest steps are the same; further characterization analysis and performance testing were performed, and example 4 was able to achieve the objectives of the invention.
Test results: the cobalt-based nano oxygen evolution electrocatalyst doped with sulfur is prepared by changing different sulfur doping amounts, and is subjected to X-ray diffraction, an electron scanning microscope result shows that the vulcanization is successful, and an electron microscope test shows that the vulcanization degree shows a progressive relationship. A linear voltammetric scan was performed as shown in FIG. 3, example 2 shows that when the current density was 10mA/cm 2 The overpotential of the prepared sulfur-doped cobalt-based nano oxygen evolution electrocatalyst was reduced to 332mV, example 3 shows that when the current density was 10mA/cm 2 The overpotential of the prepared sulfur-doped cobalt-based nano oxygen evolution electrocatalyst was reduced to 307mV, example 4 shows that when the current density was 10mA/cm 2 The prepared sulfur-doped cobalt-based nano oxygen evolution electrocatalystThe overpotential of (c) was reduced to 305mV. Therefore, the oxygen evolution performance of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst with different sulfur doping amounts is greatly improved on the basis of the cobaltosic oxide monomer catalyst, which is probably due to the increase of active sites caused by sulfur doping and the effective adjustment of the electronic structure of the composite material. This is more favorable to the adsorption of hydroxyl, and increases the electron transfer rate, and accelerates the kinetic process of oxygen evolution reaction. With different amounts of sulfur doping, it exhibits different overpotential, indicating that the sulfur doping content is not as high as possible, and the performance of the electrocatalyst is optimized only when the appropriate doping amount is reached.
According to the results, the method provided by the invention can be used for avoiding a complex preparation process, successfully preparing the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst with higher electrocatalytic oxygen evolution performance at a lower temperature (140 ℃) and by a simple and easy preparation method, effectively overcoming the defects of complicated preparation and poor oxygen evolution performance of a transition metal-based electrocatalyst material, and providing a new thought for improving the catalytic performance by regulating an electronic structure by anions. The sulfur-doped cobalt-based nano oxygen evolution electrocatalyst prepared by the method can also be applied to the fields of metal-air batteries, novel capacitors, novel energy sources and the like.
The invention is not a matter of the known technology. Unless specifically stated otherwise, the reagents and equipment employed in the present invention are those conventional in the art; the reagents and materials used were all commercially available.
Description: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, while the invention has been described in detail with reference to the various embodiments described above, it will be understood by those skilled in the art that the invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (4)
1. The application of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst in the electrocatalytic oxygen evolution is characterized in that the preparation steps of the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst are as follows:
(1) Respectively dispersing cobalt nitrate hexahydrate and sodium hydroxide in water for ultrasonic treatment to obtain an aqueous solution of sodium hydroxide and an aqueous solution of cobalt nitrate;
(2) Then dropwise adding the aqueous solution of sodium hydroxide into the aqueous solution of cobalt nitrate, and stirring to obtain a mixed solution;
(3) Carrying out hydrothermal reaction on the mixed solution in the step (2), wherein the temperature is 150-180 ℃ and the time is 5 hours; centrifuging, washing and drying after the reaction to obtain precursor powder;
(4) Calcining the precursor powder in the step (3) in a muffle furnace to obtain cobaltosic oxide powder; respectively dispersing cobaltosic oxide powder and thioacetamide in absolute ethyl alcohol for ultrasonic treatment to obtain an ethanol solution of the cobaltosic oxide and an ethanol solution of the thioacetamide; wherein the dosage ratio of the cobaltosic oxide powder to the absolute ethyl alcohol is 1.5mg:1mL; then mixing the ethanol solution of cobaltosic oxide and the ethanol solution of thioacetamide to obtain a mixed solution; wherein when the ethanol solution of cobaltosic oxide and the ethanol solution of thioacetamide are mixed, the dosage ratio of the cobaltosic oxide in the ethanol solution of the cobaltosic oxide to the thioacetamide in the ethanol solution of the thioacetamide is 1.5mg: 1.2-14.4 mg; stirring and then carrying out hydrothermal reaction; the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 12 hours, and the precipitate obtained after the reaction is centrifuged, washed and freeze-dried to obtain the sulfur-doped cobalt-based nano oxygen evolution electrocatalyst.
2. Use of a sulfur-doped cobalt-based nano oxygen evolution electrocatalyst according to claim 1, wherein in step (1) the ratio of cobalt nitrate hexahydrate to water is 0.388g:1mL.
3. Use of a sulfur-doped cobalt-based nano oxygen evolution electrocatalyst according to claim 1, wherein in step (1) the sodium hydroxide to water usage ratio is 0.04g:1mL.
4. The use of a sulfur-doped cobalt-based nano oxygen evolution electrocatalyst according to claim 1, wherein in step (2), the ratio of the amount of sodium hydroxide in the aqueous solution of sodium hydroxide to the amount of cobalt nitrate in the aqueous solution of cobalt nitrate is 0.04g:0.388g; the stirring time is 30-40 min.
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