CN111437836B - High-efficiency oxygen evolution catalyst CuCo 2 S 4 And method of preparation - Google Patents

High-efficiency oxygen evolution catalyst CuCo 2 S 4 And method of preparation Download PDF

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CN111437836B
CN111437836B CN202010162062.8A CN202010162062A CN111437836B CN 111437836 B CN111437836 B CN 111437836B CN 202010162062 A CN202010162062 A CN 202010162062A CN 111437836 B CN111437836 B CN 111437836B
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oxygen evolution
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CN111437836A (en
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饶德伟
杨欢
颜晓红
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Jiangsu University
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract

The invention belongs to the field of electrocatalysis, and relates to a high-efficiency oxygen evolution catalyst CuCo 2 S 4 And a preparation method. The invention takes nano copper sulfide modified by citric acid as a template, adsorbs cobalt ions through electrostatic action, and prepares copper cobalt sulfide (CuCo) with a spinel structure by a hydrothermal method 2 S 4 ) Nanospheres. More active sites are exposed by controlling the particle size of the catalyst to increase more active area; meanwhile, the coordination of the electronic structure between the bimetallic elements is utilized to adjust the geometric locus and the valence state of the cobalt atom so as to improve the catalytic performance.

Description

High-efficiency oxygen evolution catalyst CuCo 2 S 4 And method of preparation
Technical Field
The invention belongs to the field of electrocatalysis, and relates to a high-efficiency oxygen evolution catalyst CuCo 2 S 4 And a preparation method thereof, in particular to CuCo 2 S 4 Nanospheres, a preparation method and application in electrocatalytic OER.
Background
Oxygen Evolution Reaction (OER) is the key to renewable energy technology, and its slow kinetic process inhibits the development of energy-producing devices, currently relying mainly on noble metal oxides such as ruthenium oxide (RuO) 2 ) And iridium oxide (IrO) 2 ) The OER catalytic efficiency is improved, but the noble metal has the restriction factors of high cost and low storage quantity.
In recent years, considerable work has been done by researchers to develop alternative non-noble metal catalysts that have superior catalytic performance, i.e., the ability to accelerate the OER reaction at lower overpotentials. Among them, transition metal cobalt-based catalysts have been widely studied as non-noble metal OER catalysts, such as Co-based sulfides, nitrides, phosphides, etc., but their commercialization is limited due to the cumbersome preparation process and the need for further improvement of OER catalytic performance.
In order to solve the problems, the invention provides a simple preparation method of spinel-type copper cobalt sulfide, which mainly uses nano copper sulfide modified by citric acid as a template, adsorbs cobalt ions through electrostatic action and prepares copper cobalt sulfide (CuCo) with a spinel-type structure by a hydrothermal method 2 S 4 ) Nanospheres. More active sites are exposed by controlling the particle size of the catalyst to increase more active area; meanwhile, the coordination of the electronic structure between the bimetallic elements is utilized to adjust the geometric locus and the valence state of the cobalt atom, so as to improve the catalytic performance.
Disclosure of Invention
The invention aims to provide a spinel type copper cobalt sulfide CuCo with high-efficiency oxygen evolution catalytic performance 2 S 4 The simple preparation method of (1).
The specific technical scheme is as follows:
preparation of CuCo 2 S 4 The preparation process of the high-efficiency oxygen evolution catalyst comprises the following steps:
(1) Preparation of copper sulfide according to the method reported in the literature (M.Zhou, R.Zhang, M.Huang, W.Lu, S.Song, M.P.Melanon, M.Tian, D.Liang and C.Li.A. chemical-free multifunctional [ ], [ M.ZHou, M.Huang, W.Lu, S.Song, M.P.Melanon, M.Tian, D.Liang, and C.Li.A. chemical-free multifunctional ] 64 Cu]CuS nanoparticule platform for single and multiple micro-PET/CT imaging and photothermal imaging therapy.J.am.chem.Soc.,2010,132, 15351-15358).
The adopted specific technical scheme is as follows:
weighing copper chloride dihydrate and trisodium citrate dihydrate, adding deionized water, and magnetically stirring at room temperature to dissolve the copper chloride dihydrate and the trisodium citrate dihydrate into a uniform light blue solution; weighing sodium sulfide nonahydrate, and adding deionized water to prepare Na 2 S·9H 2 O aqueous solution, followed by adding Na 2 S·9H 2 Quickly adding the O aqueous solution into the light blue solution, and magnetically stirring at room temperature for reaction until the mixed solution turns into dark brown; transferring the mixed solution into a constant-temperature water bath kettle, heating in water bath to 90 ℃, reacting to obtain dark green copper sulfide nanoparticle solution, and carrying out ice-water bathCooling, and finally placing the solution in a refrigerator for standby overnight.
In the light blue solution, the ratio of copper chloride dihydrate, trisodium citrate dihydrate and deionized water is 1mmol:0.68mmol:180mL.
The Na is 2 S·9H 2 The volume ratio of the O aqueous solution to the light blue solution is 1 2 S·9H 2 The concentration of the O aqueous solution was 50mmol/L.
The reaction time was 5min with magnetic stirring at room temperature.
The temperature is raised to 90 ℃ by water bath heating, and the reaction time is 15min.
The refrigerator temperature was 4 ℃.
(2) Weighing cobalt chloride hexahydrate, stirring and dissolving the cobalt chloride hexahydrate into a nano copper sulfide solution, uniformly mixing the cobalt chloride hexahydrate and the nano copper sulfide solution, placing the mixture on a platform stirrer, and stirring the mixture at room temperature to obtain a uniformly mixed solution 1;
(3) Transferring the solution 1 prepared in the step (2) into a high-pressure reaction kettle, and putting the reaction kettle into an oven to react for 10 hours at the temperature of 150-180 ℃;
(4) After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging the product, washing the product with water and ethanol, and drying the product in vacuum at room temperature to obtain CuCo 2 S 4 High efficiency OER catalyst.
In the step (2), the molar ratio of the cobalt chloride hexahydrate to the nano copper sulfide of the nano copper sulfide solution is as follows: 0.25 to 1:0.2, stirring for 10-20 min at room temperature.
And (4) washing the mixture for 3 to 5 times by using water and ethanol, and performing vacuum drying at room temperature for 24 hours.
The spinel-structured copper-cobalt sulfide CuCo obtained in the invention 2 S 4 The nanosphere has a large specific surface area, can expose more active sites, is beneficial to improving the catalytic performance and the electrochemical stability, and has a simple hydrothermal reaction preparation method without complex processes such as high-temperature heat treatment and the like.
CuCo obtained in the invention 2 S 4 The nanosphere catalyst shows excellent electrocatalytic OER performance, and the test shows that the prepared optimal CuCo 2 S 4 Nanosphere electrocatalystIn the catalytic oxygen precipitation reaction, the current density reaches 10mA/cm 2 The overpotential of the time is only 297mV, far exceeding that of the commercial RuO 2 Performance of OER (10 mA/cm) 2 The overpotential at (b) is 321 mV). Moreover, the catalyst has good electrochemical stability, and in a chronoamperometric test, 89.9 percent of the initial current is still maintained after 12 hours.
The raw materials used in the preparation process are mainly copper and cobalt sources with rich reserves in the earth, and the raw materials are wide in sources, environment-friendly, green and high in safety. The preparation method is simple, and the obtained product is nontoxic, has better OER catalytic performance and can replace commercial RuO in the future 2 Has better prospect in large-scale application of hydrogen and oxygen production by electrolyzing water.
Drawings
FIG. 1 shows the copper cobalt sulfide CuCo of spinel structure prepared in example 1 2 S 4 XRD pattern of nanospheres.
FIG. 2 shows the copper cobalt sulfide CuCo with spinel structure prepared in example 1 2 S 4 SEM image of nanospheres.
FIG. 3 shows CuCo prepared in examples 1 to 5 2 S 4 Nanospheres, respectively (OER) Linear Scan (LSV) plot of oxygen evolution reaction under alkaline electrolyte.
FIG. 4 shows the copper cobalt sulfide CuCo with spinel structure prepared in example 1 2 S 4 I-t plot of nanospheres in alkaline electrolyte (chronoamperometry).
Detailed Description
Reagents and instrumentation: the reagents used in the invention are all analytically pure, and the reagents are directly applied without any special treatment without special indication.
Cupric chloride dihydrate (CuCl) 2 ·2H 2 O), sodium sulfide nonahydrate (Na) 2 S·9H 2 O), trisodium citrate dihydrate (C) 6 H 5 Na 3 O 7 ·2H 2 O), cobalt chloride hexahydrate (CoCl) 2 ·6H 2 O), potassium hydroxide (KOH) used for electrochemical tests are analytically pure and purchased from chemical reagents of national drug group, inc.; without waterRuthenium oxide (RuO) 2 99.9% metals basis, alfa Aesar), nafion perfluorinated resin solution (5 wt%, sigma Aldrich).
Analytical balance (Precisa, XJ 220A), centrifuge (hunan xiang instrument, TG 16-WS), forced air drying cabinet (shanghai essence macro, DFG-9076A), vacuum drying cabinet (shanghai essence macro, DZF-6090), electrochemical workstation (shanghai chenhua, CHI 760E), rotating disk ring electrode assembly (pone corporation, usa).
Electrochemical testing: the electrochemical oxygen evolution performance test adopts a Chenghua electrochemical workstation and a three-electrode test system, a glassy carbon electrode loaded with a catalyst is used as a working electrode, and a reversible hydrogen reference electrode and a graphite rod electrode are respectively used as a reference electrode and a counter electrode. Adding a copper cobalt sulfide catalyst into a prepared membrane solution (water: ethanol: 5wt% Nafion volume ratio of 40: 10) 2 Testing the electrochemical OER performance of the electrode in a saturated 1M KOH solution to obtain an LSV curve when the sweep rate is 5 mV/s; the electrochemical stability of the catalyst was then tested by chronoamperometry.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The present invention will be described in detail with reference to specific examples.
Example 1 (best mode)
(1) Synthesizing a nano copper sulfide aqueous solution: adding 0.1705g of copper chloride dihydrate (1 mmol) and 0.2g of trisodium citrate dihydrate (0.68 mmol) into 180mL of deionized water at room temperature, and magnetically stirring uniformly until the solution is light blue; 0.6005g of sodium sulfide nonahydrate is weighed and added with deionized waterContained in a 50mL volumetric flask, to prepare an aqueous solution with a concentration of 50mmol/L, followed by adding 20mL of Na 2 S·9H 2 Rapidly adding the O aqueous solution into the solution, and continuously magnetically stirring at room temperature for 5min to convert the reaction solution into dark brown; and transferring the mixed solution into a constant-temperature water bath kettle, heating in a water bath to 90 ℃, continuously heating for continuous reaction for 15min to obtain a dark green copper sulfide nanoparticle solution, cooling in an ice water bath, and finally placing the solution in a refrigerator at 4 ℃ for later use.
(2) Synthesis of CuCo 2 S 4 Nanosphere catalyst: weighing 0.1189g of cobalt chloride hexahydrate (0.5 mmol), stirring and dissolving into 40mL of nano copper sulfide solution (containing 0.2mmol of nano copper sulfide), uniformly mixing, placing on a platform stirrer, and magnetically stirring at room temperature for 10min to obtain uniformly mixed solution; then, transferring the solution to a 100mL high-pressure reaction kettle, and putting the reaction kettle into a 150-DEG oven for reaction for 10 hours; after the reaction is finished, after the reaction kettle is cooled to room temperature, centrifuging the product, washing the product with water and ethanol for 3 times respectively, drying the product in a vacuum drying oven for 24 hours at room temperature, and uniformly grinding the dried sample in an agate mortar to obtain the copper cobalt sulfide.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the copper cobalt sulfide catalyst was weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio of 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
Example 1 the copper cobalt sulfide produced was CuCo as the major component 2 S 4 The phase analysis result is shown in an XRD (X-ray diffraction) spectrum of figure 1; FIG. 2 shows the SEM micrograph of the product, as shown, cuCo 2 S 4 The nanospheres are ultra-small nanospheres with uniform size and 20nm particle size, which is beneficial to increase the specific surface area of the catalyst and expose more active sitesThe results of the OER performance test are shown in FIG. 3, at a current density of 10mA/cm 2 At an overpotential of 297mV, well in excess of commercial RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV). The chronoamperometric curve of the catalyst was tested at a voltage of 1.5V (vs. RHE), and as shown in FIG. 4, the catalyst still retained 89.9% of the initial current density after 12 hours, indicating that the test results indicate CuCo 2 S 4 The nanosphere catalyst has excellent OER catalytic performance and electrochemical stability.
Example 2 (comparative example, insufficient amount of cobalt chloride hexahydrate)
(1) Synthesizing a nano copper sulfide aqueous solution: 0.1705g of copper chloride dihydrate (1 mmol) and 0.2g of trisodium citrate dihydrate (0.68 mmol) are weighed into a 250mL round-bottom flask respectively, 180mL of deionized water is weighed and added into the flask, and the mixture is magnetically stirred at room temperature to be dissolved into a uniform light blue solution; weighing 0.6005g of sodium sulfide nonahydrate, adding deionized water to a constant volume in a 50mL volumetric flask to prepare an aqueous solution with the concentration of 50mmol/L, then quickly adding 20mL of the sodium sulfide nonahydrate aqueous solution into the solution, magnetically stirring for 5min at room temperature, and converting the reaction mixed solution into dark brown; transferring the mixed solution into a constant-temperature water bath kettle, heating in water bath to 90 ℃, continuing to heat for continuous reaction for 15min to obtain dark green nano copper sulfide solution, cooling in ice water bath, and finally placing the solution in a refrigerator at 4 ℃ for later use at night.
(2) Synthesizing a copper cobalt sulfide catalyst: weighing 0.0238g of cobalt chloride hexahydrate (0.1 mmol), stirring and dissolving into 40mL of nano copper sulfide solution (containing 0.2mmol of nano copper sulfide), uniformly mixing, placing on a platform stirrer, and magnetically stirring at room temperature for 10min to obtain uniform solution; then, transferring the solution to a 100mL high-pressure reaction kettle, and putting the reaction kettle into a 150-DEG oven for reaction for 10 hours; after the reaction is finished, after the reaction kettle is cooled to room temperature, centrifuging the product, washing the product with water and ethanol for 3 times respectively, drying the product in a vacuum drying oven for 24 hours at room temperature, and uniformly grinding the dried sample in an agate mortar to obtain the copper cobalt sulfide.
(3) Electrochemical OER performance testing: test adopted standardAnd (3) performing three-electrode test, namely selecting a Reversible Hydrogen Electrode (RHE) as a reference electrode, a graphite rod as a counter electrode and a Glassy Carbon (GC) disc electrode as a working electrode. 3mg of the copper cobalt sulfide catalyst was weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio of 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
The results of the OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 Has an overpotential of 406mV lower than that of commercial RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV).
Example 3 (preferably, different amounts of cobalt chloride hexahydrate)
(1) Synthesizing a nano copper sulfide aqueous solution: 0.1705g of copper chloride dihydrate (1 mmol) and 0.2g of trisodium citrate dihydrate (0.68 mmol) are weighed into a 250mL round-bottom flask respectively, 180mL of deionized water is weighed and added into the flask, and the mixture is magnetically stirred at room temperature to be dissolved into a uniform light blue solution; weighing 0.6005g of sodium sulfide nonahydrate, adding deionized water to a constant volume in a 50mL volumetric flask to prepare an aqueous solution with the concentration of 50mmol/L, then quickly adding 20mL of the sodium sulfide nonahydrate aqueous solution into the solution, magnetically stirring the solution at room temperature for 5min, and converting the reaction mixed solution into dark brown; and transferring the mixed solution into a constant-temperature water bath kettle, heating in a water bath to 90 ℃, continuously heating for continuous reaction for 15min to obtain a dark green nano copper sulfide solution, cooling in an ice water bath, and finally placing the solution in a refrigerator at 4 ℃ for later use.
(2) Synthesizing a copper cobalt sulfide catalyst: weighing 0.0595g of cobalt chloride hexahydrate (0.25 mmol), stirring and dissolving into 40mL of nano copper sulfide solution (containing 0.2mmol of nano copper sulfide), uniformly mixing, placing on a platform stirrer, and magnetically stirring at room temperature for 10min to obtain uniform solution; then, transferring the solution to a 100mL high-pressure reaction kettle, and putting the reaction kettle into a 150-DEG C oven for reaction for 10 hours; after the reaction is finished, after the reaction kettle is cooled to room temperature, centrifuging the product, washing the product with water and ethanol for 3 times respectively, drying the product in a vacuum drying oven for 24 hours at room temperature, and uniformly grinding the dried sample in an agate mortar to obtain the copper cobalt sulfide.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the copper cobalt sulfide catalyst was weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio of 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
The results of the OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 The overpotential of the electrode is 317mV, which is better than RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV).
Example 4 (preferably, different amounts of cobalt chloride hexahydrate)
(1) Synthesizing a nano copper sulfide aqueous solution: 0.1705g of copper chloride dihydrate (1 mmol) and 0.2g of trisodium citrate dihydrate (0.68 mmol) are weighed into a 250mL round-bottom flask respectively, 180mL of deionized water is weighed and added into the flask, and the mixture is magnetically stirred at room temperature to be dissolved into a uniform light blue solution; weighing 0.6005g of sodium sulfide nonahydrate, adding deionized water to a constant volume in a 50mL volumetric flask to prepare an aqueous solution with the concentration of 50mmol/L, then quickly adding 20mL of the sodium sulfide nonahydrate aqueous solution into the solution, magnetically stirring for 5min at room temperature, and converting the reaction mixed solution into dark brown; transferring the mixed solution into a constant-temperature water bath kettle, heating in water bath to 90 ℃, continuing to heat for continuous reaction for 15min to obtain dark green nano copper sulfide solution, cooling in ice water bath, and finally placing the solution in a refrigerator at 4 ℃ for later use at night.
(2) Synthesizing the copper cobalt sulfide catalyst: weighing 0.1784g of cobalt chloride hexahydrate (0.75 mmol), stirring and dissolving into 40mL of nano copper sulfide solution (containing 0.2mmol of nano copper sulfide), uniformly mixing, placing on a platform stirrer, and magnetically stirring at room temperature for 10min to obtain uniform solution; then, transferring the solution to a 100mL high-pressure reaction kettle, and putting the reaction kettle into a 150-DEG oven for reaction for 10 hours; after the reaction is finished, after the reaction kettle is cooled to room temperature, centrifuging the product, washing the product with water and ethanol for 3 times respectively, drying the product in a vacuum drying oven for 24 hours at room temperature, and uniformly grinding the dried sample in an agate mortar to obtain the copper cobalt sulfide.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the copper cobalt sulfide catalyst was weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio of 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
The results of the OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 At an overpotential of 331mV, close to that of commercial RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV).
Example 5 (preferably, different amounts of cobalt chloride hexahydrate)
(1) Synthesizing a nano copper sulfide aqueous solution: respectively weighing 0.1705g of copper chloride dihydrate (1 mmol) and 0.2g of trisodium citrate dihydrate (0.68 mmol) into a 250mL round-bottom flask, weighing 180mL deionized water, adding the deionized water, and magnetically stirring at room temperature to dissolve the deionized water into a uniform light blue solution; weighing 0.6005g of sodium sulfide nonahydrate, adding deionized water to a constant volume in a 50mL volumetric flask to prepare an aqueous solution with the concentration of 50mmol/L, then quickly adding 20mL of the sodium sulfide nonahydrate aqueous solution into the solution, magnetically stirring for 5min at room temperature, and converting the reaction mixed solution into dark brown; and transferring the mixed solution into a constant-temperature water bath kettle, heating in a water bath to 90 ℃, continuously heating for continuous reaction for 15min to obtain a dark green nano copper sulfide solution, cooling in an ice water bath, and finally placing the solution in a refrigerator at 4 ℃ for later use.
(2) Synthesizing a copper cobalt sulfide catalyst: weighing 0.2379g of cobalt chloride hexahydrate (1 mmol), stirring and dissolving into 40mL of nano copper sulfide solution (containing 0.2mmol of nano copper sulfide), uniformly mixing, placing on a platform stirrer, and magnetically stirring at room temperature for 10min to obtain uniform solution; then, transferring the solution to a 100mL high-pressure reaction kettle, and putting the reaction kettle into a 150-DEG oven for reaction for 10 hours; after the reaction is finished, after the reaction kettle is cooled to room temperature, centrifuging the product, washing the product with water and ethanol for 3 times respectively, drying the product in a vacuum drying oven for 24 hours at room temperature, and uniformly grinding the dried sample in an agate mortar to obtain the copper cobalt sulfide.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the copper cobalt sulfide catalyst was weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio of 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
The results of the OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 The overpotential of (1) is 311mV, which is superior to that of commercial RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV).
It should be understood that while the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein, and any combination of the various embodiments may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims (7)

1. High-efficiency oxygen evolution catalyst CuCo 2 S 4 Characterized in that the high-efficiency oxygen evolution catalyst CuCo 2 S 4 Is an ultra-small nanosphere and is loaded on glassy carbon as a catalystThe electrode is used as a working electrode for high-efficiency catalytic oxygen evolution reaction, and the preparation method comprises the following steps:
(1) Weighing cobalt chloride hexahydrate, stirring and dissolving the cobalt chloride hexahydrate into a nano copper sulfide solution, uniformly mixing the cobalt chloride hexahydrate and the nano copper sulfide solution, placing the mixture on a platform stirrer, and stirring the mixture at room temperature to obtain a uniformly mixed solution 1; the molar ratio of the cobalt chloride hexahydrate to the nano copper sulfide of the nano copper sulfide solution is as follows: 0.25 to 1:0.2;
(2) Transferring the solution 1 prepared in the step (1) into a high-pressure reaction kettle, and putting the reaction kettle into an oven to react for 10 hours at the temperature of 150-180 ℃;
(3) After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging the product, washing the product with water and ethanol, and drying the product in vacuum at room temperature to obtain CuCo 2 S 4 High efficiency OER catalyst.
2. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 1 2 S 4 The preparation method is characterized by comprising the following specific steps:
(1) Weighing cobalt chloride hexahydrate, stirring and dissolving the cobalt chloride hexahydrate into a nano copper sulfide solution, uniformly mixing the solution, placing the solution on a platform stirrer, and stirring the solution at room temperature to obtain a uniformly mixed solution 1; the molar ratio of the cobalt chloride hexahydrate to the nano copper sulfide of the nano copper sulfide solution is as follows: 0.25 to 1:0.2;
(2) Transferring the solution 1 prepared in the step (1) into a high-pressure reaction kettle, and putting the reaction kettle into an oven to react for 10 hours at the temperature of 150-180 ℃;
(3) After the reaction is finished, cooling the reaction kettle to room temperature, centrifuging the product, washing the product with water and ethanol, and drying the product in vacuum at room temperature to obtain CuCo 2 S 4 High efficiency OER catalyst.
3. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 2 2 S 4 The preparation method is characterized in that in the step (1), the room temperature stirring time is 10-20 min.
4. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 2 2 S 4 The preparation method is characterized in that in the step (3), the mixture is washed for 3 to 5 times by water and ethanol, and is dried for 24 hours in vacuum at room temperature.
5. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 2 2 S 4 The preparation method is characterized in that the preparation method of the nano copper sulfide solution comprises the following steps:
weighing copper chloride dihydrate and trisodium citrate dihydrate, adding deionized water, and magnetically stirring at room temperature to dissolve the copper chloride dihydrate and the trisodium citrate dihydrate into a uniform light blue solution; weighing sodium sulfide nonahydrate, and adding deionized water to prepare Na 2 S·9H 2 O aqueous solution, followed by adding Na 2 S·9H 2 Quickly adding the O aqueous solution into the light blue solution, and magnetically stirring at room temperature for reaction until the mixed solution turns into dark brown; and transferring the mixed solution into a constant-temperature water bath kettle, heating in a water bath to 90 ℃, reacting to obtain a dark green copper sulfide nanoparticle solution, cooling in an ice-water bath, and finally placing the solution in a refrigerator for later use.
6. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 5 2 S 4 The preparation method is characterized in that in the light blue solution, the ratio of copper chloride dihydrate, trisodium citrate dihydrate and deionized water is 1mmol:0.68mmol:180mL; the Na is 2 S·9H 2 The volume ratio of the O aqueous solution to the light blue solution is 1 2 S·9H 2 The concentration of the O aqueous solution was 50mmol/L.
7. The high efficiency oxygen evolution catalyst CuCo as claimed in claim 5 2 S 4 The preparation method is characterized in that the reaction time of magnetic stirring at room temperature is 5min; heating in a water bath to 90 ℃ for reaction for 15min; the refrigerator temperature was 4 ℃.
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