CN107871875B - Oxygen evolution reaction electrocatalyst, preparation method and application thereof - Google Patents

Oxygen evolution reaction electrocatalyst, preparation method and application thereof Download PDF

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CN107871875B
CN107871875B CN201610851613.5A CN201610851613A CN107871875B CN 107871875 B CN107871875 B CN 107871875B CN 201610851613 A CN201610851613 A CN 201610851613A CN 107871875 B CN107871875 B CN 107871875B
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nickel
solution
oxygen evolution
salt
ferrous
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CN107871875A (en
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杨维慎
朱凯月
朱雪峰
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • Y02E60/50—Fuel cells

Abstract

The invention relates to an oxygen evolution reaction electrocatalyst, a preparation method and application thereof, wherein the method comprises the step of exposing a mixed system of a nickel-iron salt solution and an alkali solution to an oxidizing atmosphere for reaction; the nickel-iron salt solution is obtained by dissolving soluble ferrous salt and soluble nickel salt in water and uniformly mixing; the soluble ferrous salt is selected from ferrous sulfate, ferrous chloride or ferrous acetate; the soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate. The OER catalyst produced by the method of the invention has the advantages of simple equipment, convenient operation and low cost. Fe prepared simultaneously3+Doped beta-Ni (OH)2The catalyst presents a nano-rod-shaped microscopic form, has good OER activity, and has activity and stability superior to the previously reported NiFe layered double hydroxide and the IrO with the best performance at present2. Therefore, the catalyst can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal air cells, water electrolysis and the like.

Description

Oxygen evolution reaction electrocatalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of electrochemical catalysts, and relates to Fe capable of being used for catalyzing Oxygen Evolution Reaction (OER)3+Doped beta-Ni (OH)2A method for preparing nano-rods.
Background
In modern society, people's clothes, food and residents are tightly connected with energy supply and consumption, and energy sources cannot be kept away in cooking, heating, lighting, transportation, industrial production and the like. It can be said that there is no energy industry and no modern civilization. In addition, fossil energy is unclean energy, and a great amount of waste water, waste gas and waste residues are discharged to the nature while the vast majority of energy requirements of people are met, so that the global environment such as acid rain hazard, greenhouse effect, ozone layer damage, threat of chemical timing bombs and the like is causedAnd (5) problems are solved. In the 21 st century, with the continuous development of global economy, the fossil energy sources, particularly petroleum, coal, natural gas and the like, on which the fossil energy sources depend face a serious resource exhaustion problem, and the subjects of resource conservation, efficient utilization of existing resources, development of clean energy and new technology are the world energy science and technology in the 21 st century. The metal-air battery has the advantages of rich raw materials, safety, environmental protection, high energy density and the like, and is called as a novel green energy facing the 21 st century. The anode of the metal-air battery is active metal (such as Mg, Al, Zn and the like), and the metal M is oxidized into corresponding metal ions M + during discharging; when charged, the metal ions are reduced into corresponding metals. The cathode active material is oxygen in air, and O is generated during discharge2Is reduced to OH-; OH-is oxidized by O during charging2And (4) precipitating. Fuel metal M and oxidant O for metal air fuel cell2Can be regenerated through the charging process, and has the function of energy storage.
However, due to the slow kinetic process of the oxygen evolution reaction, the voltage required for oxygen evolution is much higher than the thermodynamic potential, severely limiting the application of rechargeable metal-air batteries. Up to now, IrO2The OER catalyst with the best performance and stability in an alkaline system is rare in content on the earth and expensive, so that the commercial application of the OER catalyst is greatly limited. Therefore, the development of the low-cost, stable and efficient OER catalyst has important significance.
Besides noble metals, oxides or hydroxides containing nickel iron have high oxygen evolution catalytic activity in alkaline media. Interestingly, nickel hydroxide and iron oxide alone catalyze OER with poor performance, but the composite nickel iron hydroxide exhibits excellent OER performance. In 2014, Boettcher et al prepared Ni by in situ electrochemical methods1- xFexThe OOH film is used for oxygen precipitation, and the doped Fe not only improves the conductivity of the film, but also promotes the partial charge transfer effect of Ni, thereby obviously improving the OER performance. In 2015, Dai et al utilized the high conductivity of carbon nanotubes by mixing Ni-Fe layered double hydroxide (with alpha-Ni (OH))2Similar in structure) is compounded with the carbon nano tube to obtain the high-performance OER catalyst,and is published in the Journal of the American Chemical Society. In 2016, Yan et al, Electrochemistry Communications reported that nanosheets of Ni-Fe layered double hydroxide were produced by hydrothermal methods for catalyzing OER. Previous studies have focused on iron-doped gamma-NiOOH and Ni-Fe layered double hydroxides generated electrochemically in situ. Furthermore compared to commercial IrO2These catalysts still have problems of poor stability, complicated catalyst synthesis, and the like.
Disclosure of Invention
The invention aims to provide a solution for the problems of high price, low catalytic current density, high overpotential, poor stability and complex synthetic method of the conventional OER catalyst. The invention provides an oxygen evolution reaction electrocatalyst, a preparation method and application thereof systematically.
Firstly, the preparation method of the Oxygen Evolution Reaction (OER) electrocatalyst comprises the step of exposing a mixed system of a nickel-iron salt solution and an alkali solution to an oxidizing atmosphere for reaction; the nickel-iron salt solution is obtained by dissolving soluble ferrous salt and soluble nickel salt in water and uniformly mixing; the soluble ferrous salt is selected from ferrous sulfate, ferrous chloride or ferrous acetate; the soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate.
The synthesis method has the advantages of simple required equipment, convenient operation and low cost. On the other hand, Fe is produced by the above method3+Doped beta-Ni (OH)2. The oxygen evolution reaction electrocatalyst with a nanorod microstructure has excellent OER activity. The Tafel slope can reach 32mV dec-1The current density was 10mA cm at an overpotential of 0.26V-2And the activity and the stability are superior to NiFe layered double hydroxide reported in the prior art and IrO with the best performance at present2. Can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal air cells, water electrolysis and the like.
Based on this, it is an object of a further aspect of the present invention to provide the above-mentioned Fe of the present invention3+Doped beta-Ni (OH)2Use in Oxygen Evolution Reactions (OERs). Especially in alkaliUsed as an OER catalyst under mild conditions.
The OER catalyst produced by the method of the invention has the advantages of simple equipment, convenient operation and low cost. Fe prepared simultaneously3+Doped beta-Ni (OH)2The catalyst presents a nano-rod-shaped microscopic morphology, has good OER activity, and the Tafel slope reaches 32mV dec-1The current density was 10mA cm at an overpotential of 0.26V-2And the activity and the stability are superior to the previously reported NiFe layered double hydroxide and the IrO with the best performance at present2. Thus Fe3+Doped beta-Ni (OH)2The nano-rod can be used as an electrocatalyst in the fields of renewable fuel cells, rechargeable metal-air batteries, water electrolysis and the like.
Drawings
The invention is shown in figure 2:
FIG. 1 is Fe in example 43+Doped beta-Ni (OH)2Transmission electron micrographs of the material;
FIG. 2 shows Fe prepared in examples 1 to 93+Doped beta-Ni (OH)2An X-ray diffraction (XRD) pattern of the material.
Detailed Description
The invention provides a preparation method of an oxygen evolution reaction electrocatalyst and a catalyst prepared by the method. The oxygen evolution reaction electrocatalyst is Fe3+Doped beta-Ni (OH)2。
The invention firstly provides a preparation method of an oxygen evolution reaction electrocatalyst, which is based on an improved atom-level topological chemical conversion method and uses Ni and Fe salt solution to react with alkali solution to generate bivalent Fe-doped beta-Ni (OH) under the protection of inert gas2Then oxidized in oxidizing atmosphere by adopting an atomic-level topological chemical conversion method to generate trivalent Fe-doped beta-Ni (OH)2A catalyst.
The above method of the present invention comprises the steps of mixing a nickel iron salt solution with an alkaline solution, and exposing the mixed system to an oxidizing atmosphere.
Wherein the nickel-iron salt solution is obtained by dissolving soluble ferrous salt and soluble nickel salt in water and uniformly mixing; the soluble ferrous salt is selected from ferrous sulfate, ferrous chloride or ferrous acetate; preferably ferrous sulfate; the soluble nickel salt is selected from nickel sulfate, nickel chloride or nickel acetate; nickel sulfate is preferred. Further preferably, the concentration of the nickel-iron salt solution (according to the concentration sum of nickel ions and iron ions in the solution) is 0.1-2 mol/L. In a more preferable embodiment, in the nickel-iron salt solution, the molar ratio of the ferrous salt to the nickel salt is 0.05-0.6.
In the above method of the present invention, the alkali solution is a solution that can be used to provide hydroxide ions according to the conventional understanding in the art, and can be selected from, but not limited to, potassium hydroxide aqueous solution, sodium hydroxide or ammonia water. Among them, an aqueous potassium hydroxide solution is particularly preferred. More preferably, the alkaline solution is one in which the OH group is the same as the OH group-The concentration is 0.1-5 mol/L. The amount of alkaline solution may be based on OH-The amount of the substance (b) is 2 to 30 times of the total molar amount of the nickel ion and the iron ion.
In a specific embodiment, the process of mixing the nickel-iron salt solution with the alkali solution is to add the nickel-iron salt solution dropwise into the alkali solution to prepare a mixed system so as to control the violent side effects which may occur in the reaction. The dropping speed is 0.5-4 mL/min; preferably 1 mL/min.
In yet another embodiment, the preparation of the nickel-iron salt solution and the mixing thereof with the alkaline solution are carried out under inert gas protection. The inert gas is selected as is conventionally understood in the art.
In the method of the invention, the mixed system of the nickel-iron salt solution and the alkali solution is exposed to an oxidizing atmosphere, aiming at oxidizing 2-valent Fe into 3-valent Fe, wherein the oxidizing atmosphere is air, oxygen or ozone; air is preferred. The reaction temperature is 20-90 ℃. Preferably 80 deg.c. The reaction time is 4-6 hours.
According to the above description, the combination of the preferred technical features can obtain the preferred technical scheme of the preparation method of the invention, and such preferred technical scheme can be exemplified as follows, but is not limited thereto.
In a preferred technical scheme, the preparation method comprises the following steps:
(1) under the protection of inert atmosphere, dissolving soluble ferrous salt and soluble nickel salt in water and uniformly mixing to prepare a nickel-iron salt solution with the concentration of 0.1-2 mol/L;
(2) under the protection of inert atmosphere, dropwise adding the nickel-iron salt solution prepared in the step (1) into a potassium hydroxide aqueous solution with the concentration of 0.1-5 mol/L at the speed of 1 mL/min;
(3) exposing the mixed system prepared in the step (2) in an oxidizing atmosphere, and stirring and reacting for 4-6 hours at the temperature of 20-90 ℃; the obtained precipitate was washed with deionized water to pH 7, then with absolute ethanol for 3 times, centrifuged, dispersed in ethanol, and freeze-dried at low temperature.
Produced by the above method is Fe3+Doped beta-Ni (OH)2. Has excellent OER activity, can be applied to Oxygen Evolution Reaction (OER), and is especially used as an OER catalyst under alkaline conditions.
The invention further provides 9 examples in total in 1-9 to further illustrate the preparation method of the oxygen evolution reaction electrocatalyst, the prepared product and the application thereof.
The powder material prepared in the example of the invention shows the same characteristics by XRD test: when the scanning diffraction angle is 10-90 degrees, the diffraction peaks are respectively 20 degrees, 34 degrees, 39 degrees, 53 degrees, 61 degrees and 71 degrees, and the contrast is beta-Ni (OH)2The standard PDF cards of (1) found corresponding exactly to the respective 001 plane diffraction (19.258 degrees), 100 plane diffraction (33.064 degrees), 101 plane diffraction (38.541 degrees), 102 plane diffraction (52.100 degrees), 003 plane diffraction (60.240 degrees) and 103 plane diffraction (70.478 degrees). The nano rod is shown to be a hexagonal phase beta-Ni (OH)2 structure. Some shift of the diffraction peak to the right of the standard caliper is due to the smaller ionic radius of Fe3+(55pm) occupied beta-Ni (OH)2Ni with larger ionic radius in phase2+(69 pm). The detection results are shown in FIG. 2.
The products prepared in the examples of the present invention were further evaluated for Oxygen Evolution (OER) activity by the following methods:
(1) preparation of catalyst slurry: a certain amount of Fe3+The doped beta-Ni (OH)2 nano-rods and XC-72 are dispersed in isopropanol, then a proper amount of Nafion solution (5 w.t.%) is added into the isopropanol, and then the mixture is ultrasonically vibrated to uniformly disperse the mixture to obtain catalyst slurry.
(2) Preparing an electrode: transferring a certain amount of the prepared catalyst slurry to a rotary disk electrode by using a transfer pipette, and naturally drying in the air.
(3) Testing of electrode activity: the prepared electrodes were mounted on a rotating disk apparatus for testing. The test procedure was as follows:
1) the electrochemical test system is a three-electrode system (a glassy carbon electrode carrying a catalyst is used as a working electrode, a platinum wire or a platinum sheet is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode), and the electrolyte is 0.1mol/L KOH solution.
2) Before testing, the reactor was vented with O2To saturation, oxygen was also continuously introduced during the test.
3) Evaluating Oxygen Evolution (OER) activity, and performing polarization curve test (LSV) with voltage scan range of 0-0.8V and scan speed of 10mvs-1The rotation speed was 1600 rpm.
In contrast, IrO performs best for the catalytic OER currently commercialized2Oxygen evolution was evaluated (purchased from Johnson Matthey). Weighing commercial IrO2And XC-72 are dispersed in 2mL of isopropanol by 5mg respectively, then 50 mu L of Nafion (5 w.t.%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2When the voltage is higher than the threshold voltage, the overpotential is 0.34V; when the oxygen evolution current density is 20mA/cm2The overpotential is 0.38V.
Example 1
2.7801 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water at a nickel sulfate concentration of 0.5 mol/l. Dropwise adding 20mL of 0.5mol/L nickel sulfate solution into 80mL of 1.25mol/L potassium hydroxide solution under the protection of nitrogen atmosphere, and finishing dropwise adding for 20minThe reaction temperature was 80 ℃. The cloudy system was then exposed to air and allowed to react for 5 h. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Obtaining green powder. The obtained green powder and XC-72 are weighed and dispersed in 2mL of isopropanol by 5mg respectively, then 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and air-dried. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.42V.
Example 2
0.2628 g of ferrous sulfate heptahydrate and 2.5021 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water, the total concentration of ferrous sulfate and nickel sulfate being 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 80 ℃. The cloudy system was then exposed to air and allowed to react for 5 h. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.33V.
Example 3
0.7886 g of ferrous sulfate heptahydrate and 1.9461 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water, the total concentration of ferrous sulfate and nickel sulfate being 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1Adding 25mol/L potassium hydroxide solution, finishing dropping for 20min, and reacting at the temperature of 80 ℃. The cloudy system was then exposed to air and allowed to react for 5 h. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.27V.
Example 4
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water, the total concentration of ferrous sulfate and nickel sulfate being 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 80 ℃. The cloudy system was then exposed to air and allowed to react for 5 h. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The transmission electron micrograph is shown in FIG. 1. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.26V.
Example 5
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of nickel sulfate hexahydrate are weighed and dissolved in 20ml of water, and the total concentration of the ferrous sulfate and the nickel sulfate is 0.5mol per oneAnd (5) rising. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 80 ℃. Then oxygen is introduced into the turbid system, and the reaction is carried out for 5 hours. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.27V.
Example 6
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water, the total concentration of ferrous sulfate and nickel sulfate being 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 80 ℃. Then ozone is introduced into the turbid system for reaction for 5 hours. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.28V.
Example 7
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of nickel sulfate hexahydrate are weighed and dissolved in 20ml of water, and ferrous sulfate is dissolved inThe total concentration of iron and nickel sulphate was 0.5mol per litre. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 60 ℃. Then ozone is introduced into the turbid system for reaction for 5 hours. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.27V.
Example 8
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of nickel sulfate hexahydrate were weighed out and dissolved in 20ml of water, the total concentration of ferrous sulfate and nickel sulfate being 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 40 ℃. Then ozone is introduced into the turbid system for reaction for 5 hours. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.27V.
Example 9
1.3143 g of ferrous sulfate heptahydrate and 1.3901 g of sulfur hexahydrate are weighedThe nickel acid was dissolved in 20ml of water at a total concentration of ferrous sulfate and nickel sulfate of 0.5mol per liter. Under the protection of nitrogen atmosphere, 20mL of 0.5mol/L nickel sulfate solution is dropwise added into 80mL of 1.25mol/L potassium hydroxide solution, the dropwise addition is completed within 20min, and the reaction temperature is 80 ℃. Then ozone is introduced into the turbid system for reaction for 5 hours. Finally, the mixture was washed with water to pH 7, then washed with absolute ethanol 3 times and centrifuged. Dispersing the product into ethanol, and vacuum drying with a freeze dryer at low temperature. Thus, a yellowish brown powder was obtained. The obtained yellow-brown powder and XC-72 are weighed, 5mg of each powder is dispersed in 2mL of isopropanol, 50 mu L of Nafion (5%) solution is added, and the mixture is subjected to ultrasonic oscillation for 30min to be uniformly mixed to obtain catalyst slurry. Then 20. mu.L of the catalyst slurry was transferred onto a rotating disk electrode having a diameter of 5mm, and naturally dried in the air. The resulting electrode was evaluated for Oxygen Evolution (OER) activity according to the electrode testing procedure described in the summary of the invention above. The test result shows that when the oxygen evolution current density is 10mA/cm2The overpotential was 0.29V.
The above examples can be many, and a great deal of test data of the applicant proves that Fe can be successfully synthesized by the preparation method according to the technical scheme of the invention3+Doped beta-Ni (OH)2Nanorod, and exhibits excellent Oxygen Evolution Reaction (OER) catalytic performance under alkaline conditions.

Claims (6)

1. A method for preparing an oxygen evolution reaction electrocatalyst, said method comprising the steps of: (1) under the protection of inert atmosphere, dissolving soluble ferrous salt and soluble nickel salt in water and uniformly mixing to prepare a nickel-iron salt solution with the concentration of 0.1-2 mol/L; (2) under the protection of inert atmosphere, dropwise adding the nickel-iron salt solution prepared in the step (1) into an alkali solution at the speed of 1mL/min, wherein the alkali solution is a potassium hydroxide aqueous solution with the concentration of 0.1-5 mol/L; (3) exposing the mixed system prepared in the step (2) in an oxidizing atmosphere, and stirring and reacting for 4-6 h at the temperature of 20-90 ℃; washing the obtained precipitate with deionized water to pH =7, washing with anhydrous ethanol for 3 times, centrifuging, dispersing in ethanol, and freeze drying at low temperature.
2. The method of claim 1, wherein: in the nickel-iron salt solution, the molar ratio of ferrous salt to nickel salt is 0.05-0.6.
3. The method of claim 1, wherein the alkaline solution is in the form of OH-The amount of the substance is 2 to 30 times of the total mole number of the nickel ions and the iron ions.
4. Fe prepared by the method of claim 13+Doped beta-Ni (OH)2。
5. Fe as claimed in claim 43+Doped beta-Ni (OH)2Application in oxygen evolution reaction.
6. Use according to claim 5 as an oxygen evolution catalyst under alkaline conditions.
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