CN108855181B - Co-loaded BCNO nanosheet3O4Preparation method of oxygen evolution reaction electrocatalyst - Google Patents

Co-loaded BCNO nanosheet3O4Preparation method of oxygen evolution reaction electrocatalyst Download PDF

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CN108855181B
CN108855181B CN201810566686.9A CN201810566686A CN108855181B CN 108855181 B CN108855181 B CN 108855181B CN 201810566686 A CN201810566686 A CN 201810566686A CN 108855181 B CN108855181 B CN 108855181B
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bcno
cobalt acetate
nanosheet
melamine
boric acid
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CN108855181A (en
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张兴华
冀雪峰
贾小波
卢遵铭
李兰兰
杨晓婧
刘辉
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Hebei University of Technology
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Abstract

The invention relates to a BCNO nano-sheet loaded Co3O4The preparation method of the oxygen evolution reaction electrocatalyst. The method adopts ethylene glycol as a solvent, boric acid, melamine and cobalt acetate as raw materials, boric acid and melamine are condensed in ethylene glycol to form a BCNO nanosheet precursor, and the precursor is sintered at one time in a muffle furnace without protective atmosphere to synthesize Co3O4a/BCNO nanosheet composite catalyst, the Co3O4the/BCNO nanosheet composite catalyst has high electrocatalytic performance and electrochemical stability, and can be used as an oxygen evolution reaction electrocatalyst for the fields of development of zinc-air batteries, clean energy and the like.

Description

Co-loaded BCNO nanosheet3O4Preparation method of oxygen evolution reaction electrocatalyst
Technical Field
The invention belongs to the technical field of novel functional materials, and particularly relates to a method for loading Co on a BCNO nano-chip by utilizing solid-phase sintering3O4Preparation and application of the oxygen evolution reaction electrocatalyst.
Background
Current oxygen evolution electrocatalysts are based on noble metal oxides such as iridium dioxide (IrO)2) Or ruthenium dioxide (RuO)2) Mainly, although they have high catalytic performance, they are expensive, scarce in resources, high in synthesis cost, poor in stability in the catalytic process, and easy to dissolve under acidic or alkaline reaction conditions. Therefore, the development and application of non-noble metal oxides, particularly transition metal oxides, as oxygen evolution reaction electrocatalysts has attracted extensive attention and research by researchers. Co3O4(cobaltosic oxide) is a very useful compoundThe electro-catalytic material has the advantages of low preparation temperature (500-700 ℃), no need of protective atmosphere sintering (namely sintering in air), energy conservation, environmental protection, good catalytic performance, stable structure and the like, and has wide application prospect in the fields of electrode materials, super capacitors, bifunctional oxygen catalysts, magnetic materials and the like. Co is currently synthesized by a solid phase method3O4However, Co obtained by this method3O4The size is in the micron order, and the larger particle size has larger limitation on the application of the catalyst as the oxygen evolution reaction electrocatalyst. In order to increase Co3O4Generally supported on a carbon-based material with good conductivity such as carbon black, carbon nanotubes, graphene or redox graphene, although this method does enable Co to be increased3O4But generally the process steps are cumbersome and long, such as multiple steps through hydrothermal synthesis or long-term chemical reflux are required, and the carbon-based material is easily corroded during the electrochemical process to affect the stability of the catalyst. Boron Carbon Nitrogen Oxygen (BCNO) is a boron nitride-based semiconductor material, has very good chemical stability and thermal stability, but the conductivity of the bulk material is poor. Therefore, if the catalyst can be prepared into a two-dimensional nano material, the conductivity of the catalyst can be greatly improved, and the catalyst is very expected to be a catalyst carrier material with excellent performance. Based on the research background, how to develop a new two-dimensional BCNO nano material and a simple and easy catalyst loading method to further improve Co3O4The catalytic performance of the catalyst has very important research significance and application value.
Disclosure of Invention
The invention aims at pure-phase Co3O4The problems of poor electrocatalytic performance of oxygen evolution reaction, complex compounding mode with carbon-based materials and poor stability are solved, and the method for preparing the BCNO nanosheet loaded Co in a large scale by a simple, convenient and feasible one-step method is provided3O4The synthesis method of the oxygen evolution reaction electrocatalyst improves the performance of the electrocatalyst. The method uses ethylene glycol as a soft template, and boric acid and melamine are generated in the ethylene glycolPerforming addition and polycondensation reaction to form a BCNO nanosheet precursor, uniformly dispersing cobalt acetate on the BCNO nanosheet precursor, and finally synthesizing Co loaded by the BCNO nanosheet through one-step sintering3O4Composite catalyst (Co)3O4/BCNO). Co obtained by the invention3O4the/BCNO composite catalyst has lower overpotential and better stability, and has wide application prospect in the aspects of cleaning energy, preparing novel air batteries and the like.
The technical scheme of the invention is as follows:
co-loaded BCNO nanosheet3O4The preparation method of the oxygen evolution reaction electrocatalyst comprises the following steps:
step 1: dissolving a proper amount of cobalt acetate in a certain volume of glycol solvent, and stirring for 30-60 minutes at 25 ℃; wherein, the cobalt acetate added in every 25mL of glycol is 0.2-1 mmol;
step 2: immediately adding weighed boric acid and melamine into the cobalt acetate solution in the step 1, heating and stirring at 110 ℃, stopping stirring after the boric acid and the melamine are completely dissolved, and then heating at 110 ℃ for 4-6 hours until ethylene glycol in the boric acid and the melamine is evaporated to dryness to obtain a cobalt acetate loaded BCNO nanosheet precursor; wherein, every 25mL of ethylene glycol is added with boric acid with the molar ratio: melamine 1: 1-3, molar ratio of cobalt acetate: boric acid 1: 10-50 parts of;
and step 3: placing the cobalt acetate loaded BCNO nano sheet precursor prepared in the previous step into a muffle furnace, heating to 500-fold-at-700 ℃ at the rate of 5 ℃ per minute, sintering for 5 hours, naturally cooling to room temperature after sintering, and grinding the product for 30-60 minutes to obtain Co3O4a/BCNO nanosheet composite catalyst powder;
and 4, step 4: 5mg of Co3O4Adding the/BCNO nano-sheet composite catalyst powder into 750 mu L of deionized water and 250 mu L of isopropanol mixed solvent, performing ultrasonic treatment for 30 minutes, then adding 30 mu L of 5% perfluorinated sulfonic acid solution, and continuing ultrasonic treatment for 30 minutes to obtain Co3O4the/BCNO catalyst electrode ink.
The core of the invention is to adoptSynthesis of Co loaded by BCNO nano sheet by step method3O4The composite catalyst is prepared by using ethylene glycol as a template, directly synthesizing a BCNO nanosheet precursor by using boric acid and melamine, uniformly loading cobalt acetate on the BCNO nanosheet precursor, and synthesizing Co through one-step sintering3O4the/BCNO nano-sheet composite catalyst. The invention utilizes Co3O4The interaction between the nano-particles and BCNO nano-sheets further promotes Co3O4And the product obtained by the method as an electrocatalytic oxygen evolution reaction catalyst is in proportion to RuO2The noble metal catalyst has better catalytic performance, and provides reference for improving the performance of the non-noble metal catalyst.
The invention has the beneficial effects that:
co proposed by the invention3O4The preparation method of the/BCNO nanosheet composite catalyst is simple in step, convenient to operate, low in requirement on preparation equipment and capable of improving safety in the experimental process. Co prepared by the method of the invention3O4The supported BCNO nano-chip has good conductivity and good electrocatalytic water oxidation performance.
Co prepared by the technical scheme of the invention3O4the/BCNO nanosheet composite catalyst is subjected to performance test by utilizing an X-ray diffractometer (Rigaku Ultima IV) (the scanning range is 10-80 degrees, the scanning rate is 4 degrees/minute, the scanning step length is 0.02 degrees), an X-ray photoelectron spectrometer (PHI1600EXCA), a scanning electron microscope (Hitachi, S-4800), a transmission electron microscope (JEOL,2100) and an electrochemical workstation (Shanghai Chenghua CHI750E) (the testing range of Cyclic Voltammetry (CV) is 0-0.5V, the testing range of Linear Scanning Voltammetry (LSV) is 0-0.7V, and the testing voltage of alternating current impedance spectroscopy (EIS) is 0.56V), and the testing results show that: sample is Co3O4The nanoparticles are loaded on BCNO nano-chips, and the sample contains B, C, N, O, Co and other chemical elements. The overpotential of the prepared catalyst with the optimal performance is 320mV, compared with the common noble metal catalyst ruthenium dioxide, the overpotential is lower, compared with pure phase Co3O4The catalytic performance of the particles is greatly improved, Co3O4Composite catalysis of/BCNO nano-sheetThe electrochemical alternating-current impedance of the catalyst is obviously reduced, the Tafel slope is also obviously lower than that of other catalysts, and the activity and the stability of the catalyst are obviously improved.
Drawings
FIG. 1 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4X-ray diffraction patterns of the/BCNO composite catalyst and pure BCNO nano-sheets.
FIG. 2 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4Low power transmission electron microscope picture of the/BCNO composite catalyst.
FIG. 3 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4High-resolution transmission electron microscope images of the/BCNO composite catalyst.
FIG. 4 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4X-ray photoelectron energy spectrogram of the/BCNO composite catalyst and the pure BCNO nano sheet.
FIG. 5 is a graph of the amounts of cobalt acetate, boric acid: melamine 1: 2, Co prepared at a sintering temperature of 500 DEG C3O4The polarization curve of oxygen evolution reaction of the/BCNO composite catalyst is compared with a graph.
FIG. 6 shows the results of examples 6 to 8 in which the cobalt acetate was 0.8mmol, and the boric acid: melamine 1: 1-3 Co prepared at sintering temperature of 700 DEG C3O4The polarization curve of oxygen evolution reaction of the/BCNO composite catalyst is compared with a graph.
FIG. 7 shows the results of examples 9 to 11 in which the cobalt acetate was 0.8mmol, and the boric acid: melamine 1: 2, Co prepared at 500 deg.C, 600 deg.C, 700 deg.C respectively3O4The polarization curve of oxygen evolution reaction of the/BCNO composite catalyst is compared with a graph.
FIG. 8 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4The polarization curves of oxygen evolution reaction of the/BCNO composite catalyst and other catalysts are compared.
FIG. 9 is the boronic acid of example 9: melamine 1: 2, sintering temperatureCo prepared at 600 DEG C3O4Comparison graph of cyclic voltammetry curves of the/BCNO composite catalyst and other oxygen evolution reaction catalysts.
FIG. 10 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4Comparison graph of electrochemical AC impedance of the/BCNO composite catalyst and other oxygen evolution reaction catalysts.
FIG. 11 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4The Tafel slope of the/BCNO composite catalyst and other oxygen evolution reaction catalysts is compared.
FIG. 12 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4/BCNO composite catalyst and Co3O4The electrochemical stability test result chart of (1).
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Preparation of Co with different cobalt acetate dosage3O4the/BCNO nano-sheet composite catalyst.
Example 1:
step 1: adding 0.2mmol of cobalt acetate into 25mL of ethylene glycol, heating and stirring at 25 ℃ for 30 minutes;
step 2: adding weighed 2mmol of boric acid and 4mmol of melamine into the cobalt acetate solution obtained in the step 1, heating and stirring at 110 ℃, stopping stirring after the boric acid and the melamine are completely dissolved, and then heating at 110 ℃ for 4 hours until ethylene glycol in the solution is evaporated to dryness to obtain a BCNO nanosheet precursor loaded with cobalt acetate;
and step 3: sintering the cobalt acetate/BCNO nanosheet precursor prepared in the step 2 at 500 ℃, wherein the heating rate is 5 ℃ per minute, the sintering time is 5 hours, naturally cooling to room temperature after sintering is finished, and grinding the product for 40 minutes to obtain Co3O4a/BCNO nanosheet composite catalyst powder;
and 4, step 4: 5mg of Co3O4Adding the/BCNO nano-sheet composite catalyst powder into 750 mu L of deionized water and 250 mu L of isopropanol mixed solution, carrying out ultrasonic treatment for 30 minutes, then adding 30 mu L of 5% perfluorinated sulfonic acid solution, and continuing ultrasonic treatment for 30 minutes to obtain Co3O4the/BCNO composite catalyst electrode ink.
Example 2:
the other steps are the same as example 1, except that the cobalt acetate in step 1 is changed from 0.2mmol to 0.4 mmol;
example 3:
the other steps are the same as example 1, except that the cobalt acetate in step 1 is changed from 0.2mmol to 0.6 mmol;
example 4:
the other steps are the same as example 1, except that the cobalt acetate in step 1 is changed from 0.2mmol to 0.8 mmol;
example 5:
the other steps were the same as in example 1 except that the amount of cobalt acetate in step 1 was changed from 0.2mmol to 1 mmol.
And (3) testing results: co with different loading amounts is prepared by changing the dosage of the cobalt acetate3O4the/BCNO nanosheet composite catalyst is subjected to X-ray diffraction, a scanning electron microscope, a transmission electron microscope, X-ray photoelectron spectroscopy, cyclic voltammetry testing, linear voltammetry scanning testing, electrochemical alternating current impedance testing and stability testing, and the testing results are shown in figures 1-12.
FIG. 1 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4The BCNO nano-sheet composite catalyst and X-ray diffraction pattern of pure BCNO nano-sheet, the BCNO nano-sheet is amorphous structure, Co3O4the/BCNO sample has several stronger diffraction peaks at 32.2 degrees, 37.2 degrees, 45 degrees, 59.8 degrees and 65.1 degrees, and is indicated to be Co through comparing with a standard PDF card (PDF #42-1467)3O4The diffraction peak of (1). FIG. 2 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4The result of a low-power transmission electron microscope picture of the/BCNO nano-sheet composite catalyst shows that the appearance of the sample is of a sheet structure，Co3O4Nanoparticles are dispersed on the BCNO nanosheets. FIG. 3 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4High resolution transmission electron microscope image of/BCNO nano-sheet composite catalyst, obvious lattice stripes on the nano-sheets correspond to Co3O4The (311) crystal plane of the nanoparticles. FIG. 4 is the boronic acid of example 9: melamine 1: 2, Co prepared at a sintering temperature of 600 DEG C3O4The X-ray photoelectron energy spectrogram of the/BCNO nanosheet composite catalyst and the pure BCNO nanosheet shows that the sample contains B, C, N, O, Co and other five chemical elements. By analyzing the above 5 figures, it can be concluded that the prepared sample is Co3O4/BCNO nanosheet composite catalyst, Co3O4Nanoparticles were supported on BCNO nanoplatelets. FIG. 5 is a graph of the amounts of cobalt acetate, boric acid: melamine 1: 2, Co prepared at a sintering temperature of 500 DEG C3O4And a comparison graph of oxygen evolution reaction polarization curves of the/BCNO nanosheet composite catalyst. The results show that the overpotential is reduced with the increase of the dosage of the cobalt acetate, reaches the lowest 325mV with the dosage of the cobalt acetate of 0.8mmol, and then the overpotential is increased with the increase of the dosage of the cobalt acetate.
Preparation of Co from different molar ratios of boric acid and melamine3O4the/BCNO nano-sheet composite catalyst.
Example 6:
step 1: adding 0.8mmol of cobalt acetate into 25mL of ethylene glycol, heating, stirring and dissolving, wherein the heating temperature is 25 ℃, and the heating and stirring time is 50 minutes;
step 2: adding weighed 2mmol of boric acid and 2mmol of melamine into the cobalt acetate solution in the step 1, heating and stirring at 110 ℃, stopping stirring after the boric acid and the melamine are completely dissolved, and then heating at 110 ℃ for 5 hours until ethylene glycol in the solution is evaporated to dryness to obtain a BCNO nanosheet precursor loaded with cobalt acetate;
and step 3: sintering the cobalt acetate/BCNO nanosheet precursor prepared in the step 2 at 700 ℃, wherein the heating rate is 5 ℃ per minute, the sintering time is 5 hours, and sintering is carried outNaturally cooling to room temperature after the knot is finished, and then grinding the product for 50 minutes to obtain Co3O4a/BCNO nanosheet composite catalyst powder;
and 4, step 4: 5mg of Co3O4Adding the/BCNO nano-sheet composite catalyst powder into 750 mu L of deionized water and 250 mu L of isopropanol mixed solution, carrying out ultrasonic treatment for 30 minutes, then adding 30 mu L of 5% perfluorinated sulfonic acid solution, and continuing ultrasonic treatment for 30 minutes to obtain Co3O4the/BCNO catalyst electrode ink.
Example 7:
the other steps are the same as example 6 except that the boric acid in step 2: the molar ratio of melamine is 1: 1 is changed into 1: 2.
example 8:
the other steps are the same as example 6 except that the boric acid in step 2: the molar ratio of melamine is 1: 1 is changed into 1: 3.
and (3) testing results: co was prepared by varying the molar ratio of different boric acids and melamines3O4the/BCNO nanosheet composite catalyst is used for carrying out X-ray diffraction, a scanning electron microscope, a transmission electron microscope, X-ray photoelectron spectroscopy, cyclic voltammetry testing, linear voltammetry scanning testing, electrochemical alternating current impedance testing and stability testing on a sample. FIG. 6 shows the amount of cobalt acetate used in examples 6 to 8 of 0.8mmol, boric acid: melamine 1: 1-3 Co prepared at sintering temperature of 700 DEG C3O4And a comparison graph of oxygen evolution reaction polarization curves of the/BCNO nanosheet composite catalyst. As can be seen from fig. 6, in boric acid: melamine 1: 2, overpotential of catalyst relative to boric acid: melamine 1: 1 and 1: the sample 3 is lower, the limiting current density is higher, and the electrocatalytic performance is optimal.
Preparation of Co at different sintering temperatures3O4the/BCNO nano-sheet composite catalyst.
Example 9:
step 1: adding 0.8mmol of cobalt acetate into 25mL of ethylene glycol, heating, stirring and dissolving, wherein the heating temperature is 25 ℃, and the heating and stirring time is 60 minutes;
step 2: adding weighed 2mmol of boric acid and 4mmol of melamine into the cobalt acetate solution in the step 1, heating and stirring at 110 ℃, stopping stirring after the boric acid and the melamine are completely dissolved, and then heating at 110 ℃ for 6 hours until ethylene glycol in the solution is evaporated to dryness to obtain a BCNO nanosheet precursor loaded with cobalt acetate;
and step 3: sintering the cobalt acetate/BCNO nanosheet precursor prepared in the step 2 at the temperature of 600 ℃, wherein the heating rate is 5 ℃ per minute, the sintering time is 5 hours, naturally cooling to room temperature after sintering is finished, and grinding the product for 60 minutes to obtain Co3O4a/BCNO nanosheet composite catalyst powder;
and 4, step 4: 5mg of Co3O4Adding the/BCNO nano-sheet composite catalyst powder into 750 mu L of deionized water and 250 mu L of isopropanol mixed solution, carrying out ultrasonic treatment for 30 minutes, then adding 30 mu L of 5% perfluorinated sulfonic acid solution, and continuing ultrasonic treatment for 30 minutes to obtain Co3O4the/BCNO catalyst electrode ink.
Example 10:
the other steps were the same as in example 9 except that the sintering temperature in step 3 was changed from 600 ℃ to 500 ℃.
Example 11:
the other steps were the same as in example 9 except that the sintering temperature in step 3 was changed from 600 ℃ to 700 ℃.
And (3) testing results: co is prepared by changing different sintering temperatures3O4the/BCNO nanosheet composite catalyst is subjected to X-ray diffraction, a scanning electron microscope, a transmission electron microscope, X-ray photoelectron spectroscopy, cyclic voltammetry testing, linear voltammetry scanning testing, electrochemical alternating current impedance testing and stability testing. FIG. 7 shows the amount of cobalt acetate used in examples 9 to 11 of 0.8mmol, boric acid: melamine 1: 2, Co prepared at 500 deg.C, 600 deg.C, 700 deg.C respectively3O4And a comparison graph of oxygen evolution reaction polarization curves of the/BCNO nanosheet composite catalyst. As can be seen from fig. 7, at a sintering temperature of 600 ℃, the overpotential is lower, the limiting current density is higher, and the electrocatalytic performance is optimal compared to the samples sintered at 500 ℃ and 700 ℃. FIGS. 8-11 are boronic acids of example 9: melamine 1:2, Co prepared at a sintering temperature of 600 DEG C3O4A comparison graph of the performance of the/BCNO nano-sheet composite catalyst and other oxygen evolution reaction catalysts. As can be seen from the figure, Co3O4Compared with common noble metal catalyst RuO (RuO) by adopting/BCNO nanosheet composite catalyst2And pure phase Co3O4The oxygen evolution reaction electrocatalysis performance is better, the overpotential is lower, the conductivity is better, the Tafel slope is lower, the active surface area is larger, and the application prospect in the field of oxygen evolution reaction catalysts is wide. From FIG. 12, it can be seen that Co3O4the/BCNO nanosheet composite catalyst can stably work for 10 hours under the voltage of 0.56V, and is good in stability.
According to the results, the method provided by the invention avoids complex preparation process, and synthesizes Co with higher catalytic activity at lower temperature (600 ℃) and simple process3O4The catalyst/BCNO nanosheet composite effectively improves Co3O4The defects of poor catalytic performance, poor stability and the like of the similar material also provide reference for the preparation process of the composite of the similar material and the carbon material, and the Co is used for preparing the composite3O4the/BCNO nanosheet composite catalyst can also be applied to the fields of metal-air batteries, full water electrolysis, novel energy sources and the like.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
The invention is not the best known technology.

Claims (2)

1. Co-loaded BCNO nanosheet3O4The preparation method of the oxygen evolution reaction electrocatalyst is characterized by comprising the following steps:
step 1: adding cobalt acetate into an ethylene glycol solvent, heating, stirring and dissolving, wherein the heating temperature is 25 ℃, and the stirring time is 30-60 minutes;
step 2: adding weighed boric acid and melamine with different molar ratios into the cobalt acetate solution in the step 1, heating and stirring to completely dissolve the boric acid and the melamine, stopping stirring, and continuing heating until the solution is evaporated to dryness to obtain a cobalt acetate/BCNO nanosheet precursor, wherein the heating temperature is 100-120 ℃, and the heating time is 4-6 hours;
and step 3: putting the cobalt acetate/BCNO nanosheet precursor prepared in the step 2 into a muffle furnace for sintering, naturally cooling to room temperature after sintering, and grinding the product for 40-60 minutes to obtain Co3O4a/BCNO nanosheet composite catalyst;
and 4, step 4: 5mg of Co3O4Adding the/BCNO nano sheet composite catalyst into 750 mu L of deionized water and 250 mu L of isopropanol mixed solution, performing ultrasonic treatment for 30-40 minutes, adding 30 mu L of 5% perfluorinated sulfonic acid solution, and continuing performing ultrasonic treatment for 30-40 minutes to obtain electrode ink, so that the electrode ink is used for oxygen evolution reaction electrocatalysis test;
the amount of the cobalt acetate used per 25mL of the ethylene glycol is 0.2-1 mmol;
the molar ratio of the cobalt acetate to the boric acid is 1: 10-50 parts of;
the molar ratio of boric acid to melamine is 1: 1-3.
2. Co-loaded BCNO nanosheet as in claim 13O4The preparation method of the oxygen evolution reaction electrocatalyst is characterized in that the sintering temperature in the step 3 is 500-700 ℃, and the sintering time is 5 hours.
CN201810566686.9A 2018-06-05 2018-06-05 Co-loaded BCNO nanosheet3O4Preparation method of oxygen evolution reaction electrocatalyst Expired - Fee Related CN108855181B (en)

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CN106540734A (en) * 2016-11-03 2017-03-29 阜阳师范学院 Compound CNB photocatalysts of a kind of transition metal oxide and preparation method thereof
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CN106540734A (en) * 2016-11-03 2017-03-29 阜阳师范学院 Compound CNB photocatalysts of a kind of transition metal oxide and preparation method thereof
CN107228889A (en) * 2017-06-14 2017-10-03 上海海洋大学 The preparation and application of a kind of cobalt oxide/mesoporous carbon composite material electrochemical sensor

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