CN111041508A - Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof - Google Patents

Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof Download PDF

Info

Publication number
CN111041508A
CN111041508A CN201811190557.0A CN201811190557A CN111041508A CN 111041508 A CN111041508 A CN 111041508A CN 201811190557 A CN201811190557 A CN 201811190557A CN 111041508 A CN111041508 A CN 111041508A
Authority
CN
China
Prior art keywords
titanium mesh
cobaltosic oxide
array
electrode
oxide nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811190557.0A
Other languages
Chinese (zh)
Inventor
李新昊
张军军
陈接胜
野田克敏
原山贵司
后藤哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiaotong University
Toyota Motor Corp
Original Assignee
Shanghai Jiaotong University
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiaotong University, Toyota Motor Corp filed Critical Shanghai Jiaotong University
Priority to CN201811190557.0A priority Critical patent/CN111041508A/en
Priority to JP2019159493A priority patent/JP6932751B2/en
Publication of CN111041508A publication Critical patent/CN111041508A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention relates to a cobaltosic oxide nano beam array/titanium mesh electrode which is used as an anode reaction for water decomposition and comprises a titanium mesh and a cobaltosic oxide nano beam array grown on a mesh wire. The electrode preparation process of the invention comprises the following steps: growing cobaltosic oxide precursor basic carbonate on a titanium mesh by a hydrothermal method, calcining the precursor and treating an electrode by using a reducing agent to obtain the cobaltosic oxide nano-beam array/titanium mesh electrode. The electrode has high oxygen production catalytic activity and cycling stability, and the preparation process is simple to operate, green, safe and low in cost, and can realize large-scale continuous production. The product has wide potential application in the aspects of electrochemical water decomposition, green energy conversion and storage and the like.

Description

Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof
Technical Field
The invention belongs to the field of electrocatalytic water decomposition of transition metal oxides, and particularly relates to a cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and a preparation method thereof.
Background
In recent decades, with the increasing use of fossil energy (such as coal and petroleum) and the inevitable serious environmental pollution during the use of the energy, the world energy safety and the survival and development of human beings are affected, and the search for environment-friendly and renewable green and safe energy has become the hot door of new energy research at home and abroad. Solar energy is an inexhaustible energy source. The conversion and utilization of solar energy has been the key direction of scientific research in recent decades. With the rapid development of technologies such as solar photovoltaic power generation and perovskite solar cells, solar energy transformation is easier. However, compared with other energy forms, solar energy is greatly influenced by seasons and time, and thus the solar transformation energy has a disadvantage of unstable output. At the same time, the storage of electrical energy also presents a significant challenge. The electrochemical method is used for splitting water, generating hydrogen at a cathode, generating oxygen at an anode, and converting unstable electric energy into stable chemical energy for storage, which is a new way for solving the problems. The generated hydrogen gas is easily converted from chemical energy into electrical energy by the fuel cell. By the method, electric energy and chemical energy can be well converted. However, electrolysis of water requires electrical energy to drive. To save costs and energy, electrolysis of water requires the use of catalytic electrodes to reduce the energy required for the water splitting process. Meanwhile, electrochemical water decomposition requires that the used catalyst has high durability, physical and chemical stability and high catalytic activity. Other storage and conversion technologies related to energy sources, such as lithium air batteries, zinc air batteries, lithium sulfur batteries, electrochemical (super) capacitors, fuel cells, and the like, have not been fully utilized. The large-scale preparation of electrode materials in electrochemical devices such as electrocatalysis, photocatalysis and photoelectrocatalysis electrodes containing abundant elements and having excellent performance, various battery capacitors and the like is always a key point and a difficulty in the research fields.
Electrocatalytic decomposition of water to produce hydrogen and oxygen is a green, sustainable, and economical energy conversion process. Under the present conditions, the cathode and anode used in the electrolytic water process are noble metal (platinum) and noble metal oxide (e.g., iridium oxide and ruthenium oxide) materials, respectively. The noble metals are contained in the earth crust in low content, so the noble metals are expensive, and the scale application of electrochemical water decomposition is seriously hindered. The theoretical potential of water decomposition anodic oxidation reaction (generating oxygen) is 1.23V, and the theoretical potential of cathode reduction reaction (generating hydrogen) is 0V, so that more energy is needed for the anodic reaction to push, and a catalytic electrode required by the anodic reaction with stable performance is found to match with a hydrogen production electrode, so that it is important to achieve higher water electrolysis efficiency.
Transition metal oxides have very good chemical and physical stability, good catalytic properties and low price, which have attracted strong attention from researchers. In common transition metal oxides, the valence state of cobalt in cobaltosic oxide comprises trivalent and divalent states, and cobalt in a mixed valence state has better electrocatalytic oxygen generation performance. A good catalyst requires a suitable support for its loading to achieve high catalytic activity. The self-supporting electrode does not need the use of conductive adhesive and can provide more active sites for catalytic reaction. The close association between the support and the catalytic sites facilitates electron transport. The selection of proper support material is the key to preparing high-performance electrode material. It is known that the catalytic performance can be greatly improved by anchoring the catalytic active material in situ on a carrier such as carbon cloth, carbon paper, nickel mesh, etc. However, the above-mentioned support materials are poor in acid and alkali resistance, and for example, a nickel mesh is dissolved in an acidic system. The mechanical properties of carbon cloth-carbon paper are poor, and the electrode material is easily damaged in long-term cyclic use. The above materials are difficult to be industrially applied because the supporting materials are difficult to be recycled.
How to exert the greatest advantages of the support material on the premise of ensuring good activity and structural stability of cobaltosic oxide is undoubtedly a challenge for researchers.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor researches and discovers that a more reasonable solution is to select a titanium mesh which has good conductivity and can be recycled as a carrier material; introducing a cobaltosic oxide nano beam array with a mixed valence state as an active material to construct a cobaltosic oxide nano beam array/titanium mesh water decomposition oxygen generation composite electrode. The close contact of the cobaltosic oxide nano beam array/titanium mesh interface can obviously reduce the electron transmission resistance in the electrolytic process and enhance the electron transmission; meanwhile, the array structure greatly enhances the material transmission, and is beneficial to the application of the cobaltosic oxide nano-beam array/titanium mesh electrode in the electrochemical water splitting catalysis field and other photoelectric conversion and energy storage fields.
The invention aims to provide a cobaltosic oxide nano-beam array/titanium mesh water decomposition oxygen generation electrode, and a preparation method and application thereof.
A first aspect of the invention is a tricobalt tetraoxide nanobeam array/titanium mesh electrode for use as an oxygen electrode for decomposing water comprising a titanium mesh and a tricobalt tetraoxide nanobeam array grown on a mesh wire.
The second aspect of the invention is a preparation method of a cobaltosic oxide nano-beam array/titanium mesh electrode, which comprises the following steps: growing a precursor basic cobalt carbonate nano-beam array on a titanium mesh by using a hydrothermal method to obtain a precursor/titanium mesh complex; and calcining the precursor/titanium mesh composite body and carrying out reduction treatment by using a reducing agent to obtain the cobaltosic oxide nano-beam array/titanium mesh electrode.
The third aspect of the invention is the application of the cobaltosic oxide nano beam array/titanium mesh electrode as an anode in oxygen production by decomposing water.
The method can form the cobaltosic oxide nano-beam array/titanium mesh electrode composite oxygen generation electrode by controllable growth, and has the advantages of simple process and easy control. The obtained cobaltosic oxide nano beam array has a regular array structure, is tightly connected with a carrier, has rich pore structures on the surface, can obviously reduce the electron transmission resistance in the electrolytic process, enhances the electron transmission, and greatly enhances the material transmission. The obtained electrode has good activity and stability, and is easy to realize large-scale production.
Drawings
FIG. 1 shows schematically that the titanium mesh is subjected to hydrothermal reaction, high-temperature calcination and reduction treatment in a reaction kettle, and an array of cobaltosic oxide nano-particles is grown on the surface of the mesh.
FIG. 2 is a digital photograph of an oxygen producing electrode of titanium mesh, basic cobalt carbonate/titanium mesh and cobaltosic oxide/titanium mesh.
FIG. 3 is the scanning electron microscope photograph of cobaltosic oxide nano beam array/titanium net oxygen producing electrode.
FIG. 4 is the transmission electron microscope photograph of the cobaltosic oxide nano beam array/titanium mesh oxygen-making electrode.
FIG. 5 is a high resolution TEM image of the cobaltosic oxide nanobeam array/Ti mesh oxygen-generating electrode.
FIG. 6 is a linear sweep voltammogram of the cobaltosic oxide nanobeam array/titanium mesh oxygen-generating electrode obtained in example 1 and comparative example 1.
FIG. 7 is a plot of linear sweep voltammetry for the electrode of example 1 before and after 1000 cyclic voltammetry tests.
Detailed Description
The preparation method of the cobaltosic oxide nano-beam array/titanium mesh electrode comprises the following process steps:
cobalt salt, ammonium fluoride and urea are used as raw materials, added into water used as a reaction solvent, uniformly mixed with a titanium mesh and added into a hydrothermal reaction kettle, the hydrothermal reaction temperature is controlled to be 90-200 ℃, the time is 1-50 hours, the high-temperature calcination temperature is controlled to be 300-500 ℃, and the reduction treatment time is 5-60 minutes in a reducing agent, so that the cobaltosic oxide nano-beam array/titanium mesh composite oxygen generation electrode is obtained.
Wherein the cobalt salt is selected from the group consisting of cobalt chloride, cobalt bromide, cobalt fluoride, cobalt acetate, cobalt nitrate, cobalt sulfate, and cobalt carbonate. Ammonium fluoride as structure directing agent in hydrothermal reaction, urea hydrolysis in reaction, CO production3 2-And OH-And promoting the generation of basic cobaltous carbonate nano beam array as the precursor of cobaltosic oxide nano beam array on the titanium mesh. The obtained basic cobaltous carbonate nano-beam array/titanium mesh composite is subjected to a calcination step and a reducing agent treatment step to obtain a cobaltosic oxide nano-beam array/titanium mesh, and then the cobaltosic oxide nano-beam array/titanium mesh water oxygen generation electrode is obtained by washing. The hydrothermal reaction temperature may be more preferably 110 ℃ to 150 ℃ for 2 to 10 hours.
The high-temperature calcination temperature is preferably 300-400 ℃. The reducing agent can be selected from hydrazine hydrate and sodium borohydride, and the calcined composite body is soaked in the form of aqueous solution. The weight concentration range of the reducing agent solution can be selected to be 40-90%. The reduction treatment time (soaking) may be selected to be 5 to 30 minutes.
The titanium net can be any number of meshes, and is usually 40-120 meshes.
The addition amount and concentration of raw materials such as cobalt salt, urea, ammonium fluoride and the like, reaction time and the like can be adjusted according to the expected growth amount and array length of the cobaltosic oxide nano-beam array. The higher the concentration of the cobalt salt in the hydrothermal reaction, the more the growth amount, the longer the time and the longer the array. For example, the growth amount of the cobaltosic oxide nano beam array on the titanium mesh in the obtained electrode is generally controlled to be 0.24-3.5mg/cm2Titanium mesh, preferably 0.6-2.4mg/cm2Titanium mesh, more preferably 0.8 to 1.5mg/cm2(ii) a The length of the array (nanobeam height) is controlled to be 1 μm to 8 μm, typically 3 μm to 7 μm, preferably 4 μm to 5 μm. In order to obtain the above growth amount and array length, the concentration of cobalt salt added in the hydrothermal reaction is usually selected to be 0.02 to 0.2mol/L, preferably 0.04 to 0.1 mol/L. In the specific embodiment, the concentration of cobalt salt is 0.06mol/L, and the concentrations of urea and ammonium fluoride are 0.3mol/L and 0.16mol/L respectively.
Fig. 1 schematically shows that the titanium mesh was subjected to the hydrothermal reaction and high-temperature calcination and reduction treatment in a reaction kettle to obtain an array of cobaltosic oxide nanobeams on the surface of the mesh. In the cobaltosic oxide nanobeam array grown on the titanium mesh, the tapered nanobeam consists of nanoneedles having a diameter of about several tens of nanometers in size. In the case of the microphotographs of fig. 3 and 4, the diameter of the nanobeam is about 300nm on average, and the length of the nanobeam array is 5 μm on average, but the present invention is not limited thereto, and may be, for example, 1 to 8 μm.
Examples
The area of the titanium mesh used in the preparation examples of the electrode of the present invention was 1cm × 4cm, the diameter of the titanium wire was 100 μm, and the mesh number is shown in each example, but the present invention is not limited to these specific parameters and may be selected as needed. The growth amount (load amount) mentioned in the examples was measured by an ICP (inductively coupled plasma) _ method.
Example 1:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (aqueous solution, the concentration is 80wt percent) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh and the length of the tricobalt tetraoxide nanobeam array was 4-5 μm observed microscopically, and the nanobeam size (average diameter) was about 300 nm.
Example 2:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 10 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4-5 μm and the nano-beam size is 300nm as observed by a microscope.
Example 3:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 30 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4-5 μm and the nano-beam size is 300nm as observed by a microscope.
Example 4:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 40 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4-5 μm and the nano-beam size is 300nm as observed by a microscope.
Example 5:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 50 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4-5 μm and the nano-beam size is 300nm as observed by a microscope.
Example 6:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 60 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.843mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4-5 μm and the nano-beam size is 300nm as observed by a microscope.
Example 7:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.0mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.529mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 3.5-5 μm and the nano-beam size is 280nm as observed by a microscope.
Example 8:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 2.0mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 1.235mg/cm2Titanium mesh, and the length of the cobaltosic oxide nanobeam array is 4.8-6 μm and the nanobeam size is 350nm as observed by a microscope.
Example 9:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with molar weights of 2.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 1.59mg/cm2Titanium mesh, and the length of the cobaltosic oxide nanobeam array is 5.6-8 μm and the nanobeam size is 420nm as observed by a microscope.
Example 10:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 90 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.751mg/cm2Titanium mesh, and the length of the cobaltosic oxide nanobeam array is 3.7-4.6 μm observed by a microscope, and the size of the nanobeam is 285 nm.
Example 11:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 100 ℃, reacting for 4h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.738mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 3.4-4.8 μm and the nano-beam size is 240nm as observed by a microscope.
Example 12:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 1h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.428mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 0.8-2 μm and the nano-beam size is 180nm as observed by a microscope.
Example 13:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 2h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.593mg/cm2Titanium mesh, and the length of the cobaltosic oxide nanobeam array is 1.5-3.5 μm, and the size of the nanobeam is 251nm as observed by a microscope.
Example 14:
placing a mixed precursor of cobalt chloride, urea, ammonium fluoride and 25mL of deionized water with the molar weights of 1.5mmol, 7.5mmol and 4mmol respectively in a 50 mL reaction kettle, placing a titanium mesh (80 meshes) with the surface subjected to acid cleaning in the kettle, placing the reaction kettle in an oven, heating to 120 ℃, reacting for 6h, and finally naturally cooling to obtain the basic cobalt carbonate/titanium mesh electrode. And (3) placing the basic cobaltous carbonate/titanium mesh electrode in a muffle furnace at 350 ℃, reacting for 2h, soaking the calcined electrode in hydrazine hydrate solution (80 wt%) for 20 min, and washing and drying to obtain the cobaltosic oxide nano-beam array/titanium mesh oxygen-generating electrode.
The growth amount of the obtained cobaltosic oxide nano beam array is 0.982mg/cm2Titanium mesh, and the length of the cobaltosic oxide nano-beam array is 4.8-6 μm and the nano-beam size is 360nm as observed by a microscope.
Comparative example 1: preparation of commercial Iridium oxide powder/titanium mesh electrode
The commercial iridium oxide powder/titanium mesh comparative electrode was prepared as follows: the commercialized iridium oxide purchased from a chemical professional platform is ground, 5mg of ground sample is weighed, 350 mu L of deionized water, 700 mu L of absolute ethyl alcohol and 80 mu L of perfluorosulfonic acid macromolecule conductive adhesive solution are added and mixed evenly by ultrasonic. Collecting 177 μ L of the above mixture, and dripping onto 1cm2And (4) pickling the titanium mesh, and naturally drying to obtain the commercial iridium oxide powder/titanium mesh contrast electrode.
The following preparation examples were observed and evaluated for obtaining an oxygen electrode of cobaltosic oxide nanobeam array based mainly on example 1.
Fig. 2 is a digital photograph of basic cobalt carbonate/titanium mesh electrode (middle) and cobaltosic oxide nanobeam array/titanium mesh oxygen generation electrode (right) subjected to calcination reduction treatment obtained after hydrothermal reaction of titanium mesh (left) in example 1. Fig. 3 is a scanning electron micrograph of the cobaltosic oxide nanobeam array/titanium mesh water-splitting oxygen generation electrode prepared in example 1, and fig. 4 is a transmission electron micrograph of the cobaltosic oxide nanobeam array/titanium mesh water-splitting oxygen generation electrode prepared in example 1.
Fig. 3 shows that the cobaltosic oxide nano beam array is arranged regularly and uniformly and is tightly connected with the titanium mesh, which is beneficial to electrochemical substance transmission and electron transfer. Fig. 4 shows that the nanobeam is composed of nanoparticles, which facilitates the transport of substances in the reaction. Fig. 5 shows that the surface of the nanobeam is a porous structure, and the nanobeam has abundant pore structures, which is beneficial to the adsorption of reactants, the desorption of generated oxygen, and the like.
Fig. 6 is a linear sweep voltammogram measured in an oxygen-saturated 1.0M PBS neutral buffer solution (pH 7.0) for the tricobalt tetroxide nanobeam array/titanium mesh electrode and the commercial iridium oxide/titanium mesh electrode obtained in example 1 and comparative example 1. As is clear from the figure, the current densities of the Reversible Hydrogen Electrode (RHE) at a potential vs. 1.8V are 49.9mA and 17.63mA, respectively.
The results of the examples are shown in Table 1.
TABLE 1
Figure BDA0001827388620000091
Note: the growth amounts in the table were obtained by an ICP (inductively coupled plasma) method. The array length and the nano-beam diameter are obtained by a scanning electron microscope and a transmission electron microscope.
Fig. 7 shows the linear sweep voltammogram of the electrode of example 1 before and after 1000 cycles of cyclic voltammetry.
From the data in fig. 6-7, it can be seen that the cobaltosic oxide nanobeam array/titanium mesh of the present invention as oxygen generation electrode can not only obtain very high current output density, but also have excellent cycling stability.

Claims (10)

1. A cobaltosic oxide nano beam array/titanium mesh electrode comprises a titanium mesh and a cobaltosic oxide nano beam array growing on mesh wires.
2. The tricobalt tetraoxide nanobeam array/titanium mesh electrode of claim 1, wherein the growth amount of tricobalt tetraoxide on the titanium mesh is 0.24-3.5mg/cm2The length of the cobaltosic oxide nano beam array is 1-8 mu m.
3. The tricobalt tetraoxide nanobeam array/titanium mesh electrode of claim 1, wherein the tricobalt tetraoxide nanobeam array is grown in an amount of 0.6-2.6mg/cm2The length of the cobaltosic oxide nano beam array is 1-5 mu m, and preferably, the growth amount of the cobaltosic oxide nano beam array is 0.8-1.5mg/cm2Titanium net, and the length of the cobaltosic oxide nano beam array is 3-7 μm.
4. The tricobalt tetroxide nanobeam array/titanium mesh electrode of any of claims 1 to 3, wherein the surface of the nanobeams is a porous structure.
5. A preparation method of a cobaltosic oxide nano beam array/titanium mesh electrode comprises the following steps:
growing a precursor basic cobalt carbonate nano-beam array on a titanium mesh by using a hydrothermal method to obtain a precursor/titanium mesh complex;
and calcining the precursor/titanium mesh composite body and carrying out reduction treatment by using a reducing agent to obtain the cobaltosic oxide nano-beam array/titanium mesh electrode.
6. The production method according to claim 5, wherein:
the hydrothermal process comprises: adding cobalt salt, urea, ammonium fluoride, water and a titanium net into a hydrothermal reactor, controlling the hydrothermal reaction temperature range to be 90-200 ℃ and the reaction time to be 1-50 hours;
the calcining temperature is 300-500 ℃; and
the reduction treatment comprises the following steps: and (3) soaking for 5-60 minutes by using aqueous solution of hydrazine hydrate or sodium borohydride as a reducing agent.
7. The method according to claim 6, wherein
The cobalt salt is selected from cobalt chloride, cobalt bromide, cobalt fluoride, cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt carbonate, the addition amount is 0.02-0.2mol/L, the hydrothermal reaction temperature range is 110-150 ℃, and the time is 2-15 hours; and is
The concentration range of the aqueous solution of hydrazine hydrate or sodium borohydride is 40-90% (wt), and the soaking time is 10-30 minutes.
8. The method according to claim 7, wherein
The addition amount of the cobalt salt is 0.04-0.1 mol/L; and is
The soaking time is 15-25 minutes.
9. The method according to any one of claims 5 to 8, wherein the growth amount of the tricobalt tetraoxide nanobeam array in the prepared tricobalt tetraoxide nanobeam array/titanium mesh electrode is 0.6 to 2.6mg/cm2The length of the cobaltosic oxide nano beam array is 1-8 mu m, and the surface of the nano beam is in a porous structure.
10. The tricobalt tetraoxide nanobeam array/titanium mesh electrode of any one of claims 1 to 4 or obtained by the preparation method of any one of claims 5 to 9 is used as an anode in oxygen production by decomposing water.
CN201811190557.0A 2018-10-12 2018-10-12 Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof Pending CN111041508A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201811190557.0A CN111041508A (en) 2018-10-12 2018-10-12 Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof
JP2019159493A JP6932751B2 (en) 2018-10-12 2019-09-02 Tricobalt tetraoxide array / titanium mesh electrode for generating hydrolyzed oxygen and its manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811190557.0A CN111041508A (en) 2018-10-12 2018-10-12 Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111041508A true CN111041508A (en) 2020-04-21

Family

ID=70219409

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811190557.0A Pending CN111041508A (en) 2018-10-12 2018-10-12 Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof

Country Status (2)

Country Link
JP (1) JP6932751B2 (en)
CN (1) CN111041508A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113247993A (en) * 2021-05-17 2021-08-13 南昌航空大学 All-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst and preparation method and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111717937B (en) * 2020-05-22 2022-06-21 太原科技大学 Preparation method of nano-scale cobaltosic oxide
CN114655996B (en) * 2020-12-03 2024-02-27 上海电力大学 Oxygen evolution electrocatalyst of chiral cobaltosic oxide and preparation method thereof
CN114890508A (en) * 2021-09-24 2022-08-12 中国船舶重工集团公司第七二五研究所 Metal oxide nanowire array mesh electrode material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103318978A (en) * 2013-06-03 2013-09-25 中南大学 Preparation method of mesoporous nickel cobaltate fiber and application thereof
CN104810162A (en) * 2015-03-27 2015-07-29 吉林化工学院 Preparation method of layered cobaltosic oxide super-capacitor electrode material grown on titanium mesh in-situ
JP2015148010A (en) * 2014-01-10 2015-08-20 パナソニックＩｐマネジメント株式会社 Method for generating oxygen and water electrolysis device
CN105332003A (en) * 2015-11-30 2016-02-17 天津理工大学 Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies
CN106025302A (en) * 2016-07-18 2016-10-12 天津理工大学 Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material
CN108611659A (en) * 2018-05-03 2018-10-02 山东大学 A kind of Co of efficient stable3O4Nano-band array analyses chloride electrode

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2419985A1 (en) * 1978-03-13 1979-10-12 Rhone Poulenc Ind ELECTRODE FOR ELECTROLYSIS OF SODIUM CHLORIDE
WO2017154134A1 (en) * 2016-03-09 2017-09-14 国立大学法人弘前大学 Method for manufacturing electrode for electrolysis of water

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103318978A (en) * 2013-06-03 2013-09-25 中南大学 Preparation method of mesoporous nickel cobaltate fiber and application thereof
JP2015148010A (en) * 2014-01-10 2015-08-20 パナソニックＩｐマネジメント株式会社 Method for generating oxygen and water electrolysis device
CN104810162A (en) * 2015-03-27 2015-07-29 吉林化工学院 Preparation method of layered cobaltosic oxide super-capacitor electrode material grown on titanium mesh in-situ
CN105332003A (en) * 2015-11-30 2016-02-17 天津理工大学 Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies
CN106025302A (en) * 2016-07-18 2016-10-12 天津理工大学 Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material
CN108611659A (en) * 2018-05-03 2018-10-02 山东大学 A kind of Co of efficient stable3O4Nano-band array analyses chloride electrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RAVINDER KUMAR ET AL.: "Potential of porous Co3O4 nanorods as cathode catalyst for oxygen reduction reaction in microbialfuel cells", 《BIORESOURCE TECHNOLOGY》 *
YONGCHENG ET AL.: "Reduced Mesoporous Co3O4 Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes", 《ADV. ENERGY MATER.》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113247993A (en) * 2021-05-17 2021-08-13 南昌航空大学 All-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst and preparation method and application thereof

Also Published As

Publication number Publication date
JP2020059917A (en) 2020-04-16
JP6932751B2 (en) 2021-09-08

Similar Documents

Publication Publication Date Title
CN108754532B (en) Molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and preparation method and application thereof
CN108080034B (en) Preparation method and application of nickel-based three-dimensional metal organic framework catalyst
CN108630438B (en) Cobalt selenide/titanium mesh water decomposition oxygen generation electrode and preparation method thereof
CN110752380A (en) ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof
CN111041508A (en) Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof
CN107020075B (en) Simple substance bismuth catalyst for electrochemical reduction of carbon dioxide and preparation and application thereof
CN109718822B (en) Method for preparing metal-carbon composite catalytic material and application thereof
CN105529472A (en) Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof
CN109433228B (en) Angular Ni with hierarchical structure3S2/VS4Electrode material and preparation method thereof
CN109706476B (en) Carbon cloth surface in-situ growth W18O49Preparation method of self-supporting electrode material
CN113737200B (en) Water splitting catalyst and its prepn and application
CN107792884B (en) A kind of air electrode catalyst material nano hexagon ZnMnO3Preparation method and application
CN110538650B (en) Cerium oxide supported bismuth nano catalyst and preparation method and application thereof
CN111001414A (en) Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof
CN111777102A (en) Metal oxide-based bifunctional water decomposition nano material and preparation method thereof
CN109301249B (en) Foamed nickel in-situ loaded SnO2Preparation method and application of nano particle doped graphite carbon composite material
CN113512738B (en) Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof
CN113718270A (en) Carbon-supported NiO/NiFe2O4Preparation method and application of spinel type solid solution water electrolysis oxygen evolution catalyst
CN114481204B (en) Preparation of cobalt phosphide loaded noble metal nano material
CN103252248A (en) Preparation method of ordered mesoporous non-noble-metal-nitrogen-graphitized carbon material
CN115305480A (en) Alloy nano material catalyst and preparation method and application thereof
CN113684499A (en) Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency
CN111841567A (en) Preparation method and application of nickel-manganese oxyhydroxide film with Tuoling structure
CN112626553B (en) Hollow carbon tube composite material and preparation method and application thereof
CN113649054B (en) NiFe@NC/Al-SrTiO 3 Composite photocatalyst and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination