CN115261915B - Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof - Google Patents
Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof Download PDFInfo
- Publication number
- CN115261915B CN115261915B CN202211039239.0A CN202211039239A CN115261915B CN 115261915 B CN115261915 B CN 115261915B CN 202211039239 A CN202211039239 A CN 202211039239A CN 115261915 B CN115261915 B CN 115261915B
- Authority
- CN
- China
- Prior art keywords
- source
- cobalt
- nickel
- aqueous solution
- cfp
- 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.)
- Active
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
- 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
- C25B11/089—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- 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
- C25B11/065—Carbon
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The CFP is used as a substrate, so that the binder is avoided, and the catalytic performance of the prepared catalyst is prevented from being reduced by the binder; in situ deposition of CoS on CFP surface 2 And NiCo 2 S 4 Avoiding CoS 2 Exposing more active catalytic sites, wherein CoS 2 The hydrogen evolution and oxygen evolution kinetics process is faster, the conductivity is excellent, and the bimetallic sulfide NiCo 2 S 4 There is itself a rich redox couple, coS 2 And NiCo 2 S 4 The heterojunction is formed by recombination, so that the transfer rate of electrons in the electrocatalytic process is accelerated, defects and vacancies are generated when the heterojunction is formed, more catalytic active sites are provided, the electrocatalytic performance is further improved, and CoS 2 And NiCo 2 S 4 The synergistic effect of the cobalt and nickel-containing composite electrocatalyst is fully utilized, and the hydrogen evolution, oxygen evolution and electrolyzed water catalysis performances of the prepared cobalt and nickel-containing composite electrocatalyst are obviously improved.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a composite electrocatalyst containing cobalt and nickel, a preparation method and application thereof.
Background
With the rapid development of human society, the problems of energy shortage and environmental pollution are becoming increasingly a hotspot of social concern, which also promotes people to pay high attention to ecological environment protection and sustainable development of energy. Currently, the supply of human energy is gradually changed from fossil energy to pollution-free sustainable green energy such as solar energy, tidal energy, wind energy and the like. However, these green energy sources have some disadvantages, such as being easily affected by weather, time and region, being unable to be continuously and stably supplied, and being difficult to meet the demands of human production and life. The hydrogen energy has no pollution in the use process, the energy density is high, the supply form is more stable than other green energy sources, and the hydrogen energy becomes one of the green energy sources with the most application prospect.
The hydrogen production means are various, and mainly include a methane steam conversion method, a natural gas hydrogen production method and an electrolytic water hydrogen production method. The industry mainly adopts a methane steam conversion method and a natural gas hydrogen production method, but greenhouse gas carbon dioxide is generated in the preparation process. In the process of preparing hydrogen by electrolyzing water, the cathode and the anode respectively generate reduction reaction and oxidation reaction, only hydrogen and oxygen are generated, the preparation method is more green and environment-friendly, and the other product oxygen is widely applied in the aspects of medical care, national defense industry and the like.
In the process of preparing hydrogen and oxygen by using the electrolytic water method, a certain energy barrier needs to be overcome. The introduction of a catalyst in the electrolysis of water is an effective means of solving this problem. At present, noble metal catalysts such as Pt, pd, ru and the like are commercially used as more catalysts, however, the reserves of noble metals in the crust are relatively low and the cost is relatively high, which seriously hinders the wide popularization and application of water electrolysis hydrogen production and oxygen production. Therefore, providing an electrolyzed water catalyst with high electrocatalytic performance and low cost is a problem to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a cobalt and nickel-containing composite electrocatalyst, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a composite electrocatalyst containing cobalt and nickel, which comprises the following steps:
(1) Carrying out hydrophilic treatment on the carbon fiber paper to obtain pretreated carbon fiber paper;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper;
(3) And (3) immersing the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then carrying out hydrothermal reaction to obtain the composite electrocatalyst containing cobalt and nickel.
Preferably, the hydrophilic treatment in the step (1) is one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment and microwave treatment.
Preferably, the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) and the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) are independently CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or two of O.
Preferably, the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) is 3.75X10 -2 ～4.60×10 -2 mmol/mL。
Preferably, the temperature of the hydrothermal reaction in the step (2) is 160-200 ℃, and the time of the hydrothermal reaction is 16-20 h.
Preferably, the ratio of the amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the amount of the substance of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1 (0.15 to 5.5).
Preferably, the temperature of the impregnation in the step (3) is room temperature, and the time of the impregnation is 20-40 min.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 170-190 ℃, and the time of the hydrothermal reaction is 8-12 h.
The invention also provides the composite electrocatalyst containing cobalt and nickel, which is prepared by the preparation method of the technical proposal, and comprises carbon fiber paper, cobalt disulfide nano particles grown on the surface of the carbon fiber paper in situ, and cobalt tetrasulfide nickel oxide microspheres grown on the surfaces of the carbon fiber paper and the cobalt disulfide nano particles in situ.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method of the technical scheme or the application of the composite electrocatalyst containing cobalt and nickel in water electrolysis.
The invention provides a preparation method of a composite electrocatalyst containing cobalt and nickel, which comprises the steps of firstly carrying out hydrophilic treatment on CFP (carbon fiber paper), leading the surface of the CFP to have polarity, introducing rich oxygen-containing groups, improving the surface activity of the CFP, facilitating the growth of transition metal sulfide on the surface of the CFP in the subsequent hydrothermal reaction, obtaining pretreated carbon fiber paper, and then sequentially carrying out impregnation and hydrothermal reaction to deposit cobalt disulfide CoS on the pretreated carbon fiber paper in situ 2 Obtaining cobalt disulfide/carbon fiber paper, and then sequentially carrying out impregnation and hydrothermal reaction to obtain a composite electrocatalyst containing cobalt and nickel, namely NiCo 2 S 4 /CoS 2 CFP electrocatalyst. The CFP is adopted as a substrate, so that the use of a binder is avoided, and the reduction of the catalytic performance of the prepared catalyst by using the binder is avoided; in-situ deposition of transition metal sulfide CoS on CFP surface by hydrothermal synthesis 2 And NiCo 2 S 4 Simple and efficient, avoid CoS 2 Exposing more active catalytic sites, wherein CoS 2 The method has the advantages of quick metallic, hydrogen evolution and oxygen evolution kinetics processes, excellent conductivity and bimetallic sulfide NiCo 2 S 4 The catalyst has rich redox couple and excellent electrocatalytic performance; and forming NiCo in hydrothermal reaction 2 S 4 In the process of (2), coS 2 Simultaneously and generated NiCo 2 S 4 The electrons are compounded into a heterojunction, so that the transfer rate of the electrons in the electrocatalytic process is accelerated, and the electrocatalytic performance is cooperatively improved; and also create certain defects and vacancies in the formation of the heterojunction that provide more catalytically active sites, further enhancing the electrocatalytic performance of the catalyst, allowing CoS 2 And NiCo 2 S 4 Is obtained by the synergistic effect ofThe hydrogen evolution, oxygen evolution and electrolyzed water catalysis performances of the prepared cobalt and nickel-containing composite electrocatalyst are obviously improved by fully utilizing the cobalt and nickel-containing composite electrocatalyst, and the raw materials used in the application are wide in source and low in cost. The results of the examples show that NiCo prepared in example 1 2 S 4 /CoS 2 The CFP electrocatalyst has excellent electrocatalysis performance in hydrogen evolution and oxygen evolution performance tests, and has excellent electrolyzed water catalysis performance; at a current density of 10mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The hydrogen evolution overpotential of the CFP electrocatalyst is 244mV, and the Tafel slope is 151mV dec -1 The method comprises the steps of carrying out a first treatment on the surface of the At a current density of 50mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The oxygen evolution overpotential of the CFP electrocatalyst is 367mV, and the Tafel slope is 120mV dec -1 The method comprises the steps of carrying out a first treatment on the surface of the At a current density of 10mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The potential of the electrolyzed water of the/CFP electrocatalyst was 1.61V.
Drawings
FIG. 1 is a CoS prepared in example 1 of the present invention 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 XRD pattern of CFP electrocatalyst;
FIG. 2 shows NiCo prepared in example 1 of the present invention 2 S 4 /CoS 2 SEM image of CFP electrocatalyst;
FIG. 3 is a CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 LSV plot for hydrogen evolution performance test of CFP electrocatalyst;
FIG. 4 is a CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 Tafel slope plot of hydrogen evolution performance test of CFP electrocatalyst;
FIG. 5 is a CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparative examplePrepared NiCo 2 S 4 LSV plot for oxygen evolution performance test of CFP electrocatalyst;
FIG. 6 is a CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 Tafel slope plot of oxygen evolution performance test of CFP electrocatalyst;
FIG. 7 is a NiCo prepared in example 1 2 S 4 /CoS 2 LSV plot of electrolyzed water performance of CFP electrocatalyst.
Detailed Description
The invention provides a preparation method of a composite electrocatalyst containing cobalt and nickel, which comprises the following steps:
(1) Carrying out hydrophilic treatment on the carbon fiber paper to obtain pretreated carbon fiber paper;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper;
(3) And (3) immersing the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then carrying out hydrothermal reaction to obtain the composite electrocatalyst containing cobalt and nickel.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
According to the invention, the carbon fiber paper is subjected to hydrophilic treatment to obtain the pretreated carbon fiber paper.
In the present invention, the carbon fiber paper is preferably subjected to a decontamination treatment before use. In the invention, the decontamination treatment preferably comprises cutting carbon fiber paper, sequentially carrying out ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 8-12 min respectively, and then drying in a blast drying oven.
In the present invention, the hydrophilic treatment is preferably one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment, and microwave treatment. In the invention, the surface of the CFP is provided with polarity by hydrophilic treatment, and abundant oxygen-containing groups are introduced to improve the surface activity of the CFP, so that the growth of transition metal sulfide on the surface of the CFP in the subsequent hydrothermal reaction is facilitated.
In the present invention, the electrochemical treatment preferably comprises providing a working electrode of carbon fiber paper, a reference electrode of Saturated Calomel Electrode (SCE), and a counter electrode of platinum sheet to form a three-electrode system, using 0.5M H 2 SO 4 The solution is used as electrolyte, and the cyclic voltammetry is used for carrying out hydrophilic treatment on the carbon fiber paper.
After the hydrophilic treatment is completed, the carbon fiber paper after the hydrophilic treatment is preferably subjected to ultrasonic treatment by sequentially using absolute ethyl alcohol and deionized water, and then is dried to obtain the pretreated carbon fiber paper.
The invention has no special limit to the power and time of ultrasonic treatment, and can clean the impurities on the surface of the carbon fiber paper.
After the pretreated carbon fiber paper is obtained, the pretreated carbon fiber paper is immersed into an aqueous solution containing a cobalt source and a sulfur source, and then hydrothermal reaction is carried out to obtain cobalt disulfide/carbon fiber paper.
The preparation method of the aqueous solution containing the cobalt source and the sulfur source is not particularly limited, and the conventional technical scheme in the field can be adopted.
In the present invention, the temperature of the impregnation is preferably room temperature; the time of the impregnation is preferably 20 to 40 minutes, more preferably 25 to 35 minutes. The invention controls the dipping temperature and time in the above range, which is beneficial to the uniform mixing of the aqueous solution containing cobalt source and sulfur source.
In the present invention, the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is preferably CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or two of O. In the present invention, the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is preferably 3.75X10 -2 ～4.60×10 -2 mmol/mL, more preferably 4.00×10 -2 ～4.40×10 -2 mmol/mL. The concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source is controlled within the range, so that the cobalt source is fully dissolved in the aqueous solution.
In the present invention, the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is preferably Na 2 S 2 O 3 ·5H 2 O and Na 2 S·9H 2 One or two of O. In the present invention, the ratio of the amounts of the substances of the cobalt source and the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is preferably 1 (2 to 4), more preferably 1 (2.5 to 3.5). The invention controls the mass ratio of the cobalt source and the sulfur source in the aqueous solution containing the cobalt source and the sulfur source within the above range, which is beneficial to preparing pure-phase cobalt disulfide CoS 2 。
In the present invention, the temperature of the hydrothermal reaction is preferably 160 to 200 ℃, more preferably 170 to 190 ℃; the time of the hydrothermal reaction is preferably 16 to 20 hours, more preferably 17 to 19 hours. The invention controls the temperature and time of the hydrothermal reaction in the above range to promote the cobalt source and the sulfur source to fully perform the chemical reaction, and in-situ deposits cobalt disulfide CoS with good crystallinity on the pretreated carbon fiber paper CFP 2 The cobalt disulfide/carbon fiber paper is obtained, the problems that the temperature is too low and the time is too short, the reaction is insufficient, the target product cannot be obtained, meanwhile, the temperature is too high and the time is too long, the grain size of the precipitated cobalt disulfide product is too large, and the electrocatalytic performance is reduced are avoided.
After the hydrothermal reaction is finished, the product of the hydrothermal reaction is preferably cooled, washed and dried in sequence to obtain cobalt disulfide/carbon fiber paper.
In the present invention, the cooling means is preferably natural cooling. In the present invention, the washing is preferably sequentially rinsed with absolute ethanol and deionized water. The number of times of the washing is not particularly limited, and the purpose of completely removing impurities can be achieved. The drying mode is not particularly limited in the present invention, and the purpose of removing moisture may be achieved.
After cobalt disulfide/carbon fiber paper is obtained, the cobalt disulfide/carbon fiber paper is immersed into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then hydrothermal reaction is carried out, so that the composite electrocatalyst containing cobalt and nickel is obtained.
In the present invention, the cobalt-containing source, nickel source and sulfur source are water-solubleThe cobalt source in the liquid is preferably CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or two of O. In the present invention, the concentration of the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is preferably 1X 10 -2 ～45×10 -2 mmol/mL, more preferably 1.67×10 -2 ～41.67×10 -2 mmol/mL. The invention controls the concentration of the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source within the range, which is beneficial to controlling the NiCo loaded on the cobalt disulfide/carbon fiber paper 2 S 4 So that the prepared composite electrocatalyst containing cobalt and nickel has optimal electrocatalysis performance.
In the present invention, the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is preferably Ni (NO) 3 ) 2 ·6H 2 O and NiCl 2 ·6H 2 One or two of O. In the present invention, the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is preferably CH 4 N 2 S and CH 3 CSNH 2 One or two of them. In the present invention, the ratio of the amounts of the substances of the nickel source, the cobalt source and the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is preferably 1: (1-3): (3 to 5), more preferably 1: (1.5-2.5): (3.5 to 4.5), more preferably 1:2:4. the invention controls the mass ratio of the cobalt source, the nickel source and the sulfur source in the aqueous solution containing the nickel source, the cobalt source and the sulfur source within the range, and is favorable for preparing pure-phase cobalt tetrasulfide nickel cobalt 2 S 4 。
In the present invention, the ratio of the amounts of the cobalt source and the nickel source in the aqueous solution containing the cobalt source and the sulfur source is preferably 1 (0.15 to 5.5), more preferably 1 (0.2 to 5). The invention controls the ratio of the amounts of the cobalt source and the nickel source in the aqueous solution containing the cobalt source and the sulfur source to the amount of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source within the range, thereby being beneficial to controlling the NiCo loaded on the pretreated carbon fiber paper 2 S 4 With CoS 2 The ratio of the amounts of the substances in the catalyst can be used to obtain the cobalt-nickel-containing composite electrocatalyst with optimal electrocatalysis performanceAvoiding NiCo 2 S 4 With CoS 2 Too low or too high content of (c) does not allow the prepared composite electrocatalyst comprising cobalt and nickel to exhibit an optimal electrocatalytic synergistic effect.
The preparation method of the aqueous solution containing the cobalt source, the nickel source and the sulfur source is not particularly limited, and the conventional technical scheme in the field can be adopted.
In the present invention, the temperature of the impregnation is preferably room temperature; the time of the impregnation is preferably 20 to 40 minutes, more preferably 25 to 35 minutes. The invention controls the dipping temperature and time in the above range, which is beneficial to the uniform mixing of the aqueous solution containing cobalt source, nickel source and sulfur source.
In the present invention, the temperature of the hydrothermal reaction is preferably 170 to 190 ℃, more preferably 175 to 185 ℃; the time of the hydrothermal reaction is preferably 8 to 12 hours, more preferably 9 to 11 hours. The invention controls the temperature and time of the hydrothermal reaction in the above range to promote the cobalt source, the nickel source and the sulfur source to fully perform chemical reaction, and deposit and separate out NiCo with good crystallinity on cobalt disulfide/carbon fiber paper in situ 2 S 4 The composite electrocatalyst containing cobalt and nickel is obtained, the problems that the temperature is too low and the time is too short, the reaction is not carried out sufficiently, the target product cannot be obtained, and the NiCo is precipitated due to the too high temperature and the too long time are avoided 2 S 4 The grain size of the product is too large, and the electrocatalytic performance is lowered.
After the hydrothermal reaction is finished, the product of the hydrothermal reaction is preferably naturally cooled, washed and dried in sequence to obtain the composite electrocatalyst containing cobalt and nickel.
In the present invention, the washing is preferably sequentially rinsed with absolute ethanol and deionized water. The invention has no special limit to the washing times, and can completely remove impurities. The drying mode is not particularly limited, and the purpose of removing moisture can be achieved.
The preparation method provided by the invention is simple to operate, wide in raw material source, low in cost, mild in reaction condition, and suitable for large-scale production, and the prepared composite electrocatalyst containing cobalt and nickel has excellent electrocatalysis in hydrogen evolution reaction, oxygen evolution reaction and electrolysis water.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method. In the invention, the composite electrocatalyst containing cobalt and nickel comprises carbon fiber paper, cobalt disulfide nano particles which grow on the surface of the carbon fiber paper in situ, and cobalt tetrasulfide nickel oxide microspheres which grow on the surfaces of the carbon fiber paper and the cobalt disulfide nano particles in situ.
The composite electrocatalyst containing cobalt and nickel prepared by the preparation method provided by the invention has excellent electrocatalysis performance in hydrogen evolution reaction, oxygen evolution reaction and electrolysis water.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method of the technical scheme or the application of the composite electrocatalyst containing cobalt and nickel in water electrolysis.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the composite electrocatalyst containing cobalt and nickel comprises the following steps:
(1) Cutting CFP of carbon fiber paper into small pieces with the size of 1cm multiplied by 1.5cm, performing decontamination treatment on the cut CFP, namely respectively performing ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 10min, then drying in a blast drying oven, setting a working electrode to be the decontaminated CFP by using an electrochemical workstation, setting a reference electrode to be a Saturated Calomel Electrode (SCE), and setting a counter electrode to be a platinum sheet to form a three-electrode system, wherein 0.5M H is adopted 2 SO 4 The solution is used as electrolyte, CFP is subjected to hydrophilic treatment by cyclic voltammetry, after the hydrophilic treatment is finished, the carbon fiber paper subjected to hydrophilic treatment is washed by absolute ethyl alcohol and deionized water for a plurality of times and then driedDrying to obtain pretreated carbon fiber paper;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source for 30min at room temperature, fully contacting the pretreated carbon fiber paper with the aqueous solution containing the cobalt source and the sulfur source, then transferring the carbon fiber paper and the aqueous solution containing the cobalt source and the sulfur source into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 18h at 180 ℃ in a blast drying box, naturally cooling a product of the hydrothermal reaction after the hydrothermal reaction is finished, flushing for multiple times by using absolute ethyl alcohol and deionized water, and obtaining cobalt disulfide/carbon fiber paper, namely CoS after the drying treatment 2 /CFP；
The preparation method of the aqueous solution containing the cobalt source and the sulfur source comprises the following steps: 48mL of deionized water was weighed and placed in a beaker, and 2mmol of CoCl was weighed 2 ·6H 2 O and 3mmol Na 2 S 2 O 3 ·5H 2 Placing O into a beaker filled with deionized water, stirring for 30min by using a magnetic stirrer, and fully dissolving to obtain an aqueous solution containing a cobalt source and a sulfur source; cobalt source CoCl in the aqueous solution containing cobalt source and sulfur source 2 ·6H 2 O concentration of 4.17X10 -2 mmol/mL；
(3) Immersing the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source for 30min, fully contacting the cobalt disulfide/carbon fiber paper with the aqueous solution containing the cobalt source, the nickel source and the sulfur source, transferring the cobalt disulfide/carbon fiber paper and the aqueous solution containing the cobalt source, the nickel source and the sulfur source into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 180 ℃ in a blast drying box, naturally cooling a product of the hydrothermal reaction after the hydrothermal reaction is finished, flushing for a plurality of times by using absolute ethyl alcohol and deionized water, and obtaining the composite electrocatalyst containing cobalt and nickel, namely NiCo after the drying treatment 2 S 4 /CoS 2 CFP electrocatalyst;
the preparation method of the aqueous solution containing the cobalt source, the nickel source and the sulfur source comprises the following steps: 48mL of deionized water was weighed into a beaker, and 6mmol of Ni (NO 3 ) 2 ·6H 2 O、12mmol Co(NO 3 ) 2 ·6H 2 O and 24mmol CH 4 N 2 S, placing the mixture into a beaker filled with deionized water, and stirring the mixture for 30 minutes by using a magnetic stirrer to fully dissolve the mixture so as to obtain an aqueous solution containing a cobalt source, a nickel source and a sulfur source; the concentration of the cobalt source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is 0.25mmol/mL; the ratio of the amounts of the substances of the nickel source, the cobalt source and the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is 1:2:4, a step of;
the ratio of the amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the amount of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1:3.
Comparative example
NiCo 2 S 4 Preparation method of CFP electrocatalyst:
(1) Cutting CFP of carbon fiber paper into small pieces with the size of 1cm×1.5cm, setting working electrode as CFP after decontamination treatment by using electrochemical workstation, and forming three-electrode system with reference electrode as Saturated Calomel Electrode (SCE) and counter electrode as platinum sheet, wherein 0.5M H is adopted 2 SO 4 The solution is used as electrolyte, CFP is subjected to hydrophilic treatment by cyclic voltammetry, after the hydrophilic treatment is finished, the carbon fiber paper subjected to hydrophilic treatment is washed by absolute ethyl alcohol and deionized water for a plurality of times, and then is subjected to drying treatment, so that pretreated carbon fiber paper is obtained;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source for 30min, fully contacting the carbon fiber paper with the aqueous solution containing the cobalt source, the nickel source and the sulfur source, transferring the carbon fiber paper and the aqueous solution containing the cobalt source, the nickel source and the sulfur source into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 180 ℃ in a blast drying box, naturally cooling a product of the hydrothermal reaction after the hydrothermal reaction is finished, flushing for a plurality of times by using absolute ethyl alcohol and deionized water, and obtaining NiCo after drying treatment 2 S 4 CFP electrocatalyst;
the preparation method of the aqueous solution containing the cobalt source, the nickel source and the sulfur source comprises the following steps: 48mL of deionized water was weighed into a beaker, and 2mmol of Ni (NO 3 ) 2 ·6H 2 O、4mmol Co(NO 3 ) 2 ·6H 2 O and 8mmol CH 4 N 2 S, placing the mixture into a beaker filled with deionized water, and stirring the mixture for 30 minutes by using a magnetic stirrer to fully dissolve the mixture so as to obtain an aqueous solution containing a cobalt source, a nickel source and a sulfur source.
For CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 The CFP electrocatalyst was subjected to X-ray diffraction (XRD) testing, resulting in an XRD pattern as shown in figure 1; as can be seen from FIG. 1, the CoS, in addition to the strong diffraction peak of CFP 2 Diffraction peak of CFP and CoS 2 Is matched with a standard PDF card (JCPDS No. 70-2865), niCo 2 S 4 Diffraction peak of/CFP and NiCo 2 S 4 Is matched with a standard PDF card (JCPDS No. 43-1477), niCo 2 S 4 /CoS 2 Co-presence of CFP electrocatalyst 2 And NiCo 2 S 4 And no other impurity phases, indicating that example 1 successfully produced NiCo 2 S 4 /CoS 2 CFP electrocatalyst.
NiCo prepared in example 1 was examined by Scanning Electron Microscopy (SEM) 2 S 4 /CoS 2 Performing morphology characterization on the CFP electrocatalyst to obtain an SEM (scanning electron microscope) graph shown in FIG. 2; as can be seen from FIG. 2, in NiCo 2 S 4 /CoS 2 Two different morphologies exist in the CFP electrocatalyst, one being a bulk CoS 2 The nano particles are tightly covered on the surface of the carbon fiber rod in CFP, and the distribution is favorable for promoting the electron transfer between the catalyst and the substrate, and the other is in CoS 2 NiCo with clearly observable spherical surface 2 S 4 The particles are uniform in size.
Electrochemical performance test:
(1) CoS prepared in example 1 was used separately in a three electrode system using an electrochemical workstation 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 The CFP electrocatalyst is used as a sample to be tested for hydrogen evolution and oxygen evolution performance test, and comprises the following specific steps:
setting a working electrode as a sample to be tested, setting a graphite rod as a counter electrode, performing electrochemical performance test in 1M KOH electrolyte, and testing the electrocatalytic performance by using a linear voltammetry (LSV), wherein the voltage interval corresponding to the hydrogen evolution reaction is-1.6-0V, the voltage interval corresponding to the oxygen evolution reaction is 0-1.8V, and the scanning speed is 5mV s -1 ；
(2) For NiCo prepared in example 1 2 S 4 /CoS 2 The electrolytic water performance of the CFP electrocatalyst is tested, and the specific steps are as follows:
in a two electrode system, niCo prepared in example 1 was used 2 S 4 /CoS 2 The CFP electrocatalyst is respectively used as a cathode and an anode, the electrolyte is 1M KOH solution, the voltage window is 1.2-1.8V, and the scanning speed is 5mV s -1 。
CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 Hydrogen evolution performance test of CFP electrocatalyst, LSV graph was obtained as shown in fig. 3; as can be seen from FIG. 3, the current density was 10mA cm -2 At the time of CoS 2 /CFP、NiCo 2 S 4 CFP electrocatalyst and NiCo 2 S 4 /CoS 2 The hydrogen evolution overpotential of the/CFP electrocatalyst was 310mV, 324mV and 244mV, respectively, which would be seen for CoS 2 And NiCo 2 S 4 Compounding to form heterojunction to prepare NiCo 2 S 4 /CoS 2 The hydrogen evolution performance of the CFP electrocatalyst is obviously improved, because the CFP electrocatalyst and the CFP electrocatalyst show synergistic enhancement after being compounded;
CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 The LSV curve of the CFP electrocatalyst is converted to obtain a Tafel slope chart shown in figure 4; the Tafel slope is an effective means for determining the speed of the catalytic reaction kinetics process, as can be seen from FIG. 4, coS 2 /CFP、NiCo 2 S 4 CFP electrocatalyst and NiCo 2 S 4 /CoS 2 Tafel slopes of the/CFP electrocatalysts, respectively266mV dec -1 、171mV dec -1 And 151mV dec -1 . With CoS 2 CFP and NiCo 2 S 4 NiCo compared to CFP electrocatalyst 2 S 4 /CoS 2 Tafel slope of the/CFP electrocatalyst was significantly smaller, indicating NiCo 2 S 4 /CoS 2 The CFP electrocatalyst has faster hydrogen evolution reaction kinetics;
CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 The CFP electrocatalyst was tested for oxygen evolution performance, resulting in an LSV graph as shown in fig. 5; as can be seen from FIG. 5, when the current density is 50mA cm -2 At the time of CoS 2 /CFP、NiCo 2 S 4 CFP electrocatalyst and NiCo 2 S 4 /CoS 2 The oxygen evolution overpotential of the/CFP electrocatalyst was 446mV, 481mV and 367mV, respectively, as seen by NiCo 2 S 4 /CoS 2 Oxygen evolution Performance ratio CoS of CFP electrocatalyst 2 CFP and NiCo 2 S 4 The oxygen evolution performance of the CFP electrocatalyst is more excellent.
CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and NiCo prepared in comparative example 2 S 4 The LSV curve of the CFP electrocatalyst is converted to obtain a Tafel slope chart shown in FIG. 6; as can be seen from FIG. 6, coS 2 /CFP、NiCo 2 S 4 CFP electrocatalyst and NiCo 2 S 4 /CoS 2 Tafel slopes of the/CFP electrocatalyst were 221mV dec, respectively -1 、154mV dec -1 And 120mV dec -1 ，NiCo 2 S 4 /CoS 2 The Tafel slope of the/CFP electrocatalyst is the smallest and the oxygen evolution kinetics is the fastest.
For NiCo prepared in example 1 2 S 4 /CoS 2 The electrolysis performance of the/CFP electrocatalyst was tested to obtain an LSV graph as shown in FIG. 7, and it can be seen from FIG. 7 that the electrolysis performance was measured at a current density of 10mA cm -2 When NiCo 2 S 4 /CoS 2 The potential of the/CFP electrocatalyst electrolyzed water was 1.61V, so to speakMing NiCo 2 S 4 /CoS 2 The CFP electrocatalyst has excellent electrolyzed water catalytic performance.
In summary, with the CoS of example 1 2 NiCo prepared in comparative example/CFP 2 S 4 Compared with the CFP electrocatalyst, niCo prepared in example 1 2 S 4 /CoS 2 The CFP electrocatalyst has excellent electrocatalysis performance in hydrogen evolution and oxygen evolution performance tests, and has excellent electrolyzed water catalysis performance; at a current density of 10mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The hydrogen evolution overpotential of the CFP electrocatalyst is 244mV, and the Tafel slope is 151mV dec -1 The method comprises the steps of carrying out a first treatment on the surface of the At a current density of 50mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The oxygen evolution overpotential of the CFP electrocatalyst is 367mV, and the Tafel slope is 120mV dec -1 The method comprises the steps of carrying out a first treatment on the surface of the At a current density of 10mA cm -2 When NiCo prepared in example 1 2 S 4 /CoS 2 The potential of the electrolyzed water of the/CFP electrocatalyst was 1.61V.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a composite electrocatalyst containing cobalt and nickel comprises the following steps:
(1) Carrying out hydrophilic treatment on the carbon fiber paper to obtain pretreated carbon fiber paper;
(2) Immersing the pretreated carbon fiber paper obtained in the step (1) into an aqueous solution containing a cobalt source and a sulfur source, and then carrying out hydrothermal reaction to obtain cobalt disulfide/carbon fiber paper; the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is Na 2 S 2 O 3 ·5H 2 O and Na 2 S·9H 2 One or two of O, wherein the ratio of the mass of the cobalt source to the mass of the sulfur source in the aqueous solution containing the cobalt source and the sulfur source is 1 (2-4);
(3) Immersing the cobalt disulfide/carbon fiber paper obtained in the step (2) into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then carrying out hydrothermal reaction to obtain NiCo 2 S 4 /CoS 2 CFP electrocatalyst; the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is CH 4 N 2 S and CH 3 CSNH 2 The ratio of the amounts of the substances of the nickel source, the cobalt source and the sulfur source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source is 1: (1-3): (3-5);
the ratio of the amount of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the amount of the substance of the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1 (0.15-5.5).
2. The method according to claim 1, wherein the hydrophilic treatment in the step (1) is one of electrochemical treatment, thermal oxidation, liquid phase treatment, plasma treatment, and microwave treatment.
3. The method according to claim 1, wherein the cobalt source in the aqueous solution containing a cobalt source and a sulfur source in the step (2) and the cobalt source in the aqueous solution containing a cobalt source, a nickel source and a sulfur source in the step (3) are independently CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or two of O.
4. The method according to claim 1, wherein the concentration of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) is 3.75X10 -2 ～4.60×10 -2 mmol/mL。
5. The method according to claim 1, wherein the hydrothermal reaction in the step (2) is carried out at a temperature of 160 to 200 ℃ for 16 to 20 hours.
6. The method according to claim 1, wherein the temperature of the impregnation in the step (3) is room temperature, and the time of the impregnation is 20 to 40 minutes.
7. The method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 170 to 190 ℃ for 8 to 12 hours.
8. The composite electrocatalyst comprising cobalt and nickel prepared by the method of any one of claims 1 to 7.
9. The composite electrocatalyst according to claim 8, comprising carbon fiber paper, cobalt disulfide nanoparticles grown in situ on the surface of the carbon fiber paper, and nickel cobalt tetrasulfide microspheres grown in situ on the surfaces of the carbon fiber paper and cobalt disulfide nanoparticles.
10. Use of the cobalt and nickel containing composite electrocatalyst according to claim 8 for the electrolysis of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211039239.0A CN115261915B (en) | 2022-08-29 | 2022-08-29 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211039239.0A CN115261915B (en) | 2022-08-29 | 2022-08-29 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115261915A CN115261915A (en) | 2022-11-01 |
| CN115261915B true CN115261915B (en) | 2023-07-07 |
Family
ID=83755606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211039239.0A Active CN115261915B (en) | 2022-08-29 | 2022-08-29 | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115261915B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116272424A (en) * | 2023-04-20 | 2023-06-23 | 中国长江三峡集团有限公司 | CuFeS 2 Modified catalytic ceramic membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108411324A (en) * | 2018-03-29 | 2018-08-17 | 华南理工大学 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN110714209A (en) * | 2019-10-21 | 2020-01-21 | 太原理工大学 | Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof |
| CN111111699A (en) * | 2019-09-30 | 2020-05-08 | 天津大学 | Nickel-cobalt disulfide composite material and preparation method and application thereof |
| CN111180216A (en) * | 2020-01-15 | 2020-05-19 | 兰州理工大学 | Composite material for super capacitor and preparation method thereof |
-
2022
- 2022-08-29 CN CN202211039239.0A patent/CN115261915B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108411324A (en) * | 2018-03-29 | 2018-08-17 | 华南理工大学 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN111111699A (en) * | 2019-09-30 | 2020-05-08 | 天津大学 | Nickel-cobalt disulfide composite material and preparation method and application thereof |
| CN110714209A (en) * | 2019-10-21 | 2020-01-21 | 太原理工大学 | Cobalt-nickel hydroxide sleeve type modified carbon fiber composite material and preparation method and application thereof |
| CN111180216A (en) * | 2020-01-15 | 2020-05-19 | 兰州理工大学 | Composite material for super capacitor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication of hierarchical NiCo2S4@CoS2 nanostructures on highly conductive flexible carbon cloth substrate as a hybrid electrode material for supercapacitors with enhanced electrochemical performance;Mani Govindasamy et al.;Electrochimica Acta;第328-337页 * |
| Superdispersed NiCo2S4 nanoparticles anchored on reduced graphene oxide for efficient hydrogen evolution reaction in acidic and alkaline media;Xiong Chen et al.;Journal of Alloys and Compounds;第1-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115261915A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109019602B (en) | Molybdenum carbide material, molybdenum carbide @ molybdenum sulfide composite material, and preparation method and application thereof | |
| CN109797405B (en) | Preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode | |
| CN111111707B (en) | Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN109621981B (en) | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN111825127B (en) | Preparation method and application of metallic nickel-based nanomaterial | |
| CN111883367B (en) | Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof | |
| CN113019398B (en) | High-activity self-supporting OER electrocatalyst material and preparation method and application thereof | |
| CN112981455B (en) | Efficient cobalt-based nanosheet water electrolysis catalyst and preparation method and application thereof | |
| CN111495394A (en) | Carbon cloth loaded CoS2/MoS2Heterojunction composite material and preparation method and application thereof | |
| CN109599565B (en) | Preparation method of difunctional cobalt and nitrogen-doped carbon composite in-situ electrode | |
| CN111957336A (en) | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst | |
| CN113637997A (en) | Co2P/CuP2Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| CN115261915B (en) | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof | |
| CN109585856B (en) | Preparation method of dual-functional cobalt sulfide and sulfur and nitrogen doped carbon in-situ composite electrode | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN109585861B (en) | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode | |
| CN110592616A (en) | Method for preparing platinum/titanium dioxide nanotube composite electrode by electroplating method | |
| CN113846346B (en) | Composite material, preparation method thereof and method for preparing hydrogen by electrocatalytic hydrolysis | |
| CN110354870B (en) | Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst | |
| CN113304766A (en) | Preparation method of Co1-xS-MoS 2-nitrogen-doped carbon HER/OER bifunctional catalyst | |
| CN108855139B (en) | Titanium sheet with surface modified sulfur-doped titanium dioxide nanosheet, preparation method and application thereof | |
| CN113381030B (en) | Co 9 S 8 Preparation method of-Co @ NCNTs composite electrode | |
| CN114045521A (en) | Preparation method of nano-scale electrocatalyst |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |