CN115261915A - 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
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- 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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The CFP is used as a substrate, so that a binder is not used, and the catalytic performance of the prepared catalyst is not reduced by using the binder; in-situ deposition of CoS on CFP surface 2 And NiCo 2 S 4 Avoidance of CoS 2 Exposing more active catalytic sites, wherein CoS 2 The kinetic process of hydrogen evolution and oxygen evolution is faster, the conductivity is excellent, and the bimetallic sulfide NiCo 2 S 4 The existence of abundant redox couple, coS 2 And NiCo 2 S 4 The heterojunction is formed by recombination, so that the transfer rate of electrons in the electrocatalysis process is accelerated, defects and vacancies are generated when the heterojunction is formed, more catalytic active sites are provided, and the electrocatalysis performance, namely CoS, is further improved 2 And NiCo 2 S 4 The synergistic effect of the cobalt and nickel composite electrocatalyst is fully utilized, and the catalytic performance of hydrogen evolution, oxygen evolution and electrolyzed water of the prepared cobalt and nickel composite electrocatalyst is 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 and a preparation method and application thereof.
Background
With the rapid development of human society, the problem of energy shortage and environmental pollution increasingly become hot issues of social attention, which also makes people pay high attention to ecological environment protection and sustainable development of energy. At present, the human energy supply is gradually changed from fossil energy to pollution-free and sustainable green energy such as solar energy, tidal energy, wind energy and the like. However, these green energy sources also have some disadvantages, such as being easily affected by weather, time and regions, being unable to supply stably and being difficult to meet the requirements of human production and life. The hydrogen energy has no pollution in the using process, has high energy density, is more stable in supply form than other green energy sources, and becomes one of the green energy sources with the most application prospect.
There are many ways to produce hydrogen, mainly including methane steam reforming, natural gas hydrogen production, and electrolytic water hydrogen production. The methane steam reforming method and the natural gas hydrogen production method are mainly adopted in the industry, but greenhouse gas carbon dioxide is generated in the preparation process. In the process of preparing hydrogen by electrolyzing water, a cathode and an anode respectively carry out reduction reaction and oxidation reaction, only hydrogen and oxygen are generated, the preparation method is more green and more environment-friendly, and the other product of oxygen is widely applied to the aspects of medical care, national defense industry and the like.
In the process of preparing hydrogen and oxygen by using an electrolytic water method, certain energy barrier needs to be overcome. The introduction of a catalyst in the electrolysis of water is an effective means to solve this problem. At present, the catalysts used commercially are noble metal catalysts such as Pt, pd and Ru, however, the reserves of noble metals in earth crust are relatively low and the cost is relatively high, which seriously hinders the wide popularization and application of hydrogen and oxygen production by water electrolysis. Therefore, it is an urgent problem to provide an electrolytic water catalyst with high electrocatalytic performance and low cost.
Disclosure of Invention
The preparation method provided by the invention has wide raw material sources and low cost, and the prepared composite electrocatalyst containing cobalt and nickel has excellent electrocatalytic performance in hydrogen evolution reaction, oxygen evolution reaction and water electrolysis.
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) Dipping 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) soaking 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 step (1) is one of electrochemical treatment, thermal treatment 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 3.75 × 10 -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 cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to 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).
Preferably, the temperature of the immersion in the step (3) is room temperature, and the immersion time 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 a composite electrocatalyst containing cobalt and nickel prepared by the preparation method in the technical scheme, which comprises carbon fiber paper, cobalt disulfide nanoparticles growing on the surface of the carbon fiber paper in situ, and cobaltosic sulfide nickel microspheres growing on the surfaces of the carbon fiber paper and the cobalt disulfide nanoparticles in situ.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method in the technical scheme or the application of the composite electrocatalyst containing cobalt and nickel in the technical scheme in electrolyzed water.
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 carbon fiber paper CFP (carbon fiber paper) to enable the surface of the CFP to have polarity, introducing rich oxygen-containing groups to improve the surface activity of the CFP, facilitating the growth of transition metal sulfides on the surface of the CFP in the subsequent hydrothermal reaction to obtain pretreated carbon fiber paper, then sequentially carrying out impregnation and hydrothermal reaction, and depositing cobalt disulfide CoS (cobalt disulfide) 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 used as the 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; sequentially utilizing a hydrothermal synthesis method to deposit transition metal sulfide CoS on the surface of CFP in situ 2 And NiCo 2 S 4 Simple and efficient, and avoids CoS 2 Exposing more active catalytic sites, wherein CoS 2 Has the advantages of metallicity, quick kinetic processes of hydrogen evolution and oxygen evolution, excellent conductivity, and double-metal sulfide NiCo 2 S 4 The catalyst has abundant redox couples and has excellent electrocatalytic performance; and isForm NiCo in hydrothermal reaction 2 S 4 In process (ii), coS 2 Simultaneously with the NiCo produced 2 S 4 The heterojunction is compounded, so that the transfer rate of electrons in the electrocatalysis process is accelerated, and the electrocatalysis performance is synergistically improved; and certain defects and vacancies are generated when the heterojunction is formed, and the defects and the vacancies provide more catalytic active sites to further improve the electrocatalytic performance of the catalyst, so that the CoS 2 And NiCo 2 S 4 The synergistic effect of the cobalt and nickel-containing composite electrocatalyst is fully utilized, the catalytic performance of hydrogen evolution, oxygen evolution and electrolyzed water of the prepared cobalt and nickel-containing composite electrocatalyst is obviously improved, and the cobalt and nickel-containing composite electrocatalyst has the advantages of wide raw material source and low cost. The results of the examples show that NiCo, prepared in example 1 2 S 4 /CoS 2 The CFP electro-catalyst has excellent electro-catalysis performance in hydrogen evolution and oxygen evolution performance tests, and has excellent electrolytic water catalysis performance; at a current density of 10mA cm -2 NiCo prepared in example 1 2 S 4 /CoS 2 The hydrogen evolution overpotential of the/CFP electrocatalyst is 244mV, the Tafel slope is 151mV dec -1 (ii) a At a current density of 50mA cm -2 NiCo prepared in example 1 2 S 4 /CoS 2 The oxygen evolution overpotential of the/CFP electrocatalyst is 367mV, the Tafel slope is 120mV dec -1 (ii) a At a current density of 10mA cm -2 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 shows CoS prepared in example 1 of the present invention 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst, and comparably prepared NiCo 2 S 4 XRD pattern of CFP electrocatalyst;
FIG. 2 is a NiCo product of example 1 of the present invention 2 S 4 /CoS 2 SEM image of/CFP electrocatalyst;
FIG. 3 is CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 LSV plot of hydrogen evolution performance test of CFP electrocatalyst;
FIG. 4 is CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 Tafel slope diagram of hydrogen evolution performance test of CFP electrocatalyst;
FIG. 5 is CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst, and comparably prepared NiCo 2 S 4 LSV curve chart of oxygen evolution performance test of CFP electrocatalyst;
FIG. 6 is CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 Tafel slope diagram of oxygen evolution performance test of CFP electrocatalyst;
FIG. 7 is a NiCo preparation from example 1 2 S 4 /CoS 2 LSV plot of electrolytic 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) Dipping 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) dipping 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 those conventionally commercially available 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 desmear treatment before use. In the invention, the decontamination treatment preferably comprises cutting the carbon fiber paper, then respectively carrying out ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 8-12 min in sequence, and then placing the paper in a forced air drying oven for drying.
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 has polarity by utilizing hydrophilic treatment, and rich oxygen-containing groups are introduced to improve the surface activity of the CFP, thereby being beneficial to the growth of transition metal sulfides on the surface of the CFP in the subsequent hydrothermal reaction.
In the invention, the electrochemical treatment preferably comprises setting a working electrode as carbon fiber paper, a reference electrode as Saturated Calomel Electrode (SCE), a counter electrode as platinum sheet to form a three-electrode system, and adopting 0.5M H 2 SO 4 The solution is used as electrolyte, and the carbon fiber paper is subjected to hydrophilic treatment by cyclic voltammetry.
After the hydrophilic treatment is finished, the carbon fiber paper after the hydrophilic treatment is preferably subjected to ultrasonic treatment by using absolute ethyl alcohol and deionized water in sequence, and then is dried to obtain the pretreated carbon fiber paper.
The invention has no special limit on the power and time of ultrasonic treatment, and can clean impurities on the surface of the carbon fiber paper.
After the pretreated carbon fiber paper is obtained, the pretreated carbon fiber paper is soaked into an aqueous solution containing a cobalt source and a sulfur source, and then hydrothermal reaction is carried out to obtain the 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 for the immersion is preferably 20 to 40min, more preferably 25 to 35min. The invention controls the dipping temperature and time in the range, which is beneficial to evenly mixing the water solution containing the cobalt source and the sulfur source.
In the invention, the water solution containing the cobalt source and the sulfur sourceThe source of cobalt 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 and the sulfur source is preferably 3.75X 10 -2 ～4.60×10 -2 mmol/mL, more preferably 4.00X 10 -2 ～4.40×10 -2 mmol/mL. The invention controls the concentration of the cobalt source in the water solution containing the cobalt source and the sulfur source within the range, thereby being beneficial to fully dissolving the cobalt source in the water solution.
In the present invention, the sulfur source in the aqueous solution containing a cobalt source and a 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 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 quantity ratio of the cobalt source to the sulfur source in the aqueous solution containing the cobalt source and the sulfur source within the range, and is beneficial to preparing pure-phase cobalt disulfide CoS 2 。
In the invention, the temperature of the hydrothermal reaction is preferably 160-200 ℃, and more preferably 170-190 ℃; the hydrothermal reaction time is preferably 16 to 20 hours, and more preferably 17 to 19 hours. The temperature and time of the hydrothermal reaction are controlled in the range to promote the cobalt source and the sulfur source to fully carry out chemical reaction, and the cobalt disulfide CoS with good crystallinity is precipitated on the carbon fiber paper CFP in situ 2 The cobalt disulfide/carbon fiber paper is obtained, the problems that the target product cannot be obtained due to insufficient reaction caused by too low temperature and too short time are avoided, and the problems that the electrocatalysis performance is reduced due to too large crystal grain size of the precipitated cobalt disulfide product caused by too high temperature and too long time are also avoided.
After the hydrothermal reaction is finished, the product of the hydrothermal reaction is preferably sequentially cooled, washed and dried to obtain the cobalt disulfide/carbon fiber paper.
In the present invention, the cooling method is preferably natural cooling. In the present invention, the washing is preferably sequentially washed with absolute ethanol and deionized water. The invention has no special limit on the washing times, and can achieve the purpose of completely removing impurities. The present invention is not particularly limited in the manner of drying, and the object of removing moisture may be achieved.
After obtaining the cobalt disulfide/carbon fiber paper, the cobalt disulfide/carbon fiber paper is dipped into an aqueous solution containing a cobalt source, a nickel source and a sulfur source, and then hydrothermal reaction is carried out to obtain the composite electrocatalyst containing cobalt and nickel.
In the present invention, the cobalt source in the aqueous solution containing a cobalt source, a nickel source and a 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, the nickel source and the sulfur source is preferably 1X 10 -2 ～45×10 -2 mmol/mL, more preferably 1.67X 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, and is beneficial to controlling NiCo loaded on the cobalt disulfide/carbon fiber paper 2 S 4 The amount of the substances in the catalyst can ensure that the prepared composite electrocatalyst containing cobalt and nickel has optimal electrocatalytic 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 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 cobaltosic nickel tetrasulfide NiCo 2 S 4 。
In the present invention, the cobalt source and the sulfur source are contained in the aqueous solution containing the cobalt source and the sulfur sourceThe ratio of the amount of the nickel source in the aqueous solution containing the cobalt source, the nickel 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 cobalt source in the aqueous solution containing the cobalt source and the sulfur source to the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source within the range, and is favorable for controlling NiCo loaded on the pretreated carbon fiber paper 2 S 4 And CoS 2 So that the prepared composite electrocatalyst containing cobalt and nickel has optimal electrocatalytic performance and avoids NiCo 2 S 4 And CoS 2 Too low or too high a content of (a) does not allow the prepared composite electrocatalyst containing cobalt and nickel to show 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 is adopted.
In the present invention, the temperature of the impregnation is preferably room temperature; the time for the immersion is preferably 20 to 40min, more preferably 25 to 35min. The invention controls the dipping temperature and time in the range, which is beneficial to evenly mixing the water solution containing the cobalt source, the nickel source and the sulfur source.
In the present invention, the temperature of the hydrothermal reaction is preferably 170 to 190 ℃, more preferably 175 to 185 ℃; the hydrothermal reaction time is preferably 8 to 12 hours, and more preferably 9 to 11 hours. The invention controls the temperature and time of the hydrothermal reaction within the range to promote the cobalt source, the nickel source and the sulfur source to fully carry out the chemical reaction, and the NiCo with good crystallinity is precipitated on the cobalt disulfide/carbon fiber paper by in-situ deposition 2 S 4 The composite electrocatalyst containing cobalt and nickel is obtained, the problems that the temperature is too low, the time is too short, the reaction is insufficient, the target product cannot be obtained are avoided, and the problems that the temperature is too high, the time is too long and NiCo is separated out are simultaneously avoided 2 S 4 The grain size of the product is too large and the electrocatalytic properties are reduced.
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 washed with absolute ethanol and deionized water. The invention has no special limit on the washing frequency, and can completely remove impurities. The present invention is not particularly limited in the manner of drying, and the object of removing moisture is 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 shows excellent electrocatalytic performance in the aspects of hydrogen evolution reaction, oxygen evolution reaction and water electrolysis.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method in the technical scheme. In the invention, the composite electrocatalyst containing cobalt and nickel comprises carbon fiber paper, cobalt disulfide nanoparticles growing on the surface of the carbon fiber paper in situ, and cobaltosic sulfide nickel microspheres growing on the surfaces of the carbon fiber paper and the cobalt disulfide nanoparticles in situ.
The composite electrocatalyst containing cobalt and nickel prepared by the preparation method provided by the invention has excellent electrocatalytic performance in hydrogen evolution reaction, oxygen evolution reaction and water electrolysis.
The invention also provides the composite electrocatalyst containing cobalt and nickel prepared by the preparation method in the technical scheme or the application of the composite electrocatalyst containing cobalt and nickel in the technical scheme in electrolyzed water.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The preparation method of the composite electrocatalyst containing cobalt and nickel comprises the following steps:
(1) Cutting the CFP into small pieces of 1cm × 1.5cm, and performing decontamination treatment on the cut CFP, namely separatingRespectively performing ultrasonic treatment in acetone, anhydrous ethanol and deionized water for 10min, drying in a forced air drying oven, setting a working electrode as the CFP after decontamination treatment by using an electrochemical workstation, setting a reference electrode as a Saturated Calomel Electrode (SCE) and a counter electrode as a platinum sheet to form a three-electrode system, and adopting 0.5M H 2 SO 4 Using the solution as electrolyte, carrying out hydrophilic treatment on CFP by using cyclic voltammetry, and after the hydrophilic treatment is finished, washing the carbon fiber paper subjected to hydrophilic treatment for multiple times by using absolute ethyl alcohol and deionized water in sequence, and then drying to obtain pretreated carbon fiber paper;
(2) Soaking 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 to fully contact 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 an air-blowing drying box, naturally cooling a product of the hydrothermal reaction after the hydrothermal reaction is finished, washing the product with absolute ethyl alcohol and deionized water for multiple times, and drying to obtain cobalt disulfide/carbon fiber paper, namely CoS 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 into a beaker, and 2mmol of CoCl was weighed 2 ·6H 2 O and 3mmol Na 2 S 2 O 3 ·5H 2 O, putting the mixture into a beaker filled with deionized water, and stirring the mixture for 30min by using a magnetic stirrer to fully dissolve the mixture 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 The concentration of O is 4.17X 10 -2 mmol/mL；
(3) Soaking the cobalt disulfide/carbon fiber paper obtained in the step (2) into a water solution containing a cobalt source, a nickel source and a sulfur source for 30min to ensure that the cobalt disulfide/carbon fiber paper is fully contacted with the water solution containing the cobalt source, the nickel source and the sulfur source, transferring the cobalt disulfide/carbon fiber paper and the water 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 oven, and finishing the hydrothermal reactionThen, the product of the hydrothermal reaction is naturally cooled, is washed for a plurality of times by absolute ethyl alcohol and deionized water, and is dried to obtain the composite electrocatalyst containing cobalt and nickel, namely NiCo 2 S 4 /CoS 2 a/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) was weighed 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 and treating the mixture for 30min by using a magnetic stirrer to fully dissolve the mixture 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 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;
the ratio of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the nickel source in the aqueous solution containing the cobalt source, the nickel source and the sulfur source in the step (3) is 1.
Comparative example
NiCo 2 S 4 The preparation method of the CFP electrocatalyst comprises the following steps:
(1) Cutting carbon fiber paper CFP into small pieces of 1cm × 1.5cm, setting working electrode as CFP after decontamination treatment by electrochemical workstation, reference electrode as Saturated Calomel Electrode (SCE), and counter electrode as platinum sheet to form three-electrode system, and adopting 0.5M H 2 SO 4 Using the solution as electrolyte, carrying out hydrophilic treatment on CFP by using cyclic voltammetry, and after the hydrophilic treatment is finished, washing the carbon fiber paper subjected to hydrophilic treatment for multiple times by using absolute ethyl alcohol and deionized water in sequence, and then drying to obtain pretreated carbon fiber paper;
(2) Dipping 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 to ensure that the carbon fiber paper is fully contacted with the aqueous solution containing the cobalt source, the nickel source and the sulfur source, and 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 liningCarrying out hydrothermal reaction for 10h at 180 ℃ in a blast drying oven, after the hydrothermal reaction is finished, naturally cooling a product of the hydrothermal reaction, washing the product for multiple times by using absolute ethyl alcohol and deionized water, and drying the product to obtain NiCo 2 S 4 a/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 measured and placed in a beaker, and 2mmol of Ni (NO) was weighed 3 ) 2 ·6H 2 O、4mmol Co(NO 3 ) 2 ·6H 2 O and 8mmol CH 4 N 2 And S, placing the mixture into a beaker filled with deionized water, and stirring and treating the mixture for 30min by using a magnetic stirrer to fully dissolve the mixture 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 comparably prepared NiCo 2 S 4 the/CFP electrocatalyst is subjected to X-ray diffraction (XRD) test, and an XRD pattern is obtained and shown in figure 1; from FIG. 1, it can be found that CoS is a strong diffraction peak of CFP 2 Diffraction Peak of/CFP and CoS 2 Matched standard PDF card (JCPDS No. 70-2865), niCo 2 S 4 Diffraction Peak of CFP and NiCo 2 S 4 Matched with standard PDF card (JCPDS No. 43-1477), niCo 2 S 4 /CoS 2 CoS coexisting in CFP electrocatalyst 2 And NiCo 2 S 4 And no diffraction peak of other impurity phase, indicating that example 1 successfully produces NiCo 2 S 4 /CoS 2 /CFP electrocatalyst.
Scanning Electron Microscopy (SEM) was used to align the NiCo prepared in example 1 2 S 4 /CoS 2 the/CFP electrocatalyst is subjected to morphology characterization, and an SEM image is obtained and is shown in figure 2; as can be seen from FIG. 2, in NiCo 2 S 4 /CoS 2 There are two different morphologies in the/CFP electrocatalyst, one is bulk CoS 2 The nanoparticles tightly cover the surface of the carbon fiber rods in the CFP, and such distribution is beneficial for promoting electron transfer between the catalyst and the substrate, and the other is CoS 2 Spherical NiCo with clearly observable surface 2 S 4 And the particle size is uniform.
And (3) electrochemical performance testing:
(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 comparably prepared NiCo 2 S 4 The method comprises the following steps of taking a CFP electrocatalyst as a sample to be tested to test the hydrogen evolution performance and the oxygen evolution performance, and comprises the following specific steps:
setting a working electrode as a sample to be tested, a counter electrode as a graphite rod, carrying out electrochemical performance test in 1M KOH electrolyte, and testing the electrocatalytic performance by using a linear voltammetry (LSV), wherein the voltage interval corresponding to a hydrogen evolution reaction is-1.6-0V, the voltage interval corresponding to an 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 electro-catalyst of CFP is respectively used as a cathode and an anode, the electrolyte is 1M KOH solution, the voltage window is 1.2 to 1.8V, and the scanning speed is 5mV s -1 。
For each CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 the/CFP electro-catalyst is subjected to a hydrogen evolution performance test, and an LSV curve chart is obtained and is shown in figure 3; as can be seen from FIG. 3, the current density was 10mA cm -2 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, as can be seen for CoS 2 And NiCo 2 S 4 NiCo prepared by compounding to form heterojunction 2 S 4 /CoS 2 The hydrogen evolution performance of the/CFP electrocatalyst is obviously improved, because the two catalysts show a synergistic enhancement effect after being compounded;
for each CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 The LSV curve of the/CFP electrocatalyst is converted to obtain a Tafel slope diagram as shown in FIG. 4; wherein, the Tafel slope is an effective means for judging the speed of the catalytic reaction kinetics process, and as can be seen from FIG. 4, coS 2 /CFP、NiCo 2 S 4 /CFP electrocatalyst and NiCo 2 S 4 /CoS 2 Tafel slope of/CFP electrocatalyst is 266mV dec -1 、171mV dec -1 And 151mV dec -1 . And CoS 2 CFP and NiCo 2 S 4 Comparative CFP electrocatalyst, niCo 2 S 4 /CoS 2 The Tafel slope of the/CFP electrocatalyst is significantly smaller, indicating NiCo 2 S 4 /CoS 2 The CFP electro-catalyst has a faster hydrogen evolution reaction kinetic process;
for each CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst and comparably prepared NiCo 2 S 4 the/CFP electrocatalyst is subjected to an oxygen evolution performance test, and an LSV curve chart is obtained and is shown in FIG. 5; as can be seen from FIG. 5, when the current density was 50mA cm -2 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 is 446mV, 481mV and 367mV, respectively, and it can be seen that 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.
For each CoS prepared in example 1 2 CFP and NiCo 2 S 4 /CoS 2 CFP electrocatalyst, and comparably prepared NiCo 2 S 4 The LSV curve of the/CFP electrocatalyst is converted to obtain a Tafel slope diagram as 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 The Tafel slope of the/CFP electrocatalyst is 221mV dec -1 、154mV dec -1 And dec of 120mV -1 ，NiCo 2 S 4 /CoS 2 The Tafel slope of the/CFP electrocatalyst is the smallest, and the oxygen evolution kinetic process is the fastest.
NiCo prepared in example 1 2 S 4 /CoS 2 The electrolytic water performance of the CFP electrocatalyst is tested, and an LSV curve chart is obtained and shown in figure 7, and the LSV curve chart is shown in figure 7, and can be known from figure 7, when the current density is 10mA cm -2 Whilst NiCo 2 S 4 /CoS 2 The potential of the water electrolyzed by the CFP electrocatalyst is 1.61V, which indicates that NiCo 2 S 4 /CoS 2 the/CFP electrocatalyst has excellent electrolytic water catalysis performance.
In conclusion, the same as CoS in embodiment 1 2 CFP, niCo prepared by comparative example 2 S 4 Comparative CFP electrocatalyst, niCo prepared in example 1 2 S 4 /CoS 2 The CFP electrocatalyst has excellent electrocatalytic performance in hydrogen evolution and oxygen evolution performance tests, and has excellent electrolytic water catalytic performance; at a current density of 10mA cm -2 NiCo prepared in example 1 2 S 4 /CoS 2 The hydrogen evolution overpotential of the/CFP electrocatalyst is 244mV, the Tafel slope is 151mV dec -1 (ii) a At a current density of 50mA cm -2 NiCo prepared in example 1 2 S 4 /CoS 2 The oxygen evolution overpotential of the CFP electrocatalyst is 367mV, the Tafel slope is 120mV dec -1 (ii) a At a current density of 10mA cm -2 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 only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection 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) Dipping 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) soaking 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.
2. The method according to claim 1, wherein the hydrophilic treatment in the step (1) is one of electrochemical treatment, thermal treatment 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 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.
4. The production 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 3.75X 10 -2 ～4.60×10 -2 mmol/mL。
5. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 160 to 200 ℃, and the time of the hydrothermal reaction is 16 to 20 hours.
6. The production method according to claim 1, wherein the ratio of the amounts of the cobalt source in the aqueous solution containing the cobalt source and the sulfur source in the step (2) to the amounts 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).
7. 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 40min.
8. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (3) is 170 to 190 ℃, and the time of the hydrothermal reaction is 8 to 12 hours.
9. The composite electrocatalyst containing cobalt and nickel prepared by the preparation method of any one of claims 1 to 8, comprising carbon fiber paper, cobalt disulfide nanoparticles grown in situ on the surface of the carbon fiber paper, and cobaltosic sulfide nickel microspheres grown in situ on the surfaces of the carbon fiber paper and the cobalt disulfide nanoparticles.
10. Use of a composite electrocatalyst containing cobalt and nickel prepared by the preparation process according to any one of claims 1 to 8 or according to claim 9 in electrolysis of water.
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