CN110760882B - Preparation method and application of nano Ag/CoS flexible electrode material - Google Patents
Preparation method and application of nano Ag/CoS flexible electrode material Download PDFInfo
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Abstract
The invention belongs to the field of energy raw materials, and particularly relates to a preparation method and application of a nano Ag/CoS flexible electrode material. The preparation process is simple, the prepared material has porous pore channels, the specific surface area is large, the appearance is novel, the catalytic materials with different nano-scales and appearances and different catalytic performances can be prepared by adjusting positive and negative voltages, and the electrode adopts the carbon cloth which can be folded for many times, so that the flexible wearable electrode material can be popularized and is a potential electro-catalytic full-hydrolysis catalyst.
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a nano Ag/CoS flexible electrode material which has potential application space in the aspects of full hydrolysis hydrogen production and oxygen production.
Background
The ever-increasing demand for sustainable energy supply and environmental protection has led to intensive research into high-performance devices for energy storage and conversion. Electrochemical methods may provide promising solutions for energy storage and conversion due to high thermodynamic efficiency and environmental factors. Transition metals with quasi-three-dimensional (3D) electronic structures have been a hot topic in the field of electrode materials because of their unique structure, arranged on a conductive substrate, such that noble metal/transition self-supporting binder-free electrode materials show significant effects.
Electrochemical water splitting to achieve electrical energy conversion from intermittent sources (solar and wind) to hydrogen is considered one of the most promising approaches. As a reference electrocatalyst, Pt-based materials close to zero overpotential are the most advanced catalysts for Hydrogen Evolution Reaction (HER), Ru/Ir oxide is the most powerful catalyst Oxygen Evolution Reaction (OER). However, the scarcity and cost of these expensive catalysts severely limits their large-scale utilization. Therefore, there has been an effort to explore metal-based electrocatalysts, such as transition metal sulfides/nitrides/phosphides for HER, and compounds where transition metal oxides and (oxy) hydroxides are converted from metals to OER.
CN109321959A discloses an electrochemical preparation method of a nano Ag embedded electrode material, which adopts the electrochemical preparation method to prepare multilayer nano Ag to support Co3O4Nanosheets in the preparation of Co3O4Heating conditions are adopted, so that the Ag nano-rod can agglomerate at high temperature, and finally the conductivity of the nano-wire is reduced.
CN110010875A discloses a preparation method of a flaky cobalt sulfide composite flexible carbon cloth electrode material, which adopts a hydrothermal method for preparation, and a support material is selected from C fiber. The adhesive force is not strong enough, and the cycling stability is not good enough.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an Ag-supported CoS embedded flexible electrode material, which forms a single-layer or multi-layer Ag/CoS sheet structure by controlling the electrodeposition time and times so as to generate the required electrocatalysis effect.
The specific technical scheme is as follows:
a preparation method of a nano Ag/CoS flexible electrode material comprises the following steps:
(1) dissolving silver nitrate in deionized water, and uniformly mixing, wherein the using amount of the deionized water is 5-10 times of the molar weight of the silver nitrate to obtain a solution A;
(2) dissolving ammonia water in deionized water, wherein the using amount of the deionized water is 10-20 times of the molar weight of the ammonia water, and uniformly mixing to obtain a solution B;
(3) dissolving sodium dodecyl sulfate in an alcohol solution, wherein the molar weight of the alcohol solution is 10-20 times of that of the sodium dodecyl sulfate, and completely dissolving to obtain a solution C; mixing the solution A and the solution B, slowly pouring the solution C, and carrying out ultrasonic treatment for 30-60 min; standing to obtain a solution D;
(4) adding CoCl2·6H2Dissolving O in deionized water with the dosage of CoCl2·6H2Adding 1.2 times of CoCl into the mixture according to the molar weight of the O being 20-30 times of that of the mixture2·6H2O, stirring thioacetamide with the molar weight by magnetic force, and uniformly mixing to obtain a solution E;
(5) preparing an original Ag support material in a D solution by an electrodeposition method by taking carbon cloth as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode, wherein the voltage of a positive direct current electric field and a negative direct current electric field is-1V to +1V, and the reaction time is 30s-90 s; rinsing to obtain a product F;
(6) putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30-90 s, rinsing, and blow-drying to obtain an Ag/CoS electrode embedded with silver;
(7) and (5) repeating the steps (5) and (6) to deposit for 1-3 times to obtain the nano Ag/CoS flexible electrode material.
And (3) magnetically stirring in the dissolving process of the steps (1), (2) and (4), wherein the stirring speed is 500r/min-800 r/min.
In the step (2), the concentration of the ammonia water is 25%, and the ratio of the silver nitrate to the ammonia water is 1:1-1: 3.
The molar weight of the sodium dodecyl sulfate in the step (3) is 0.5-1 time of that of the silver nitrate;
the alcohol solution in the step (3) can be alcohol with small molecular weight such as methanol, ethanol, propanol, butanol and the like.
CoCl in the step (4)2·6H2The molar weight of O is 2 to 5 times of the molar weight of silver nitrate.
In the step (5), the carbon cloth is 1cm multiplied by 1 cm.
In the steps (5) and (6), deionized water and ethanol are used in the rinsing process, and rinsing is carried out for 3-5 times.
The nano Ag/CoS flexible electrode material can be applied to a catalyst for hydrogen production by full decomposition.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the nano Ag/CoS flexible electrode material provided by the invention, the shape and structure of a nano material precipitated by chemical reaction can be effectively controlled through controlling the electrodeposition time and controlling the size and direction (positive and negative voltages) of direct current voltage, so that the controllable preparation of different shapes of Ag/CoS embedding is realized; the electrodeposition time is short, so that the precipitated CoS can present different nano appearances and sizes, and nano-structure materials with different requirements can be obtained; the microstructure of the prepared material can be adjusted by controlling the electro-deposition for different times, and single-layer and multi-layer Ag/CoS structures can be formed to generate the required catalytic effect; the preparation process is simple, the prepared material has porous pore channels, the specific surface area is large, the appearance is novel, the catalytic materials with different nano-scales and appearances and different catalytic performances can be prepared by adjusting positive and negative voltages, and the electrode can be popularized as a flexible wearable electrode material by selecting carbon cloth which can be folded for many times and can be widely applied to the fields of energy conversion, catalysis and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the material prepared in example 1.
FIG. 2 is a scanning electron micrograph of the material prepared in example 2.
FIG. 3 is a scanning electron micrograph of the material prepared in example 3.
FIG. 4 is a scanning electron micrograph of the material prepared in example 4.
Figure 5 is a graph of HER activity for the different examples tested.
FIG. 6 is a graph of OER activity for different examples tested.
Detailed Description
To date, many methods have been used to prepare composites, such as Guo Rui et al, the patent of Qinhuang island of northeast university, the electrochemical fabrication of a nano-Ag embedded electrode materialThe preparation method (application No. 201811236257.1) adopts carbon cloth as an electrolyte carrier, has wider applicability, and is embodied in flexible materials, larger specific surface area and stronger single-loading capacity. Different from the patents, the preparation method is completely prepared at normal temperature and normal pressure in the preparation process of the patent, and does not adopt any heating condition. In the electrochemical preparation method of nano Ag embedded electrode material, applied in Guo Rui et al, Co is prepared3O4By adopting a heating condition, the Ag nano-rod can agglomerate at a high temperature, and finally the conductivity of the nano-wire is reduced. Furthermore, the sulfides employed in the present invention have better activity than the oxides due to low coordination at the edges of the particles. The S atom is more active, which makes Ag/Co3O4The ORE over potential of the prepared sample is 366mV, while the ORE over potential of the carbon cloth prepared by the patent application for the nano Ag/CoS flexible electrode material is 200 mV.
Compared with the patent of yellow Jianfeng et al of Shanxi university of science and technology, the preparation method of the flaky cobalt sulfide composite flexible carbon cloth electrode material (application No. 201910289347.5) adopts a hydrothermal method for preparation, and the support material is C fiber. In the preparation method of the nano Ag/CoS flexible electrode material, nano Ag particles are introduced to improve the conductivity among particles, and meanwhile, the growth of the particles is inhibited, so that the material particles are nano-sized. As the Ag rod is used as an inter-particle conductive material, the unit area single-loading capacity is more, and the Ag rod is more suitable for preparing a large-current device. Compared with hydrothermal preparation, the sample prepared by the electrodeposition method has stronger adhesive force and better circulation stability.
The Ag-supported CoS embedded flexible electrode material is prepared by adopting different external voltage electrodeposition methods and is used for HER and OER electrocatalysis. The material is deposited on the flexible material carbon cloth, and the result shows that CoS grown on the carbon cloth and the Ag layer has completely different morphologies. When Ag/CoS is electrodeposited for 2 times alternately, a sheet structure with large holes is formed, Ag is a support body, and CoS is sheet-shaped, so that the preparation of the self-supporting controllable electrode material is realized. Due to this unique 3D layering and the large number of active sites on the outermost layer, the prepared flexible material shows very high catalytic activity towards HER and OER reactions.
The present invention will be described in detail with reference to the following embodiments and drawings, but the scope of the present invention is not limited by the embodiments and drawings.
Example 1
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution A.
(2) Dissolving 1mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution B.
(3) 0.5mmol of sodium dodecyl sulfate is dissolved in 5mmol of ethanol solution, and solution C is prepared after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, and performing ultrasonic treatment for 30 min; standing to obtain a solution D.
(4) 2mmol of CoCl2·6H2O was dissolved in 40mmol of deionized water, and 1.2 times of CoCl was added2·6H2And (3) performing magnetic stirring on thioacetamide with the molar weight of O, and uniformly mixing to obtain a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +1V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) The product F was placed in solution E with the Pt electrode as the counter electrode, and after electrodeposition for 30s, the Ag-supported CoS embedded flexible electrode material was formed by carefully rinsing several times with deionized water and ethanol.
FIG. 1 is a scanning electron micrograph of the material prepared in example 1, FIG. 5 is a graph of HER activity measured in various examples, and FIG. 6 is a graph of OER activity measured in various examples.
As shown in FIG. 1, the prepared nano Ag/CoS flexible electrode material is of a lamellar structure, the thickness of the lamellar is only 20-30 nanometers, the dispersion is uniform, and the boundary is unclear;
the electro-catalysis hydrogen evolution and oxygen evolution performance of the nano Ag/CoS flexible electrode material is tested by adopting a three-electrode system, a Pt sheet is taken as a counter electrode, a Saturated Calomel Electrode (SCE) is taken as a reference electrode, and a working electrode is an ITO electrode of which the surface is dropwise coated with the nano Ag/CoS flexible electrode material; the testing instrument is a PARSTAT 2273 electrochemical workstation; the test solution was 1mol/L KOH.
Fig. 5 is a HER curve, the starting point of the curve curving downward representing the starting potential for hydrogen production by reduction, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
Fig. 6 is an OER curve, and the starting point of the curve curving upward represents the starting potential for hydrogen production by oxidation, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
Example 2
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 60min at the stirring speed of 800r/min, and uniformly mixing to obtain a solution A.
(2) Dissolving 3mmol of ammonia water in 30mmol of deionized water, magnetically stirring for 60min at the stirring speed of 800r/min, and mixing uniformly to obtain solution B.
(3) Dissolving 1mmol of sodium dodecyl sulfate in 15mmol of methanol solution, and obtaining solution C after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, carrying out ultrasonic treatment for 30min, and standing to obtain a solution D.
(4) 5mmol of CoCl2·6H2O was dissolved in 100mmol of deionized water, and 1.2 times of CoCl was added2·6H2And (3) performing magnetic stirring on thioacetamide with the molar weight of O, and uniformly mixing to obtain a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +1V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30s, carefully rinsing for several times by using deionized water and ethanol, and drying by blowing to form the Ag/CoS electrode embedded with silver.
(7) And (5) repeating the steps (5) and (6) for 2 times of deposition to form the nano Ag/CoS flexible electrode material.
FIG. 2 is a scanning electron microscope image of the material prepared in example 2, and it can be seen from FIG. 2 that the prepared Ag/CoS electrode material is a uniform lamellar structure, uniform in pore size, 10-20 nm in lamellar thickness, uniform in dispersion, clear in boundary and large in specific surface area; figure 5 is a HER curve from which HER performance was best seen with 2 repeated depositions. FIG. 6 is an OER curve from which the best OER performance is seen after 2 depositions. The catalyst prepared by the embodiment has the advantages of fast surface transmission, minimum charge transfer resistance and key role of the catalytic activity charge transfer speed in the catalytic process.
Example 3
(1) Dissolving 1mmol of silver nitrate in 8mmol of deionized water, magnetically stirring for 30min at the stirring speed of 800r/min, and uniformly mixing to obtain a solution A.
(2) Dissolving 2mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 800r/min, and mixing uniformly to obtain solution B.
(3) 0.8mmol of sodium dodecyl sulfate is dissolved in 10mmol of butanol solution, and solution C is prepared after the sodium dodecyl sulfate is completely dissolved. Mixing A and B, slowly pouring the solution C, carrying out ultrasonic treatment for 30min, and standing to obtain a solution D.
(4) 3mmol of CoCl2·6H2O was dissolved in 60mmol of deionized water, and 1.2 times of CoCl was added2·6H2And (3) performing magnetic stirring on thioacetamide with the molar weight of O, and uniformly mixing to obtain a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, adding a voltage of a direct current electric field +1V, reacting for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30s, carefully rinsing for several times by using deionized water and ethanol, and drying by blowing to form the Ag/CoS electrode embedded with silver.
(7) And (5) repeating the steps (5) and (6) for 3 times, and forming the nano Ag/CoS flexible electrode material.
FIG. 3 is a scanning electron micrograph of the material prepared in example 3, FIG. 5 is a HER curve, and FIG. 6 is an OER curve.
As can be seen from FIG. 3, the Ag-supported CoS embedded flexible electrode material prepared by repeating the electrodeposition for 3 times has the advantages of compact nanosheet layer, increased lamella thickness and unclear boundary, so that the charge transfer resistance of the electrode is higher, and the diffusion behavior of the electrochemical active species on the surface is more difficult.
Example 4
(1) Dissolving 1mmol of silver nitrate in 10mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution A.
(2) Dissolving 1mmol of ammonia water in 20mmol of deionized water, magnetically stirring for 30min at the stirring speed of 700r/min, and mixing uniformly to obtain solution B.
(3) 0.5mmol of sodium dodecyl sulfate is dissolved in 5mmol of propanol solution, and after the sodium dodecyl sulfate is completely dissolved, solution C is prepared. Mixing A and B, slowly pouring the solution C, carrying out ultrasonic treatment for 30min, and standing to obtain a solution D.
(4) 2mmol of CoCl2·6H2O was dissolved in 40mmol of deionized water, and 1.2 times of CoCl was added2·6H2And (3) performing magnetic stirring on thioacetamide with the molar weight of O, and uniformly mixing to obtain a solution E.
(5) And (2) preparing an original Ag support material in the solution D by using carbon cloth (1cm multiplied by 1cm) as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode through an electrodeposition method, externally applying a voltage of-1V of a direct current electric field for reaction for 30s, and carefully rinsing the carbon cloth electrode for 3 times by using deionized water and ethanol to obtain a product F.
(6) And putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30s, carefully rinsing for several times by using deionized water and ethanol, and blow-drying to form the nano Ag/CoS flexible electrode material.
(7) And (4) repeating the steps (5) and (6) for deposition, and forming the nano Ag/CoS flexible electrode material.
FIG. 4 is a scanning electron microscope image of the material prepared in example 4, and it can be seen from the scanning electron microscope that the prepared electrode material sheets are bonded together to form small nano-bulk, which is not favorable for surface charge transmission.
Comparative example 1 (Nano Ag/Co)3O4Preparation of Flexible electrode Material
The patent of Qinhuangdai of northeast university Guo Rui et al, an electrochemical preparation method of nano Ag embedded electrode material (application number 201811236257.1), firstly obtaining original Co by electrodeposition method3O4Nanosheet array of virgin Co3O4Calcining the nano-sheet array at 400-500 ℃ for 1-2 hours to convert the nano-sheet array into Co3O4A nanosheet of (a); secondly, supporting Co by electrodepositing multi-layer nano Ag on the basis of the above3O4Nanosheets, multilayered Co3O4And supporting and fixing the nano sheets by virtue of nano Ag to prepare the nano Ag embedded electrode material. In the preparation of Co3O4Heating conditions are adopted in the process, so that the Ag nano-rod can be agglomerated at high temperature, and finally the conductivity of the nano-wire is reduced.
The invention is different from the patent, firstly, the invention adopts the carbon cloth as the electrolyte carrier, has wider applicability, the prepared material has larger specific surface area and stronger single-loading capacity, and the carbon cloth is used as a flexible material, and has wider application space. Secondly, different from the above patents, the preparation method of the invention is completely prepared at normal temperature and normal pressure without any heating condition. Furthermore, the sulfides employed in the present invention have better activity than the oxides due to low coordination at the edges of the particles. And compared with an O atom, the S atom has stronger activity and better catalytic effect by adopting the S atom as an active site. This makes Ag/Co3O4The ORE over-potential of the prepared sample is 366mV, while the ORE over-potential of the nano Ag/CoS flexible electrode material prepared by the invention is 200 mV.
Comparative example 2 (lamellar cobalt sulfide composite flexible carbon cloth electrode material)
Comparative example 2 is a flaky cobalt sulfide composite flexible carbon cloth electrode material prepared according to the method in CN 110010875A. A preparation method of a flaky cobalt sulfide composite flexible carbon cloth electrode material comprises the steps of adding analytically pure cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol to obtain a solution A; adding analytically pure thioacetamide into deionized water to obtain a solution B; mixing the solution A and the solution B to obtain a precursor solution C; adding CBTA into the solution C to obtain a solution D; carrying out anodic oxidation pretreatment on the carbon cloth; and completely soaking the pretreated carbon cloth into the solution D, putting the solution D and the carbon cloth into a hydrothermal reaction kettle for hydrothermal reaction, taking out the carbon cloth, cleaning, and freeze-drying to obtain the flaky cobalt sulfide composite flexible carbon cloth material.
Compared with the material for preparing the nano Ag/CoS flexible electrode material in the comparative example 2, the method adopts a normal temperature and pressure method, the preparation process is simple and feasible, and the industrialization degree is high. Compared with hydrothermal preparation, the sample prepared by the electro-deposition method has stronger adhesive force and better circulation stability. Comparative example 2 was prepared by hydrothermal method, and the support material was selected as C fiber. In the preparation method of the nano Ag/CoS flexible electrode material, nano Ag particles are introduced to improve the conductivity among particles, and meanwhile, the growth of the particles is inhibited, so that the material particles are nano-sized. As the Ag rod is used as an inter-particle conductive material, the unit area single-loading capacity is more, and the Ag rod is more suitable for preparing a large-current device.
In summary, many sulfide powders reported in the literature at the present stage have different preparation methods and morphologies from those of the sulfide powders of the present invention. The embedded electrode material prepared by the invention does not adopt higher temperature and pressure in the preparation process, well overcomes the defects of the existing material preparation, ensures the safety in the preparation process, and is an innovation of the invention; the electrode material prepared by the invention is a flexible electrode material, and is an innovation of the invention. In addition, the embedded quasi-three-dimensional electrode material prepared by the invention can regulate and control the appearance and size of a product by regulating and controlling the electrodeposition time, and is beneficial to improving the electrochemical performance of the product.
Claims (8)
1. A preparation method of a nano Ag/CoS flexible electrode material comprises the following steps:
(1) dissolving silver nitrate in deionized water, and uniformly mixing, wherein the using amount of the deionized water is 5-10 times of the molar weight of the silver nitrate to obtain a solution A;
(2) dissolving ammonia water in deionized water, wherein the using amount of the deionized water is 10-20 times of the molar weight of the ammonia water, and uniformly mixing to obtain a solution B;
(3) dissolving sodium dodecyl sulfate in an alcohol solution, wherein the molar weight of the alcohol solution is 10-20 times of that of the sodium dodecyl sulfate, and completely dissolving to obtain a solution C; mixing the solution A and the solution B, slowly pouring the solution C, and carrying out ultrasonic treatment for 30-60 min; standing to obtain a solution D;
(4) adding CoCl2·6H2Dissolving O in deionized water with the dosage of CoCl2·6H2Adding 1.2 times of CoCl into the mixture according to the molar weight of the O being 20-30 times of that of the mixture2·6H2O, stirring thioacetamide with the molar weight by magnetic force, and uniformly mixing to obtain a solution E;
(5) preparing an original Ag support material in a D solution by an electrodeposition method by taking carbon cloth as a working electrode, a Pt electrode as a counter electrode and a saturated calomel electrode as a reference electrode, wherein the voltage of a positive direct current electric field and a negative direct current electric field is-1V to +1V, and the reaction time is 30s-90 s; rinsing to obtain a product F;
(6) putting the product F into the solution E, taking the Pt electrode as a counter electrode, carrying out electrodeposition for 30-90 s, rinsing, and blow-drying to obtain an Ag/CoS electrode embedded with silver;
(7) repeating the steps (5) and (6) to deposit for 1-3 times to obtain the nano Ag/CoS flexible electrode material;
the nanometer Ag/CoS flexible electrode material is applied to a catalyst for producing hydrogen through full hydrolysis, a flexible wearable electrode material and energy conversion.
2. The preparation method according to claim 1, wherein magnetic stirring is performed during the dissolving process in the steps (1), (2) and (4), and the stirring speed is 500r/min-800 r/min.
3. The method according to claim 1, wherein the concentration of the ammonia water in the step (2) is 25%, and the molar ratio of the silver nitrate to the ammonia water is 1:1-1: 3.
4. The method according to claim 1, wherein the molar amount of sodium dodecylsulfate in the step (3) is 0.5 to 1 times the molar amount of silver nitrate.
5. The method for preparing the alcohol solution of claim 1, wherein the alcohol solution in the step (3) can be methanol, ethanol, propanol, butanol alcohol with small molecular weight.
6. The method according to claim 1, wherein the CoCl in the step (4)2·6H2The molar weight of O is 2 to 5 times of the molar weight of silver nitrate.
7. The production method according to claim 1, wherein the carbon cloth in the step (5) is 1cm x 1 cm.
8. The method of claim 1, wherein in the steps (5) and (6), the rinsing process uses deionized water and ethanol, and the rinsing process is performed 3 to 5 times.
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| US20180112318A1 (en) * | 2016-10-21 | 2018-04-26 | Industry-Academic Cooperation Foundation, Yonsei University | Catalyst for generating hydrogen and method of preparing the same |
| CN108479804A (en) * | 2018-03-14 | 2018-09-04 | 成都新柯力化工科技有限公司 | A kind of zinc sulphide bronzing catalyst and preparation method for mixing silver for hydrogen manufacturing |
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| CN105289658A (en) * | 2015-10-23 | 2016-02-03 | 吉林大学 | Carbon fiber supported cobalt sulfide nanosheet catalyst and application thereof |
| US20180112318A1 (en) * | 2016-10-21 | 2018-04-26 | Industry-Academic Cooperation Foundation, Yonsei University | Catalyst for generating hydrogen and method of preparing the same |
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