CN114345374B - Preparation method of amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth - Google Patents
Preparation method of amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 97
- 239000004744 fabric Substances 0.000 title claims abstract description 84
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 61
- 239000011733 molybdenum Substances 0.000 title claims abstract description 59
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920001021 polysulfide Polymers 0.000 title claims abstract description 51
- 239000005077 polysulfide Substances 0.000 title claims abstract description 51
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
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Abstract
The invention discloses a preparation method of an amorphous molybdenum polysulfide electrocatalytic hydrogen evolution catalyst constructed on carbon cloth. The invention takes ammonium tetrathiomolybdate and acetic acid as precursors, and successfully synthesizes the molybdenum polysulfide catalyst on carbon cloth by a multi-step water bath method. The hydrogen evolution electrocatalyst with high performance and non-noble metal has the advantages of excellent performance, low cost, simple synthesis mode, easy control and high repetition rate, and is suitable for popularization and application.
Description
Technical Field
The invention discloses a preparation method of an amorphous molybdenum polysulfide and molybdenum polysulfide electrocatalytic hydrogen evolution catalyst constructed on carbon cloth. The method belongs to the technical field of energy and catalysis.
Background information
The environmental problems are continuously aggravated by the large consumption of traditional fossil fuels, which promotes people to continuously develop new sustainable clean energy sources. Hydrogen is generally considered as a clean and efficient renewable energy source with better energy density. The technology of hydrogen production by water electrolysis is widely paid attention to, is simple and convenient to operate and is environment-friendly, so that electrocatalytic hydrogen evolution is considered as a technology with a very good application prospect.
The important research of hydrogen production by water electrolysis is to reduce the overpotential or increase the current density by a cathode catalyst, so as to realize that more hydrogen energy is obtained by using less energy consumption. Noble metals such as platinum as active sitesThe catalysts of (2) are considered to possess excellent catalytic properties, but the high price and the scarce reserves make them less dominant in large-scale industrial applications, resulting in a high technical cost. Therefore, low-cost, high-activity hydrogen evolution catalysts have become one of the targets that are continually pursued in this field. In the current study, moS 2 Has excellent hydrogen evolution catalytic activity and abundant earth reserves, and is a non-noble metal material which can be regarded as a substituted platinum-based catalyst [ Nat. Mater.,2012,11,963-969.]。
MoS 2 The catalytic activity of (2) is mainly dependent on two aspects: moS (MoS) 2 The number of active sites and charge transport properties. Based on this, zhang [ Acs Appl Mater Interfaces,2015,7 (22): 12193-12202.]Et al grow vertical MoS on carbon cloth 2 The nano-sheet enables unsaturated sulfur atoms with the edge part as an active site to be fully exposed, and meanwhile, charges between layers are avoided, and resistance of charge transmission is reduced. Studies have also shown that: amorphous molybdenum polysulfide results in exposure of more unsaturated sulfur atoms due to its irregularly arranged structure, but the problem of insufficient charge transport capacity itself still exists. At present, experiments have been carried out on molybdenum polysulfide and conductive materials to cooperatively improve the catalytic performance. Min [ International Journal of Hydrogen Energy,2018, 43 (10): 4978-4986]The et al adopts a simpler controllable electrochemical deposition method to prepare a foam Cu@ molybdenum polysulfide electrode, which has high specific surface area, rich active sites and fast electron transfer. Li [ Small,2016,12 (40): 5530-5537]The theoretical calculation by the et al shows that the semi-metal CoMoP 2 For the substrate, hydrothermally forming amorphous MoS 2 /CoMoP 2 The S atoms on the basal plane of the heterostructure can be activated or removed by bonding with hydrogen to form S vacancies, accelerating the hydrogen evolution process very rapidly. The methods have the problems of complex operation, long experimental period, low synthesis efficiency and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to synthesize the hydrogen evolution catalyst with high efficiency and low cost and the preparation method thereof. The amorphous molybdenum polysulfide molybdenum catalyst is synthesized by a multi-step water bath method, and the preparation process is simple and easy to control. The growth condition of molybdenum polysulfide in the product can be regulated and controlled by controlling the carbon cloth treatment mode and the water bath times. The catalyst provided by the invention has the characteristics of good performance, low cost and the like.
In order to obtain the high-performance hydrogen evolution electrocatalyst, the invention adopts the following technical scheme:
an amorphous molybdenum polysulfide-molybdenum hydrogen evolution catalyst constructed on carbon cloth is provided, and the amorphous molybdenum polysulfide-molybdenum is uniformly wrapped on the carbon cloth.
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst comprises the following steps:
(6) Carrying out soaking pretreatment on the carbon cloth;
(7) Ultrasonically cleaning the carbon cloth obtained in the step (1), and drying for later use;
(8) Preparing a mixed solution of ammonium tetrathiomolybdate and glacial acetic acid;
(9) Transferring the solution obtained in the step (3) and the carbon cloth obtained in the step (2) into a water bath kettle, and cooling after water bath to obtain a sample;
(10) And taking out the carbon cloth, washing with ultrapure water and drying to obtain the amorphous molybdenum polysulfide material constructed on the carbon cloth.
In the above scheme, the step (1) is: soaking carbon in acetone or butanone at normal temperature for 4-5 hr.
In the above scheme, the step (2) is as follows: and washing and drying the carbon cloth in ultrapure water and ethanol for later use.
In the above scheme, the step (3) is as follows: and weighing ammonium tetrathiomolybdate by an electronic balance, dissolving in ultrapure water, adding glacial acetic acid, and uniformly stirring at room temperature.
In the scheme, the mass volume ratio of the ammonium tetrathiomolybdate to the glacial acetic acid in the step (3) is 16-24:1 mg/ml.
In the scheme, the water bath temperature in the step (4) is respectively 60-80 ℃.
In the scheme, the water bath time in the step (4) is 20-60 min.
In the scheme, the water bath time in the step (4) is 2-4 times.
In the above scheme, the cooling mode in the step (4) is natural cooling.
In the scheme, the ultrapure water washing frequency in the step (5) is 6-8 times.
In the scheme, the drying time in the step (5) is 3-5 h.
The invention uses a multi-step water bath method to make amorphous molybdenum polysulfide MoS x Successfully builds on carbon cloth with good conductivity, ensures the abundance of active sites and optimizes the charge transmission capacity of amorphous molybdenum polysulfide molybdenum. Finally, the high-performance molybdenum-based hydrogen evolution electrocatalyst is obtained. Provides a new reference for research and development of molybdenum-based hydrogen evolution electrocatalyst.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth, wherein a molybdenum polysulfide layer which is densely coated is formed on the carbon cloth by the pretreatment of the carbon cloth and the multi-step water bath method. The method realizes the enrichment of active sites and has excellent charge transmission capacity, thereby obtaining high-efficiency and stable hydrogen evolution performance.
2. The invention provides a transition metal molybdenum-based catalyst, which contains an amorphous molybdenum polysulfide catalyst, wherein the amorphous molybdenum polysulfide uniformly grows on carbon cloth. The material has the advantages of excellent electrocatalytic hydrogen evolution performance and low price.
3. The invention adopts a multi-step water bath method, has simple and convenient working procedures, mild and easily controlled reaction conditions and high repetition rate, and is suitable for popularization and application.
Drawings
FIG. 1 is a wide-angle diffraction XRD pattern of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 1 of the invention. Wherein the pretreatment liquid is acetone, the water bath temperature is 70 ℃, the water bath time is 30min, and a two-step water bath method is adopted. A is amorphous molybdenum polysulfide directly synthesized by a water bath method, B is a sample formed by taking acetone as pretreatment liquid of carbon cloth and carrying out water bath twice, and C is a sample obtained by synthesizing the sample B under the same conditions and carrying out calcination treatment.
FIG. 2 is an SEM image of a secondary water bath of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 1 of the invention. Wherein the pretreatment agent used is acetone, and a, b and c are SEM images of samples with different magnifications after one water bath; d, e, f are SEM images of the samples at different magnifications after the secondary water bath.
FIG. 3 is an EDX spectrum (Mapping) of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 1 of the invention. Wherein the water bath temperature is 70 ℃, the water bath time is 30min, and the two steps of water bath are carried out.
FIG. 4 is a graph showing the electrochemical performance of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 1 of the invention. Wherein the water bath temperature is 70 ℃, the water bath time is 30min, and the two steps of water bath are carried out. A is the case where the carbon cloth is untreated, and B is the case where acetone is used as a pretreatment agent for the carbon cloth.
FIG. 5 shows the electrochemical stability of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 1 of the invention. Wherein the water bath temperature is 70 ℃, the water bath time is 30min, and the two steps of water bath are carried out.
FIG. 6 is a graph showing the electrochemical performance of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 5 of the invention. Wherein the water bath temperature is 70 ℃, the water bath time is 30min, and acetone is used as the pretreatment liquid of the carbon cloth. A is the case after the primary water bath, and B is the case after the secondary water bath.
FIG. 7 is an SEM image of a secondary water bath of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth in example 2 of the invention. Wherein the pretreatment agent used is acetone, and a, b, c and d are SEM pictures of 36,40.5,49.5 and 54mg of ammonium tetrathiomolybdate respectively.
FIG. 8 is an SEM image of a secondary water bath of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth after treatment with different pretreatment fluids and a secondary water bath in comparative example 1 of the present invention. Wherein a, b and c are SEM images with different magnifications after 30% hydrogen peroxide treatment; d, e, f are SEM images of different magnification after concentrated nitric acid treatment; g, h, i are SEM pictures of different magnifications after acetone treatment;
FIG. 9 is a graph showing the electrochemical performance of an amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth after treatment with different pretreatment fluids and secondary water bath in comparative example 1.
Detailed Description
For a better understanding of the present invention, reference will be made to the following examples, which are not intended to limit the scope of the invention.
In the following examples, the drugs are all commercially available chemicals unless specifically indicated.
Example 1
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, arranging carbon in an acetone and butanone solution, and soaking for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) 45mg of ammonium tetrathiomolybdate was weighed by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and the mixture was stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 30min at 70 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4).
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
FIG. 1 is a wide-angle diffraction XRD pattern of a sample prepared at a water bath temperature of 70℃in this example. As is evident from the XRD pattern, the as-synthesized uncalcined sample B, except for the apparent carbon cloth diffraction peaks (2θ=26.2° and 43.4 °), did not exhibit other phases of diffraction peaks, and was similar to amorphous molybdenum polysulfide pattern a, did not correspond to crystalline MoS 2 The sharp diffraction peak of (2) appears; in calcined sample C, the corresponding crystalline MoS was observed 2 Diffraction peaks of (002), (100), (102) crystal planes appear.
Fig. 2 is an SEM photograph of a sample prepared in this example at 70 ℃ for 30min in a two-step water bath, and it can be seen that the amorphous molybdenum polysulfide layer formed on the carbon cloth under this condition is significantly denser than the amorphous molybdenum polysulfide layer formed on the carbon cloth after one water bath under the same conditions.
FIG. 3 shows an EDX spectrum (Mapping) of a sample prepared in two steps of water bath at 70 ℃ for 30min, wherein Mo and S elements can be uniformly distributed on carbon cloth.
FIG. 4 shows a polarization curve and a Tafil slope diagram of an amorphous molybdenum polysulfide catalyst constructed on a carbon cloth prepared in a two-step water bath at a water bath temperature of 70deg.C for 30min, showing that the catalyst obtained by subjecting an acetone-treated carbon cloth to a two-step water bath has excellent hydrogen evolution performance at a current density of 50mA/cm 2 The time overpotential was 170mV.
FIG. 5 shows the electrochemical stability of an amorphous molybdenum polysulfide catalyst constructed on a carbon cloth directly removed in a two-step water bath at a water bath temperature of 70℃for 30 min. It can be seen that the catalyst has excellent electrochemical stability.
FIG. 6 is a graph showing the polarization curve and Tafil slope of the samples obtained in the first and second water baths when the water bath temperature was 70deg.C and the water bath time was 30min and the amounts of ammonium tetrathiomolybdate and glacial acetic acid were 45mg and 2.25ml, respectively, and the samples after the two water baths exhibited better hydrogen evolution performance.
Example 2
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, and soaking carbon in an acetone solution for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) Ammonium tetrathiomolybdate 36,40.5,49.5,54mg was weighed out by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 30min at 70 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4).
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
FIG. 7 is an SEM photograph of samples prepared in this example at a water bath temperature of 70℃for 30 minutes in a two-stage water bath at different amounts of ammonium tetrathiomolybdate, which shows that the amorphous molybdenum polysulfide layer formed on a carbon cloth in this example is not quite different from that in the case of the different amounts of ammonium tetrathiomolybdate.
Example 3
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, and soaking carbon in an acetone solution for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) 45mg of ammonium tetrathiomolybdate was weighed by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and the mixture was stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 30min at 60, 70 and 80 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4).
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
Under the condition of the embodiment, the synthetic catalyst is amorphous molybdenum polysulfide and can be uniformly loaded on carbon cloth to form a relatively compact molybdenum polysulfide layer.
Example 4
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, and soaking carbon in an acetone solution for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) 45mg of ammonium tetrathiomolybdate was weighed by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and the mixture was stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 20,40,50 and 60 minutes at 70 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4).
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
Under the condition of the embodiment, the synthetic catalyst is amorphous molybdenum polysulfide and can be uniformly loaded on carbon cloth to form a relatively compact molybdenum polysulfide layer.
Example 5
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, arranging carbon in an acetone solution, and soaking for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) 45mg of ammonium tetrathiomolybdate was weighed by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and the mixture was stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 30min at 70 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4). Three or four water baths were performed.
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
Comparative example 1
The preparation method of the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth comprises the following steps:
(1) Pretreating carbon cloth, and respectively placing the carbon cloth in concentrated nitric acid or 30% hydrogen peroxide solution, and soaking for 5 hours at room temperature for later use.
(2) And (3) respectively ultrasonically cleaning the carbon cloth in the step (1) in ultrapure water and ethanol for 10min, and drying in a baking oven at 60 ℃ for later use.
(3) 45mg of ammonium tetrathiomolybdate was weighed by an electronic balance, dissolved in 17.25mL of ultrapure water, 2.25mL of glacial acetic acid was added thereto, and the mixture was stirred at room temperature for 5 minutes.
(4) Transferring the carbon cloth obtained in the step (2) and the solution obtained in the step (3) to the same container, placing the container in a water bath kettle, reacting for 30min at 70 ℃, and cooling to room temperature.
(5) And (5) repeating the water bath process in the step (4).
(6) And (3) cleaning the carbon cloth obtained in the step (5) by using ultrapure water for 6-8 times, and arranging the carbon in a baking oven at 40 ℃ for drying for 3 hours.
Fig. 8 is an SEM photograph of samples prepared by using concentrated nitric acid, 30% hydrogen peroxide and acetone as pretreatment solutions respectively in two steps of water baths at a water bath temperature of 70 ℃ for 30min in the comparative example, and shows that the amorphous molybdenum polysulfide layer constructed on the carbon cloth under the condition is obviously less dense than that after the acetone treatment.
Fig. 9 is a graph showing electrochemical performance, and it can be seen that the amorphous molybdenum polysulfide hydrogen evolution catalyst provided by the invention has excellent electrochemical performance compared with a control sample.
The foregoing has shown and described the basic principles and advantages of the invention. Other variations in form will be apparent to those skilled in the art from the foregoing description, and it is not necessary or exhaustive of all embodiments, and obvious variations are within the scope of the invention.
Claims (3)
1. A preparation method of an amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on carbon cloth is characterized in that: the method comprises the following steps:
(1) Carrying out soaking pretreatment on carbon cloth: soaking carbon in acetone or butanone at normal temperature for 4-5 h;
(2) Ultrasonically cleaning the carbon cloth obtained in the step (1), and drying for later use;
(3) Preparing a mixed solution of ammonium tetrathiomolybdate and glacial acetic acid, wherein the mass volume ratio of the ammonium tetrathiomolybdate to the glacial acetic acid is 16-24:1 mg/mL;
(4) Transferring the solution obtained in the step (3) and the carbon cloth obtained in the step (2) into a water bath kettle, and cooling after water bath to obtain a sample, wherein the water bath temperature is 60-80 ℃; the water bath time is 20-60 min; the water bath times in the step (4) are 2-4 times;
(5) And taking out the carbon cloth, washing and drying the carbon cloth by using ultrapure water to obtain the amorphous molybdenum polysulfide catalyst constructed on the carbon cloth, wherein the amorphous molybdenum polysulfide hydrogen evolution catalyst constructed on the carbon cloth is formed by uniformly wrapping the amorphous molybdenum polysulfide on the carbon cloth.
2. The method of manufacturing according to claim 1, characterized in that: the step (3) is as follows: weighing ammonium tetrathiomolybdate, dissolving in ultrapure water, adding glacial acetic acid, and stirring uniformly at room temperature.
3. The method of manufacturing according to claim 1, characterized in that: the cooling mode of the step (4) is natural cooling; the ultrapure water washing times in the step (5) are 6 to 8 times; and (5) drying time is 3-5 h.
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