CN117987864A - High-performance hydrogen evolution catalyst and preparation method and application thereof - Google Patents
High-performance hydrogen evolution catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance hydrogen evolution catalyst and a preparation method and application thereof. The preparation method comprises the following steps: bombarding a molybdenum disulfide target material by a radio frequency power supply, and synthesizing a nanoscale molybdenum disulfide nano material in an inert gas atmosphere; and depositing the molybdenum disulfide nano material on a substrate, and then annealing the obtained composite material in an ultrahigh vacuum environment to obtain the high-performance hydrogen evolution catalyst. The molybdenum disulfide nano material high-performance hydrogen evolution catalyst prepared by the invention shows extremely low overpotential and extremely long-time stability in a 1M KOH solution, the overpotential of the catalyst is as low as 148mV under 1000mA cm ‑2, and the catalyst has the characteristics of low overpotential and excellent catalytic stability, and particularly has stable catalytic activity for HER (HER) for more than 1840 hours; meanwhile, the preparation method disclosed by the invention is controllable in operation, the raw materials and the substrate are easy to obtain, the cost is low, and the catalytic performance of the molybdenum disulfide nano material can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of nano material catalysts, and particularly relates to a high-performance hydrogen evolution catalyst and a preparation method and application thereof.
Background
Due to excessive consumption of non-renewable fossil energy sources, serious energy crisis and greenhouse effect are caused. Therefore, turning to renewable energy is an effective strategy to achieve energy diversification and reduce society's dependence on fossil fuels. Hydrogen Evolution Reactions (HER) are a key technology to provide renewable energy sources. The current catalysts with excellent catalytic performance mostly depend on noble metals, are high in price and cost, and are not easy to obtain. Thus, developing a high activity HER catalyst using a rich and lower cost material remains challenging.
MoS 2 has a two-dimensional lamellar structure similar to graphite, is very stable, is nontoxic, has anisotropy in crystal, is reasonable in price, is easy to obtain materials, and has great potential in the fields of catalysis, sensing, electrochemical operation and environmental correlation. Recent researches show that MoS 2 is one of the most potential hydrogen evolution reaction electrocatalysts at present, and a plurality of strategies such as doping or co-doping are proposed for improving the catalytic performance of molybdenum disulfide, but few researches are carried out for exploring the influence between the molybdenum disulfide and a foam nickel substrate. The edge locations, voids, and boundaries are inherent HER catalytic locations of MoS 2, which may be critical to improving the catalytic performance of molybdenum disulfide. In addition, studies have shown that the smaller the size of nanoparticles, the more active sites, compared to bulk materials, and thus studies on the catalytic properties of molybdenum disulfide nanomaterials are very necessary.
Therefore, a new technology for researching and improving the catalytic performance of the molybdenum disulfide nano material is sought, and the technology has long been the direction of researchers in the industry.
Disclosure of Invention
The invention mainly aims to provide a high-performance hydrogen evolution catalyst and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a high-performance hydrogen evolution catalyst, which comprises the following steps:
Bombarding a molybdenum disulfide target material by a radio frequency power supply, and condensing and synthesizing a nanoscale molybdenum disulfide nano material in an inert gas atmosphere;
And depositing the molybdenum disulfide nano material on a substrate, and then annealing the obtained composite material in an ultrahigh vacuum environment to obtain the high-performance hydrogen evolution catalyst.
In some embodiments, the method of making comprises: placing a substrate in a reaction cavity by adopting a vacuum sputtering inert gas condensation technology, taking a molybdenum disulfide target as a target material, introducing inert gas, bombarding the target material by adopting inert ions in a vacuum environment, condensing and gathering the sputtered molybdenum disulfide nano material to form clusters, and enabling beam flow formed by the clusters to reach a deposition cavity so as to deposit on the substrate; the vacuum environment used was a vacuum of greater than 1X 10 -3 Pa.
In some embodiments, the process conditions of the vacuum sputtering inert gas condensation technique include: vacuum sputtering power of 10-36W and deposition rate of
The embodiment of the invention also provides a high-performance hydrogen evolution catalyst prepared by the preparation method, which comprises a substrate and a nano-scale molybdenum disulfide nano material loaded on the substrate.
The embodiment of the invention also provides application of the high-performance hydrogen evolution catalyst in hydrogen evolution reaction.
Compared with the existing hydrogen evolution catalyst, the invention has the following beneficial effects:
the molybdenum disulfide nano material high-performance hydrogen evolution catalyst prepared by the invention shows extremely low overpotential and extremely long-time stability in a 1M KOH solution, particularly has stable catalytic activity for HER (HER) exceeding 1840 hours, and has the characteristics of low overpotential and excellent catalytic stability; meanwhile, the preparation method disclosed by the invention is controllable in operation, the raw materials and the substrate are easy to obtain, the cost is low, and the catalytic performance of the molybdenum disulfide nano material can be obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIGS. 1 a-1 b are linear sweep voltammograms and overpotential maps corresponding to 1000mA cm -2 current densities of the high-performance hydrogen evolution catalyst molybdenum disulfide nanomaterial prepared in example 1 of the present invention at different annealing temperatures of 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃;
FIGS. 2 a-2 b illustrate deposition on a molybdenum mesh prepared in accordance with example 2 of the present invention Transmission electron microscope photograph and size distribution diagram of the thickness high-performance hydrogen evolution catalyst molybdenum disulfide nano material;
FIGS. 3 a-3 d are schematic illustrations of deposition onto a molybdenum mesh prepared at different Ar gas flows in example 3 of the present invention HRTEM images of molybdenum disulfide nanoparticles of the high-performance hydrogen evolution catalyst;
FIGS. 4 a-4 h are schematic illustrations of deposition onto a molybdenum mesh prepared at different Ar gas flows in example 3 of the present invention TEM image and size distribution histogram of thickness high-performance hydrogen evolution catalyst molybdenum disulfide nano particles;
FIGS. 5 a-5 f illustrate deposition onto a molybdenum mesh prepared in accordance with example 4 of the present invention Transmission electron microscope pictures and diffraction patterns of different annealing temperatures of the high-performance hydrogen evolution catalyst molybdenum disulfide nano material;
FIGS. 6 a-6 b are linear sweep voltammograms and overpotential maps corresponding to 1000mA cm -2 current densities for a molybdenum disulfide nanomaterial of example 5 of the present invention using a carbon cloth substrate and a foam nickel substrate, respectively, that were not annealed and annealed at 400 ℃;
FIG. 7 is a graph showing constant voltage polarization corresponding to a current density of 1000mA cm -2 for a molybdenum disulfide room temperature catalyst using a foam nickel substrate in accordance with example 6 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has provided a technical scheme of the present invention through long-term research and a great deal of practice, mainly through the bombardment of a radio frequency power supply on a molybdenum disulfide target material, condensation synthesis of a nanoscale molybdenum disulfide nano material in an inert gas atmosphere, deposition of the molybdenum disulfide nano material on foam nickel, and annealing in an ultra-high vacuum environment. The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the high-performance hydrogen evolution catalyst comprises the following steps:
In some specific embodiments, the invention is based on the principle of vapor synthesis, adopts vacuum sputtering inert gas condensation technology, uses a high-temperature sintered molybdenum disulfide target, and introduces high-purity sputtering gas at the target. And applying radio frequency current on the molybdenum disulfide target material through a radio frequency power supply to generate an electric field between the anode and the cathode, bombarding the target material at a high speed under the action of the electric field to form a gaseous precursor of metal atoms, and cooling to supersaturation by liquid nitrogen (-171 ℃) to form the nanoscale solid molybdenum disulfide nanoparticles. The vacuum degree of the vacuum environment is better than 1X 10 -3 Pa.
The invention also deposits the molybdenum disulfide nano material on the substrate, and then anneals the obtained composite material in a vacuum environment, and the proper annealing temperature can effectively change the structure of the catalyst, thereby obviously improving the performance of the catalyst and preparing the high-performance hydrogen evolution catalyst.
In some embodiments, the method of making comprises: placing a substrate (such as foam nickel-NF, carbon cloth CC and the like) in a reaction cavity by adopting a vacuum sputtering inert gas condensation technology, taking a molybdenum disulfide target as a target material, introducing inert gas, bombarding the target material at a high speed by adopting inert ions Ar 2+、He2+ under a vacuum environment, condensing and gathering a large amount of sputtered gaseous precursors of Mo atoms and S atoms through liquid nitrogen to form clusters, and enabling a beam composed of the clusters to reach a deposition cavity so as to deposit on the substrate; the vacuum environment used was a vacuum of greater than 1X 10 -3 Pa.
In some more specific embodiments of the invention, the process conditions of the vacuum sputtering inert gas condensation technique include: vacuum sputtering power of 10-36W and deposition rate of
In some more specific embodiments of the present invention, the inert gas includes at least any one of argon, helium, etc., but is not limited thereto. Further, the flow of the argon is 20-300 sccm, and the flow of the helium is 20-5000 sccm.
In some more specific embodiments of the invention, the average size (particle size range) of the molybdenum disulfide nanomaterial is 5 to 40nm, preferably 20 to 25nm.
Further, the morphology of the molybdenum disulfide nanomaterial includes nanoparticles, nanosheets, or the like, preferably nanoparticles.
Further, the substrate comprises any one of carbon cloth, molybdenum net, foam nickel, foam copper, glass carbon sheet, gold sheet and the like, preferably foam nickel, and the combination effect of the molybdenum disulfide material and the metal substrate is better.
Further, the foam nickel substrate is thinner and has smaller aperture, and the foam nickel substrate with the specification of 1-100 mu m and the thickness of 0.1-2 mm is preferably selected.
In some embodiments, the vacuum degree range of the ultra-high vacuum environment is 10 -3～10-7 Pa, the annealing treatment temperature is 200-700 ℃ and the annealing treatment time is 10 min-1 h. Specifically, the annealing treatment temperature may be preferably 200 ℃,300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, or the like, and the HER performance is best when the annealing temperature is preferably 400 ℃ to 500 ℃.
In some embodiments, the method of making further comprises: before the molybdenum disulfide nano material is deposited on the substrate, the substrate is subjected to acid washing and natural air drying treatment.
Further, the pickling includes: and sequentially carrying out ultrasonic cleaning on the substrate by using a mixed solution of absolute ethyl alcohol and acetone, a dilute hydrochloric acid solution, water and absolute ethyl alcohol.
Further, the step of pickling the nickel foam comprises the steps of: ultrasonic treatment was performed for 10min each in the order of absolute ethanol: acetone=1:1 solution, 10% dilute hydrochloric acid solution, deionized water, absolute ethanol.
In some more specific embodiments, taking a substrate as an example of foam nickel, the preparation method of the high-performance foam nickel-supported sulfide hydrogen evolution catalyst provided by the invention comprises the following steps:
The method comprises the steps of bombarding a molybdenum disulfide target material through a radio frequency power supply, synthesizing nanoscale molybdenum disulfide nano particles in an inert gas atmosphere, depositing the molybdenum disulfide nano particles on foam nickel, and carrying out annealing treatment in an ultrahigh vacuum environment, so that the nickel-based hydrogen evolution catalyst with good stability and excellent HER performance is prepared.
Specifically, a vacuum sputtering inert gas condensation technology is adopted, a foam nickel substrate is placed in a deposition cavity, a molybdenum disulfide target is used as a target material, ar 2+、He2+ is introduced to bombard the target material, clusters are formed through condensation aggregation, beam flows formed by the clusters reach the deposition cavity, and the foam nickel is deposited on the foam nickel to form molybdenum disulfide nano particles loaded by the foam nickel.
In the whole process, the vacuum degree is better than 1 x 10 -3 Pa, the foam nickel substrate is subjected to a special pickling step before being used, firstly, foam nickel is ultrasonically cleaned in absolute ethyl alcohol and acetone (1:1) solution for 10 minutes to clean residual organic matters on the surface of the substrate, then 10% diluted hydrochloric acid solution diluted by concentrated hydrochloric acid is ultrasonically cleaned for 10 minutes to remove the oxides on the surface of the substrate, then deionized water is used for rinsing to be neutral, then the foam nickel substrate is soaked in absolute ethyl alcohol and ultrasonically cleaned for 10 minutes to remove the residual moisture, and finally the foam nickel substrate is put in absolute ethyl alcohol solution for standby. The target material is molybdenum disulfide metal target material.
Further, the foam nickel substrate is thinner, preferably has a pore size of 20-80 microns and a thickness of 0.5-1.5 mm.
Further, the target used in the preparation method is specifically a molybdenum disulfide target, and the deposited molybdenum disulfide nano material has the overpotential of the foam nickel-loaded molybdenum disulfide nano particles in 1000mA cm -2 current density of 1M KOH solution as low as 148mV and the stability of 1840h in a constant current polarization curve through a linear sweep voltammetry test.
In another aspect, the present invention provides a high performance hydrogen evolution catalyst prepared by the above preparation method. The high-performance hydrogen evolution catalyst comprises a substrate and a nanoscale molybdenum disulfide nanomaterial supported on the substrate.
In some preferred embodiments, the thickness of the deposition of the molybdenum disulfide nanomaterial clusters in the high performance hydrogen evolution catalyst is in the range of 20 to 25nm.
Further, the high-performance hydrogen evolution catalyst prepared by the invention shows extremely low overpotential and long-time stability in a 1M KOH solution, specifically, the HER overpotential of the catalyst at 1000mA cm -2 is as low as 148mV, the catalyst shows good stability, and the catalytic activity for keeping stable to HER at the current density of 1000mA cm -2 exceeds 1840 hours.
Another aspect of the embodiments of the present invention also provides the use of the aforementioned high performance hydrogen evolution catalyst in hydrogen evolution reactions.
In conclusion, the molybdenum disulfide nanomaterial high-performance hydrogen evolution catalyst prepared by the method provided by the invention has extremely low overpotential and extremely long-time stability in a 1M KOH solution, and particularly has the characteristics of low overpotential and excellent catalytic stability when the catalytic activity for keeping stable HER exceeds 1840 hours; meanwhile, the preparation method disclosed by the invention is controllable in operation, the raw materials and the substrate are easy to obtain, the cost is low, and the catalytic performance of the molybdenum disulfide nano material can be obviously improved.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
All processes and equipment of the present invention are well known in the art, and each is well known and understood in the art for its associated use, and from the names, one skilled in the art can understand the steps of the process and the corresponding equipment used.
Example 1
Washing a foam nickel substrate by acid washing, firstly, ultrasonically cleaning residual organic matters on the surface of the substrate by using foam nickel in absolute ethyl alcohol and acetone (1:1) solution for 10 minutes, ultrasonically removing the oxide on the surface of the substrate by using 10% diluted hydrochloric acid solution diluted by concentrated hydrochloric acid for 10 minutes, then rinsing to be neutral by using deionized water, soaking in absolute ethyl alcohol, ultrasonically cleaning for 10 minutes to remove residual moisture, and finally placing in absolute ethyl alcohol solution for standby. Before use, the foam nickel is taken out from the absolute ethyl alcohol and dried by N gas, and finally the foam nickel is put into a vacuum cavity for waiting to deposit the MoS 2 nanometer material.
Adopting vacuum sputtering inert gas condensation technology, drying a foam nickel substrate by N gas, placing the foam nickel substrate in a deposition cavity, taking a molybdenum disulfide target as a target material, introducing inert gas Ar gas and He gas, wherein Ar gas flow is 160sccm, he gas flow is 180sccm, setting vacuum sputtering power to be 27W, and measuring deposition rate to beThe beam composed of MoS 2 clusters reaches the deposition cavity, so as to be deposited on the foam nickel substrate, and the uniform annealing treatment is carried out for 20min at the temperature of 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ and 700 ℃ in an ultra-high vacuum environment of not less than 10 -3 Pa.
The inventor carries out HER electrochemical test on the high-performance hydrogen evolution catalyst nano material prepared in the embodiment in a 1M KOH solution, and the result is as follows:
Referring to FIGS. 1 a-1 b, the linear sweep voltammogram of the high performance hydrogen evolution catalyst molybdenum disulfide nanomaterial annealed at different temperatures of 200 ℃, 300 ℃,400 ℃, 500 ℃, 600 ℃, 700 ℃ and the overpotential map corresponding to 1000mA cm -2 current density in this example are shown. As can be seen from fig. 1a to fig. 1b, in the test results of the catalytic performance of 1M KOH HER, the molybdenum disulfide nanomaterial with different thickness has the lowest overpotential at 400 ℃ and the best catalytic performance, wherein the overpotential of 1000mA cm -2 is 148mV, which is similar to the current density of the industrial catalyst, and the performance is also excellent. The catalytic performance of the molybdenum disulfide nano material with different annealing temperatures is better than that of hollow foam nickel.
Example 2
The preparation method of this example is different from that of example 1 in that: the substrate used was a molybdenum mesh, the remaining conditions being the same.
The inventor carries out Transmission Electron Microscope (TEM) characterization on the high-performance hydrogen evolution catalyst molybdenum disulfide nano material prepared by the embodiment, and the result is as follows:
Referring to FIGS. 2 a-2 b, a deposition prepared in this example Transmission electron microscope photograph and size distribution diagram of the thickness high-performance hydrogen evolution catalyst molybdenum disulfide nano material. As can be seen from the figures 2 a-2 b, the high-performance hydrogen evolution catalyst molybdenum disulfide nano material is uniformly distributed, and the particle size is between 5 and 40 nm.
Example 3
The preparation method of this example is different from that of example 1 in that: the used substrate is a molybdenum net, the inert gas Ar gas flow is different, and the morphology and the size of the MoS 2 nano clusters can be obviously changed by changing the Ar gas flow.
The high-performance hydrogen evolution catalyst molybdenum disulfide nanomaterial prepared in the embodiment is subjected to Transmission Electron Microscope (TEM) characterization, and the result is as follows:
Referring to FIGS. 3 a-3 d, a deposition prepared for this example The Ar gas flow with the thickness is respectively 60sccm, 145sccm, 160sccm and 245sccm of the transmission electron microscope photograph of the single particles of the molybdenum disulfide nano material. It can be seen from the figures 3 a-3 d that the interplanar spacing is 0.65nm for the molybdenum disulfide (002) plane, 0.23nm for the (103) plane, 0.26nm for the (100) plane, and 0.17nm for the (110) plane. The Ar flow rate increases, the average size of the particles increases, and a polycrystalline domain structure appears. Wherein, the particles of the nano particles are smaller when the Ar flow is 160sccm, and the polycrystalline domain structure is more obvious.
Referring to FIGS. 4 a-4 h, a deposition prepared for this exampleThe thickness of Ar gas flow is 60sccm, 145sccm, 160sccm, 245sccm of high performance hydrogen evolution catalyst molybdenum disulfide nanomaterial transmission electron microscope photograph (FIG. 4a, FIG. 4c, FIG. 4e, FIG. 4 g) and size distribution diagram (FIG. 4b, FIG. 4d, FIG. 4f, FIG. 4 h) respectively. From the above figures, it can be seen that the particle size differences at different gas flows are large.
Example 4
The preparation method of this example is different from that of example 1 in that: the substrate used was a molybdenum network, and different annealing temperatures made the polycrystalline domain structure of MoS 2 nanoclusters different.
The high-performance hydrogen evolution catalyst molybdenum disulfide nanomaterial prepared in the embodiment is subjected to Transmission Electron Microscope (TEM) characterization, and the result is as follows:
referring to FIG. 5a, liquid nitrogen cooled deposition is shown High resolution TEM and diffraction patterns (upper right hand inset) of MoS 2 nanoparticles without annealing (RT), from which it can be seen that the particles are spherical, with a polycrystalline domain structure, creating many interfaces and defects. FIGS. 5 b-5 f are deposition/>The MoS 2 nano-particles were annealed at 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ for 20min, and then high-resolution TEM images and diffraction patterns were obtained. As can be seen from the figure, as the annealing temperature increases, the polycrystalline domain structure on the MoS 2 nanoparticle edge gradually decreases, the crystal orientation gradually tends to be uniform, and the interface and defect number decrease.
Example 5
The preparation method of this example is different from that of example 1 in that: the used substrate is a carbon cloth substrate and a foam nickel substrate, molybdenum disulfide nano materials are respectively deposited and annealed for comparison. The carbon cloth substrate is subjected to acid washing and high-temperature cleaning in the vacuum cavity before deposition. The pickling step is that the substrate is soaked in concentrated nitric acid at 100 ℃ for 2 hours in argon atmosphere, rinsed to be neutral by deionized water, soaked in absolute ethyl alcohol for 20 minutes for ultrasonic cleaning, and finally dried in a vacuum drying oven for standby. The high-temperature cleaning process in the vacuum cavity is that after the carbon cloth is put into the vacuum cavity, the carbon cloth is heated for 10min at 500 ℃, and the vacuum degree of the cavity in the cleaning process is 10 -7-10-8 Pa.
HER electrochemical test is carried out on the high-performance hydrogen evolution catalyst nano material prepared in the embodiment in a 1M KOH solution, and the result is as follows:
referring to fig. 6 a-6 b, a linear sweep voltammogram and a overpotential map corresponding to a current density of 1000mA cm -2 for the present example using a molybdenum disulfide nanomaterial with a carbon cloth substrate and a foam nickel substrate annealed at room temperature and 400 ℃, respectively. According to the 1M KOH HER catalytic performance test result, the molybdenum disulfide nano material deposited on the foam nickel substrate shows better catalytic performance under the condition of the same annealing temperature.
Example 6
The preparation method of this example is different from that of example 1 in that: the molybdenum disulfide room temperature catalyst sample of the foamed nickel substrate prepared in example 1 maintained stable catalytic activity for more than 1840 hours at 1000mA cm -2 current density. The steps in fig. 7 are caused when changing electrolyte.
Referring to FIG. 7, a graph of constant voltage polarization at 1000mA cm -2 current density for the molybdenum disulfide room temperature catalyst using a foam nickel substrate of this example is shown. According to the illustration in FIG. 7, the catalytic activity was maintained stable at a current density of 1000mA cm -2 for more than 1840 hours.
Example 7
This embodiment differs from embodiment 1 in that: vacuum sputtering power of 10W, deposition rate ofThe flow of argon is 20sccm, the flow of helium is 20sccm, the vacuum degree of the ultra-high vacuum environment is 10 -3 Pa, the annealing treatment time is 10min, and the rest conditions are the same.
Example 8
This embodiment differs from embodiment 1 in that: the vacuum sputtering power was 36W and the deposition rate wasThe flow of argon is 300sccm, the flow of helium is 5000sccm, the vacuum degree of the ultra-high vacuum environment is 10 -7 Pa, the annealing treatment time is 1h, and the rest conditions are the same.
Comparative example 1
Sen Xue et al synthesized a MoS2/Ni3S2NW-NF catalyst using a one-step hydrothermal process, which had an overpotential of 200mV at 1000mA cm -2 in 1mol KOH alkaline solution and remained stable for 12h at this current density. The nano material catalyst synthesized by a chemical method is difficult to regulate and control in morphology and has higher requirement on the selection of water-soluble precursors. The catalytic performance in this comparative example was inferior to the MoS 2 -NF catalyst of the present invention and the stability retention time was also much less than that of the catalyst of the present invention (https:// doi. Org/10.1016/j. Scib. 2019.10.024.).
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (10)
1. The preparation method of the high-performance hydrogen evolution catalyst is characterized by comprising the following steps of:
bombarding a molybdenum disulfide target material by a radio frequency power supply, and synthesizing a nanoscale molybdenum disulfide nano material in an inert gas atmosphere;
And depositing the molybdenum disulfide nano material on a substrate, and then annealing the obtained composite material in an ultrahigh vacuum environment to obtain the high-performance hydrogen evolution catalyst.
2. The method of manufacturing according to claim 1, comprising: placing a substrate in a reaction cavity by adopting a vacuum sputtering inert gas condensation technology, taking a molybdenum disulfide target as a target material, introducing inert gas, bombarding the target material by adopting inert ions in a vacuum environment, condensing and gathering the sputtered molybdenum disulfide nano material to form clusters, and enabling beam flow formed by the clusters to reach a deposition cavity so as to deposit on the substrate; the vacuum environment used was a vacuum of greater than 1X 10 -3 Pa.
3. The method of claim 2, wherein the process conditions of the vacuum sputtering inert gas condensation technique include: vacuum sputtering power of 10-36W and deposition rate of
4. The method of manufacturing according to claim 1, characterized in that: the inert gas comprises at least any one of argon and helium, preferably, the flow of the argon is 20-300 sccm, and the flow of the helium is 20-5000 sccm.
5. The method of manufacturing according to claim 1, characterized in that: the particle size of the molybdenum disulfide nano material is 5-40 nm; and/or the morphology of the molybdenum disulfide nanomaterial comprises nanoparticles and/or nanoplatelets, preferably nanoparticles.
6. The method of manufacturing according to claim 1, characterized in that: the substrate comprises any one of carbon cloth, molybdenum net, foam nickel, foam copper, glass carbon sheet and gold sheet, preferably foam nickel; preferably, the pore diameter of the foam nickel is 1-100 mu m, and the thickness is 0.1-2 mm.
7. The method of manufacturing according to claim 1, further comprising: before the molybdenum disulfide nano material is deposited on a substrate, carrying out acid washing and natural air drying treatment on the substrate;
preferably, the pickling comprises: and sequentially carrying out ultrasonic cleaning on the substrate by using a mixed solution of absolute ethyl alcohol and acetone, a dilute hydrochloric acid solution, water and absolute ethyl alcohol.
8. The method of manufacturing according to claim 1, characterized in that: the vacuum degree of the ultra-high vacuum environment is 10 -3～10-7 pa, the annealing treatment temperature is 200-700 ℃, and the time is 10 min-1 h.
9. A high performance hydrogen evolution catalyst made by the method of any one of claims 1-8 comprising a substrate, and a nano-sized molybdenum disulfide nanomaterial supported on the substrate; preferably, the deposition thickness of the molybdenum disulfide nano material in the high-performance hydrogen evolution catalyst is 20-25 nm;
Preferably, the high performance hydrogen evolution catalyst has an overpotential as low as 148mV at 1000mA cm -2 and retains stable catalytic activity for HER for more than 1840 hours.
10. Use of the high performance hydrogen evolution catalyst of claim 9 in hydrogen evolution reactions.
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