A method for ion implantation loading of catalysts, catalysts prepared and uses thereof

Abstract

The application provides a method for ion implantation loading of a catalyst, and a prepared catalyst and application, and belongs to the technical field of electrochemical hydrogen production. Metal ion implantation is performed on the surface of a current collector or a carrier material, which brings two different effects, including an energy effect and a mass effect. The energy effect refers to that the metal ion implantation introduces defect sites and the like on the current collector or the carrier material, and assists in catalysis or assists in anchoring the implanted ions. The mass effect refers to that catalyst atoms are introduced on the current collector or the carrier material through the metal ion implantation mode, and the existence form of the loaded catalyst is a single atom or a few-atom cluster. The method can reduce the catalyst loading amount while increasing the specific surface area of the catalyst, so as to reduce the overpotential and improve the catalytic performance. Meanwhile, the method is a universal catalyst loading method. The results of the examples show that the catalyst prepared by the application can achieve the overpotential that can be achieved by 20wt% commercial Pt / C when the loading amount is 5wt%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrochemical hydrogen production, and particularly relates to a method for loading a catalyst by ion implantation, a prepared catalyst and application. BACKGROUND

[0002] The global demand for energy is increasing, and the environmental problems caused by the burning of fossil energy are becoming increasingly serious. It is urgent to develop renewable clean energy. Hydrogen has the advantages of high energy density (143 MJ / kg) and zero carbon emission when burned, and is considered to be the best substitute for traditional fossil energy. At present, using renewable energy such as solar energy and wind energy to electrolyze water to produce hydrogen is an effective means to convert renewable energy into green hydrogen energy. The water electrolysis hydrogen production technology has the advantages of near-zero emission and high product purity (up to 99.9%), and is the most potential clean hydrogen production technology. It is considered to be an effective solution to the energy crisis and environmental pollution problems. However, due to the complex multiple proton coupling and multiple electron transfer process involved in the cathode hydrogen evolution reaction and the anode oxygen evolution reaction in the process of water electrolysis hydrogen production, a higher cathode and anode polarization overpotential is required, which causes the actual operating voltage of the commercial electrolytic cell to be much higher than the theoretical value (1.23 V), resulting in low electrolysis efficiency and high energy consumption. It is not economical for large-scale hydrogen production. How to improve the energy conversion efficiency and reduce the power consumption has become a "bottleneck" problem to be solved. The electrocatalyst is the key to reducing the overpotential and improving the energy conversion efficiency. By selecting appropriate electrocatalysts, the kinetics of various reactions can be controlled, and the overpotential can be reduced. The most effective oxygen evolution and hydrogen evolution reaction catalysts currently recognized are Ir / Ru-based catalysts and Pt-based catalysts. At present, how to load the catalyst on the current collector mainly has the following methods: impregnation-liquid phase reduction method, colloidal method, electrochemical method or gas phase deposition method. However, the catalyst prepared by the existing method has a high noble metal loading amount, and the noble metal reserves are small and expensive, thereby limiting the large-scale application of the catalyst.

[0003] Therefore, how to make the catalyst have excellent catalytic performance under the condition of low noble metal loading or using non-noble transition metals has become a problem in the prior art. SUMMARY

[0004] The purpose of the present application is to provide a method for loading a catalyst by ion implantation, a prepared catalyst and application. The catalyst prepared by the method provided by the present application still has excellent catalytic performance when the metal loading amount is low.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] The present application provides a method for loading a catalyst by ion implantation, comprising the following steps:

[0007] carrying out metal ion implantation on the surface of the current collector to obtain a catalyst;

[0008] Or: (1) mixing the carrier material with a solvent and a binder to obtain a mixed slurry; the carrier material comprises at least one of graphene, a metal chalcogenide, a carbon nanotube and a graphyne;

[0009] (2) coating the mixed slurry obtained in step (1) onto a current collector to obtain a current collector loaded with a carrier material;

[0010] (3) carrying out metal ion implantation on the surface of the current collector loaded with the carrier material obtained in step (2) to obtain a catalyst.

[0011] Preferably, in step (1), the mass of the carrier material, the volume of the solvent and the volume of the binder are in a ratio of 1 mg:(180-220) μL:(10-20) μL.

[0012] Preferably, in step (2), the mass of the carrier material in the current collector loaded with the carrier material is in a ratio of (0.5-1.5) mg:1 cm 2 .

[0013] Preferably, in step (2), the current collector comprises one of carbon paper, carbon cloth, foamed copper and foamed nickel.

[0014] Preferably, in step (3), the metal ions comprise at least one of iron ions, cobalt ions, nickel ions, copper ions, gold ions, molybdenum ions, platinum ions, ruthenium ions, aluminum ions, niobium ions, rhodium ions, iridium ions, palladium ions, silver ions, titanium ions, zinc ions, chromium ions and manganese ions.

[0015] Preferably, in step (3), the implantation dose of the metal ions is 1×10 15 -5×10 17 ions·cm -2 .

[0016] Preferably, in step (3), the energy of the low-energy ion beam during implantation of the metal ions is 5-100 keV.

[0017] Preferably, in step (3), the implantation of the metal ions is carried out under vacuum conditions.

[0018] The present application also provides a catalyst prepared by the method of ion implantation and loading of the catalyst according to the above technical solution.

[0019] The present application also provides the use of the catalyst according to the above technical solution in the electrolysis of water to produce hydrogen.

[0020] The application provides a method for loading a catalyst by ion implantation, comprising the following steps: performing metal ion implantation on the surface of a current collector to obtain a catalyst; or: (1) mixing a carrier material, a solvent and a binder to obtain a mixed slurry; the carrier material comprises at least one of graphene, a metal chalcogenide, a carbon nanotube and a graphdiyne; (2) coating the mixed slurry obtained in the step (1) on a current collector to obtain a current collector loaded with the carrier material; (3) performing metal ion implantation on the surface of the current collector loaded with the carrier material obtained in the step (2) to obtain a catalyst. The application performs metal ion implantation on the surface of a current collector or the surface of a current collector loaded with a carrier material, which brings two different effects, including an energy effect and a mass effect. The energy effect refers to that the metal ion implantation can introduce defect sites and the like on the current collector or the carrier material, thereby assisting catalysis or assisting anchoring of the implanted ions; the mass effect refers to that the catalyst atoms are introduced on the current collector or the carrier material by the metal ion implantation, and the loaded catalyst exists in the form of a single atom or a few-atom cluster. The method can reduce the catalyst loading amount while increasing the specific surface area of the catalyst, so as to reduce the overpotential and improve the catalytic performance. Meanwhile, the method is a universal catalyst loading method. Since the uniformity of ion implantation can realize the uniformity of catalyst loading, the method can realize large-scale batch production of the catalyst, and is conducive to industrial application. The scale degree depends on the structure of the implantation machine. The results of the embodiments show that the catalyst prepared by the application can achieve the overpotential of 20wt% commercial Pt / C when the loading amount of the catalyst is 5wt%. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 A flowchart for preparing a catalyst by the method of the application and for electrochemical decomposition of water;

[0022] Figure 2 An LSV curve of an electrochemical hydrogen evolution reaction of the catalyst prepared in Example 1 of the application and commercial Pt / C;

[0023] Figure 3 A Tafel curve of an electrochemical hydrogen evolution reaction of the catalyst prepared in Example 1 of the application and commercial Pt / C;

[0024] Figure 4 An EIS curve of an electrochemical hydrogen evolution reaction of the catalyst prepared in Example 1 of the application and commercial Pt / C;

[0025] Figure 5 A C dl curve of an electrochemical hydrogen evolution reaction of the catalyst prepared in Example 1 of the application and commercial Pt / C;

[0026] Figure 6X-ray photoelectron spectroscopy (XPS) of the catalyst prepared in Example 1 of the present application;

[0027] Figure 7 X-ray photoelectron spectroscopy of Pt of the catalyst prepared in Example 1 of the present application; Figure 6 X-ray photoelectron spectroscopy of Pt of the catalyst prepared in Example 1 of the present application;

[0028] Figure 8 X-ray absorption near-edge structure spectroscopy (XANES) of Pt L3 edge of the catalyst prepared in Example 1 of the present application;

[0029] Figure 9 X-ray absorption near-edge structure spectroscopy of Pt L3 edge of the catalyst prepared in Example 1 of the present application; Figure 8 X-ray absorption near-edge structure spectroscopy of Pt L3 edge of the catalyst prepared in Example 1 of the present application;

[0030] Figure 10 Wavelet transform of the catalyst prepared in Example 1 of the present application; Figure 8 Wavelet transform of the catalyst prepared in Example 1 of the present application; Wavelet transform of the catalyst prepared in Example 1 of the present application;

[0031] High-resolution transmission electron microscopy (HRTEM) of the catalyst prepared in Example 1 of the present application; Figure 11 High-resolution transmission electron microscopy (HRTEM) of the catalyst prepared in Example 1 of the present application; Elemental EDS mapping of the catalyst prepared in Example 1 of the present application;

[0032] Elemental EDS mapping of the catalyst prepared in Example 1 of the present application; Figure 12 LSV curve of the catalyst prepared in Examples 2-4 of the present application for the electrochemical water splitting reaction for hydrogen evolution; LSV curve of the catalyst prepared in Examples 2-4 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0033] Tafel curve of the catalyst prepared in Examples 2-4 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 13 LSV curve of the catalyst prepared in Examples 1-2 of the present application for the electrochemical water splitting reaction for hydrogen evolution; LSV curve of the catalyst prepared in Examples 1-2 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0034] Tafel curve of the catalyst prepared in Examples 1-2 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 14 LSV curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; LSV curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0035] Tafel curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 15 Tafel curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0036] EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 16 EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0037] EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 17 EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0038] EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 18 EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0039] EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 19 EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution;

[0040] EIS curve of the catalyst prepared in Examples 5-6 of the present application for the electrochemical water splitting reaction for hydrogen evolution; Figure 20C curve of the catalyst prepared for the present application examples 5~6 for the hydrogen evolution reaction of the electrochemical decomposition of water dl curve;

[0041] Figure 21 LSV curve of the catalyst prepared for the present application examples 7~9 for the oxygen evolution reaction of the electrochemical decomposition of water;

[0042] Figure 22 Tafel curve of the catalyst prepared for the present application examples 7~9 for the oxygen evolution reaction of the electrochemical decomposition of water;

[0043] Figure 23 EIS curve of the catalyst prepared for the present application examples 7~9 for the oxygen evolution reaction of the electrochemical decomposition of water;

[0044] Figure 24 C curve of the catalyst prepared for the present application examples 7~9 for the oxygen evolution reaction of the electrochemical decomposition of water dl curve;

[0045] Figure 25 A target disc for placing a current collector in a process cavity of an ion implanter to perform ion implantation. DETAILED DESCRIPTION

[0046] The present application provides a method for ion implantation loading catalyst, comprising the following steps:

[0047] Performing metal ion implantation on the surface of the current collector to obtain a catalyst;

[0048] Or: (1) mixing the carrier material with a solvent and a binder to obtain a mixed slurry; the carrier material comprises at least one of graphene, metal chalcogenide, carbon nanotube and graphdiyne;

[0049] (2) coating the mixed slurry obtained in the step (1) onto the current collector to obtain a current collector loaded with the carrier material;

[0050] (3) performing metal ion implantation on the surface of the current collector loaded with the carrier material obtained in the step (2) to obtain a catalyst.

[0051] Unless otherwise specified, the present application does not have special limitations on the source of each raw material, and commercially available products known to those skilled in the art can be used.

[0052] The present application provides a method for ion implantation loading catalyst, comprising the following steps: performing metal ion implantation on the surface of the current collector to obtain a catalyst.

[0053] In the present application, the current collector preferably comprises one of carbon paper, carbon cloth, foamed copper and foamed nickel.

[0054] In the present application, the metal ions preferably include at least one of iron ions, cobalt ions, nickel ions, copper ions, gold ions, molybdenum ions, platinum ions, ruthenium ions, aluminum ions, niobium ions, rhodium ions, iridium ions, palladium ions, silver ions, titanium ions, zinc ions, chromium ions and manganese ions. In the present application, the metal ions act as catalysts.

[0055] In the present application, the injection dose of the metal ions is preferably 1 x 10 15 ~ 5 x 10 17 ions cm -2 , more preferably 3 x 10 16 ~ 2.5 x 10 17 ions cm -2 .

[0056] In the present application, the metal ions are preferably injected in the following manner: injecting a low-energy ion beam into the surface of the current collector under vacuum conditions.

[0057] In the present application, the pressure of the vacuum conditions is preferably 5 x 10 -3 ~ 5 x 10 -4 Pa, more preferably 2 x 10 -3 ~ 5 x 10 -4 Pa.

[0058] In the present application, the energy of the low-energy ion beam during the injection of the metal ions is preferably 5 ~ 100 keV, more preferably 10 ~ 50 keV, and further preferably 10 ~ 30 keV.

[0059] The present application limits the injection dose of the metal ions and the energy of the low-energy ion beam to the above ranges, so that the injected metal is a single atom or a small cluster of atoms, and the catalytic performance is further improved.

[0060] In the present application, the injection of the metal ions is preferably performed in an ion implanter. The present application does not have a special limitation on the model of the ion implanter, and any ion implanter known to those skilled in the art can be used. In the present application, the metal target in the ion implanter preferably includes at least one of iron target, cobalt target, nickel target, copper target, gold target, molybdenum target, platinum target, ruthenium target, aluminum target, niobium target, rhodium target, iridium target, palladium target, silver target, titanium target, zinc target, chromium target and manganese target. In the present application, the ion source of the ion implanter generates plasma directly from solid materials through metal vapor vacuum arc discharge, and then the metal ions are extracted through an extractor and a mass selector, and a high-current-density ion beam is obtained through acceleration.

[0061] The present application also provides a method for ion implantation loading of a catalyst, comprising the following steps:

[0062] (1) mixing the carrier material with a solvent and a binder to obtain a mixed slurry;

[0063] (2) coating the mixed slurry obtained in step (1) onto a current collector to obtain a current collector loaded with two-dimensional materials;

[0064] (3) performing metal ion implantation on the surface of the current collector loaded with two-dimensional materials obtained in step (2) to obtain a catalyst.

[0065] The present application mixes the carrier material with a solvent and a binder to obtain a mixed slurry.

[0066] In the present application, the carrier material includes at least one of graphene, metal chalcogenide, carbon nanotube and graphdiyne. In the present application, the carrier material enables subsequent metal ion to be uniformly loaded, further improving the performance of the catalyst. In the present application, the metal chalcogenide preferably includes molybdenum disulfide; the flake diameter of the molybdenum disulfide is preferably 0.2-5 μm; the thickness of the molybdenum disulfide is preferably 1-8 nm; the carbon nanotube is preferably a multi-walled carbon nanotube; the purity of the multi-walled carbon nanotube is preferably >95%, the length is preferably 0.5-2 μm, and the diameter is preferably <8 nm; the graphene is preferably reagent grade, the thickness is preferably 1-3 nm, the number of layers is preferably <3, and the diameter is preferably >50 μm. In the embodiments of the present application, the graphene, molybdenum disulfide and carbon nanotube are all purchased from Pioneer Nano. In the present application, the length of the graphdiyne is preferably 250 nm, and the thickness is preferably 2.35 nm. The present application does not have special limitations on the source of the graphdiyne, and products prepared by conventional commercial products or conventional preparation methods can be used.

[0067] In the present application, the solvent preferably includes at least one of isopropyl alcohol, anhydrous ethanol and deionized water, and more preferably isopropyl alcohol; the purity of the isopropyl alcohol is preferably >99.7%.

[0068] In the present application, the binder preferably includes at least one of Nafion solution, polyvinylidene fluoride (PVDF) and polyvinyl alcohol (PVA), and more preferably Nafion solution.

[0069] In the present application, the mass concentration of the Nafion solution is preferably 4-6%, and more preferably 5%.

[0070] In the present application, the mass of the carrier material, the volume of the solvent and the volume of the binder are preferably 1 mg:(180-220) μL:(10-20) μL, and more preferably 1 mg:185 μL:15 μL. The present application limits the mass of the carrier material, the volume of the solvent and the volume of the binder to the above range, which enables the carrier material to be sufficiently dispersed and subsequently better coated and bonded to the current collector.

[0071] The present application does not have special restrictions on the operation of mixing the carrier material with the solvent and the binder, and the raw materials are fully dispersed by using the material mixing technology known to those skilled in the art. In the embodiment of the present application, the mixing is ultrasonic; the ultrasonic time is 1 h; the ultrasonic temperature is room temperature; and the ultrasonic power is 1200 W.

[0072] After obtaining the mixed slurry, the present application coats the mixed slurry on the current collector to obtain a current collector loaded with the carrier material.

[0073] In the present application, the current collector preferably includes one of carbon paper, carbon cloth, foamed copper, and foamed nickel. The present application does not have special restrictions on the source of the carbon paper, the carbon cloth, the foamed copper, and the foamed nickel, and commercially available products known to those skilled in the art can be used. In the embodiment of the present application, the carbon paper is Toray brand from Suzhou Shengernuo Technology Co., Ltd.; the thickness of the foamed nickel is 1.6 mm, the surface density is 350 g / m 2 .

[0074] In the present application, the current collector is preferably pretreated before use.

[0075] In the present application, the pretreatment preferably includes cutting, washing, and drying in sequence.

[0076] The present application does not have special restrictions on the size of the cut current collector, and it can be selected according to actual needs. In the embodiment of the present application, the size of the cut current collector is 1*1 cm 2 .

[0077] In the present application, the washing preferably includes ultrasonic treatment with acetone, ethanol, and deionized water in sequence.

[0078] The present application does not have special restrictions on the amount of acetone, ethanol, and deionized water, and it can only cover the current collector.

[0079] The present application does not have special restrictions on the parameters of the ultrasonic treatment, and it only needs to ensure that the oil stains and impurities on the surface of the current collector are removed. In the embodiment of the present application, the ultrasonic treatment time is 30 min; the ultrasonic treatment temperature is room temperature; and the ultrasonic treatment power is 1200 W.

[0080] In the present application, the washing is used to remove the oil stains and impurities on the surface of the current collector.

[0081] In the present application, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 0.01 Pa to 1 Pa, more preferably 0.1 Pa; the temperature of the vacuum drying is preferably 60 to 80°C, more preferably 70°C; and the time of the vacuum drying is preferably 8 to 12 h, more preferably 10 h.

[0082] In the present application, the ratio of the mass of the carrier material in the carrier material-loaded current collector to the surface area of the current collector is preferably (0.5 to 1.5) mg: 1 cm 2 , more preferably 1 mg: 1 cm 2 . The present application limits the ratio of the mass of the carrier material in the carrier material-loaded current collector to the surface area of the current collector to the above range, which is more conducive to the subsequent loading of metal ions on the carrier and more conducive to the performance comparison with other loaded catalysts.

[0083] The present application does not have special limitations on the coating operation, and any coating technical solution known to those skilled in the art can be used as long as the ratio of the mass of the carrier material in the carrier material-loaded current collector to the volume of the current collector is within the above range after coating. In the embodiments of the present application, the coating is performed by using a pipette to drop the coating solution.

[0084] After the coating is completed, the present application preferably dries the coated product to obtain a carrier material-loaded current collector.

[0085] In the present application, the drying is preferably vacuum drying; the vacuum degree of the vacuum drying is preferably 0.01 Pa to 1 Pa, more preferably 0.1 Pa; the temperature of the vacuum drying is preferably 60 to 80°C, more preferably 70°C; and the time of the vacuum drying is preferably 8 to 12 h, more preferably 10 h.

[0086] After the carrier material-loaded current collector is obtained, the present application performs metal ion implantation on the surface of the carrier material-loaded current collector to obtain a catalyst.

[0087] In the present application, the metal ions preferably include at least one of iron ions, cobalt ions, nickel ions, copper ions, gold ions, molybdenum ions, platinum ions, ruthenium ions, aluminum ions, niobium ions, rhodium ions, iridium ions, palladium ions, silver ions, titanium ions, zinc ions, chromium ions, and manganese ions. In the present application, the metal ions serve as a catalyst.

[0088] In the present application, the implantation dose of the metal ions is preferably 1 x 10 15 to 5 x 10 17 ions·cm -2 , more preferably 3 x 10 16 to 2.5 x 10 17 ions·cm -2 .

[0089] In the present application, the metal ion implantation is preferably performed by implanting a low-energy ion beam into the surface of the current collector loaded with the carrier material under vacuum conditions.

[0090] In the present application, the pressure of the vacuum conditions is preferably 5x10 -3 Pa, more preferably 2x10 -4 Pa, and even more preferably 5x10 -3 Pa. -4

[0091] In the present application, the energy of the low-energy ion beam during the metal ion implantation is preferably 5-100 keV, more preferably 10-50 keV, and even more preferably 10-30 keV.

[0092] By limiting the implantation dose of the metal ions and the energy of the low-energy ion beam within the above ranges, the present application can make the implanted metal into single atoms or small atomic clusters, and further improve the catalytic performance.

[0093] In the present application, the metal ion implantation is preferably performed in an ion implanter. The present application does not have a special limitation on the type of the ion implanter, and any ion implanter known to those skilled in the art can be used. In the present application, the metal target in the ion implanter preferably includes at least one of iron target, cobalt target, nickel target, copper target, gold target, molybdenum target, platinum target, ruthenium target, aluminum target, niobium target, rhodium target, iridium target, palladium target, silver target, titanium target, zinc target, chromium target, and manganese target. In the present application, the ion source of the ion implanter generates plasma directly from solid materials through metal vapor vacuum arc discharge, and then the metal ions are extracted through an extractor and a mass selector, and a high-current-density ion beam is obtained through acceleration.

[0094] In the present application, the target source of the ion implanter excites and extracts metal ions, and when the metal ions are loaded onto the carrier, they are referred to as catalyst atoms. This is because in the current field of electrocatalysis, single-atom catalysis is a new concept proposed, which specifically refers to the monodisperse state of the catalyst on the carrier. Because the catalyst is adsorbed on the carrier, there will be more or less charge transfer and charge interaction, showing metal bonds and / or covalent bonds, and not an independent state. Even the catalyst atoms will interact with each other to form small atomic clusters.

[0095] The process schematic diagram for preparing the catalyst and for electrochemical decomposition of water by using the method of the present application is preferably as shown in Figure 1 From Figure 1 it can be seen that the carrier material is coated onto the current collector, and then the metal ion implantation is performed on the surface of the carrier material to obtain the catalyst, which can be used for electrochemical decomposition of water. ​

[0096] The present application performs metal ion implantation on the surface of the current collector or the current collector of the support carrier material, which brings two different effects, including energy effect and mass effect, the energy effect refers to that the metal ion implantation can introduce defect sites on the current collector or the carrier, which assists catalysis or anchors the implanted ions; the mass effect refers to that the catalyst atoms are introduced on the current collector or the carrier by means of metal ion implantation, the metal ions are implanted on the surface of the current collector or the carrier, and in the process of electrocatalytic decomposition of water, the metal ions continuously adsorb and desorb reaction intermediates, promote charge transmission and transfer, thereby effectively reducing the overpotential of the water oxidation-reduction reaction, controlling the preparation process, so that the loaded catalyst is a single atom or a few atom clusters, and a larger specific surface area is provided under the premise of less catalyst loading to reduce the overpotential and improve the catalytic performance.

[0097] The present application also provides a catalyst prepared by the method of ion implantation loading catalyst according to the above technical solution.

[0098] The catalyst prepared by the present application still has excellent catalytic performance when the loading amount of metal ions is low.

[0099] The present application also provides the application of the catalyst according to the above technical solution in electrolytic water hydrogen production.

[0100] The application of the present application is not specially limited, and the technical solution of the application known to those skilled in the art can be used.

[0101] The technical solutions in the present application will be described clearly and completely in combination with the embodiments in the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the present application.

[0102] Embodiment 1

[0103] A method of ion implantation loading catalyst: (1) Molybdenum disulfide (flake diameter 0.2-5 μm, thickness 1-8 nm, Xianfeng Nanometer), isopropyl alcohol and 5% mass concentration Nafion solution are mixed according to the ratio of 1 mg:185 μL:15 μL at room temperature, 1200 W power, and ultrasonic treatment is carried out for 1 h to obtain a mixed slurry;

[0104] (2) The carbon paper (Suzhou Shengernuo Technology Co., Ltd., brand Toray) is cut into 1*1 cm 2, acetone, ethanol and deionized water at room temperature, 1200W power for 30min, vacuum drying at 0.1Pa, 70℃ for 10h, then the mixed slurry obtained in step (1) was drop-coated on the surface of the cleaned and dried carbon paper by using a pipette, vacuum drying at 0.1Pa, 70℃ for 10h, to obtain the carbon paper loaded with molybdenum disulfide, wherein the mass ratio of molybdenum disulfide to the surface area of the carbon paper was 1mg:1cm 2 ;

[0105] (3) In the ion implanter, the target material of the ion implanter was platinum target, platinum ion implantation was carried out on the surface of the carbon paper loaded with molybdenum disulfide in step (2), and the low-energy ion beam was injected into the surface of the carbon paper loaded with molybdenum disulfide under the condition of vacuum at 1×10 -3 Pa, the implantation dose of platinum ions was 2.5×10 17 ions·cm -2 , and the energy of the low-energy ion beam was 20keV, to obtain a catalyst, which was recorded as MoS2-5.0Pt.

[0106] Example 2

[0107] A method for loading a catalyst by ion implantation: (1) graphene (reagent grade, thickness 1-3nm, layer number <3, diameter 50-100μm, Pioneer Nano), isopropyl alcohol and Nafion solution with a mass concentration of 5% were ultrasonically treated at room temperature for 1h under the condition of 1200W power, to obtain a mixed slurry;

[0108] (2) carbon paper (Suzhou Shengernano Technology Co., Ltd., brand Toray) was cut into 1*1cm 2 , acetone, ethanol and deionized water at room temperature, 1200W power for 30min, vacuum drying at 0.1Pa, 70℃ for 10h, then the mixed slurry obtained in step (1) was drop-coated on the surface of the cleaned and dried carbon paper by using a pipette, vacuum drying at 0.1Pa, 70℃ for 10h, to obtain the carbon paper loaded with graphene, wherein the mass ratio of graphene to the surface area of the carbon paper was 1mg:1cm 2 ;

[0109] (3) In the ion implanter, platinum ion implantation was carried out on the surface of the carbon paper loaded with graphene in step (2), and the low-energy ion beam was injected into the surface of the carbon paper loaded with graphene under the condition of vacuum at 1×10 -3 Pa, the implantation dose of platinum ions was 2.5×10 17 ions·cm -2 , and the energy of the low-energy ion beam was 20keV, to obtain a catalyst, which was recorded as 1mgGr-5.0Pt.

[0110] Example 3

[0111] A method for loading catalyst by ion implantation: (1) Molybdenum disulfide (pore size 0.2-5 μm, thickness 1-8 nm, Pioneer Nanometer), isopropyl alcohol and Nafion solution with a mass concentration of 5% are ultrasonically treated at room temperature under a power of 1200 W for 1 h in a ratio of 1 mg:185 μL:15 μL to obtain a mixed slurry;

[0112] (2) Carbon paper (Suzhou Sheng'ernuo Technology Co., Ltd., brand Toray) is cut into 1*1 cm 2 , and is sequentially ultrasonically treated in acetone, ethanol and deionized water at room temperature under a power of 1200 W for 30 min, and is vacuum dried at 0.1 Pa and 70 ℃ for 10 h, then the mixed slurry obtained in step (1) is drop-coated onto the surface of the cleaned and dried carbon paper by using a pipette gun, and is vacuum dried at 0.1 Pa and 70 ℃ for 10 h to obtain carbon paper loaded with molybdenum disulfide, wherein the mass ratio of molybdenum disulfide to the surface area of the carbon paper is 1 mg:1 cm 2 ;

[0113] (3) In an ion implanter, iron ion implantation is performed on the surface of the carbon paper loaded with molybdenum disulfide in step (2), and low-energy ion beam is implanted onto the surface of the carbon paper loaded with molybdenum disulfide under a vacuum condition of 1×10 -3 Pa, the implantation dose of iron ions is 2.5×10 17 ions·cm -2 , the energy of the low-energy ion beam is 20 keV to obtain a catalyst, which is denoted as 1 mg MoS2-5.0 Fe.

[0114] Example 4

[0115] A method for loading catalyst by ion implantation: (1) Carbon nanotubes (multi-walled carbon nanotubes, purity >95%, length 0.5-2 μm, diameter <8 nm, Pioneer Nanometer), isopropyl alcohol and Nafion solution with a mass concentration of 5% are ultrasonically treated at room temperature under a power of 1200 W for 1 h in a ratio of 1 mg:185 μL:15 μL to obtain a mixed slurry;

[0116] (2) Carbon paper (Suzhou Sheng'ernuo Technology Co., Ltd., brand Toray) is cut into 1*1 cm 2 , and is sequentially ultrasonically treated in acetone, ethanol and deionized water at room temperature under a power of 1200 W for 30 min, and is vacuum dried at 0.1 Pa and 70 ℃ for 10 h, then the mixed slurry obtained in step (1) is drop-coated onto the surface of the cleaned and dried carbon paper by using a pipette gun, and is vacuum dried at 0.1 Pa and 70 ℃ for 10 h to obtain carbon paper loaded with molybdenum disulfide, wherein the mass ratio of molybdenum disulfide to the surface area of the carbon paper is 1 mg:1 cm 2 ;

[0117] (3) In an ion implanter, nickel ions were implanted onto the carbon paper surface loaded with carbon nanotubes in step (2) at a density of 1×10⁻⁶. -3 Under vacuum conditions, a low-energy ion beam was implanted into the surface of carbon paper loaded with carbon nanotubes, with an implantation dose of 3 × 10⁻⁶ nickel ions. 16 ions·cm -2 The energy of the low-energy ion beam was 20 keV, and the catalyst was obtained, denoted as 1 mg CNT-3E16Ni.

[0118] Example 5

[0119] A method for loading a catalyst by ion implantation: (1) Carbon nanotubes (multi-walled carbon nanotubes, purity >95%, length 0.5~2μm, diameter <8nm, pioneer nanotubes), isopropanol and 5% Nafion solution are ultrasonicated at room temperature and 1200W power for 1h in a ratio of 1mg:185μL:15μL to obtain a mixed slurry;

[0120] (2) Nickel foam (1.6 mm thick, 350 g / m³ surface density) 2 Cut into 1*1cm pieces 2 The mixture was ultrasonically treated with acetone, ethanol, and deionized water at room temperature and 1200W power for 30 min, respectively, and then vacuum dried at 0.1 Pa and 70℃ for 10 h. The mixed slurry obtained in step (1) was then drop-coated onto the cleaned and dried nickel foam surface using a pipette and vacuum dried at 0.1 Pa and 70℃ for 10 h to obtain nickel foam loaded with carbon nanotubes, wherein the mass ratio of carbon nanotubes to the surface area of ​​nickel foam was 1 mg: 1 cm³. 2 ;

[0121] (3) In an ion implanter, platinum ions were implanted onto the nickel foam surface loaded with carbon nanotubes in step (2) at a density of 1×10⁻⁶. -3 Under vacuum conditions of Pa, a low-energy ion beam was implanted into the surface of nickel foam loaded with carbon nanotubes, with an implantation dose of 3 × 10⁻⁶ platinum ions. 16 ions·cm -2 The energy of the low-energy ion beam is 20keV, and the catalyst is obtained, denoted as NF-1mgCNT-3E16Pt.

[0122] Example 6

[0123] A method for loading a catalyst by ion implantation: (1) Carbon nanotubes (multi-walled carbon nanotubes, purity >95%, length 0.5~2μm, diameter <8nm, pioneer nanotubes), isopropanol and 5% Nafion solution are ultrasonicated at room temperature and 1200W power for 1h in a ratio of 1mg:185μL:15μL to obtain a mixed slurry;

[0124] (2) Foam nickel (thickness of 1.6 mm, surface density of 350 g / m 2 ) was cut into 1*1 cm 2 , and was sequentially subjected to ultrasonic treatment in acetone, ethanol and deionized water at room temperature and 1200 W power for 30 min, and vacuum drying at 0.1 Pa and 70°C for 10 h. Then the mixed slurry obtained in step (1) was drop-coated onto the surface of the cleaned and dried foam nickel by using a pipette, and vacuum drying at 0.1 Pa and 70°C for 10 h to obtain foam nickel loaded with carbon nanotubes, wherein the mass ratio of carbon nanotubes to the surface area of foam nickel was 1 mg: 1 cm 2 ;

[0125] (3) In the ion implanter, iron ion implantation was performed on the surface of the foam nickel loaded with carbon nanotubes in step (2) under the condition of 1 x 10 -3 Pa vacuum, and the low-energy ion beam was implanted into the surface of the foam nickel loaded with carbon nanotubes, and the implantation dose of iron ions was 3 x 10 16 ions·cm -2 , and the energy of the low-energy ion beam was 20 keV to obtain a catalyst, which was recorded as NF-1 mgCNT-3E16Fe.

[0126] Example 7

[0127] A method for loading a catalyst by ion implantation: (1) Carbon nanotubes (multi-walled carbon nanotubes, purity > 95%, length of 0.5-2 μm, diameter < 8 nm, Xianfeng Nanometer), isopropyl alcohol and Nafion solution with a mass concentration of 5% were ultrasonically treated at room temperature and 1200 W power for 1 h in a ratio of 1 mg: 185 μL: 15 μL to obtain a mixed slurry;

[0128] (2) Foam nickel (thickness of 1.6 mm, surface density of 350 g / m 2 ) was cut into 1*1 cm 2 , and was sequentially subjected to ultrasonic treatment in acetone, ethanol and deionized water at room temperature and 1200 W power for 30 min, and vacuum drying at 0.1 Pa and 70°C for 10 h. Then the mixed slurry obtained in step (1) was drop-coated onto the surface of the cleaned and dried foam nickel by using a pipette, and vacuum drying at 0.1 Pa and 70°C for 10 h to obtain foam nickel loaded with carbon nanotubes, wherein the mass ratio of carbon nanotubes to the surface area of foam nickel was 1 mg: 1 cm 2 ;

[0129] (3) In the ion implanter, iron ion implantation was performed on the surface of the foam nickel loaded with carbon nanotubes in step (2) under the condition of 1 x 10 -3Pa vacuum conditions, low-energy ion beam is injected to the surface of the carbon nanotube loaded nickel foam, the injection dose of iron ions is 1×10 17 ions·cm -2 , the energy of the low-energy ion beam is 20 keV, to obtain a catalyst, recorded as NF-1mgCNT-1E17Fe.

[0130] Example 8

[0131] A method for loading a catalyst by ion implantation: (1) carbon nanotubes (multi-walled carbon nanotubes, purity > 95%, length 0.5-2 μm, diameter < 8 nm, Xianfeng Nanometer), isopropyl alcohol and Nafion solution with a mass concentration of 5% are ultrasonically treated at room temperature under a power of 1200 W for 1 h in a ratio of 1 mg:185 μL:15 μL to obtain a mixed slurry;

[0132] (2) cut the nickel foam (thickness 1.6 mm, surface density 350 g / m 2 ) into 1*1 cm 2 , sequentially ultrasonically treat with acetone, ethanol and deionized water at room temperature under a power of 1200 W for 30 min, vacuum dry at 0.1 Pa and 70°C for 10 h, then drop coat the mixed slurry obtained in step (1) onto the surface of the cleaned and dried nickel foam using a pipette, vacuum dry at 0.1 Pa and 70°C for 10 h to obtain a carbon nanotube loaded nickel foam, wherein the mass ratio of the carbon nanotubes to the surface area of the nickel foam is 1 mg:1 cm 2 ;

[0133] (3) in the ion implantation machine, perform cobalt ion implantation on the surface of the carbon nanotube loaded nickel foam of step (2), under 1×10 -3 Pa vacuum conditions, low-energy ion beam is injected to the surface of the carbon nanotube loaded nickel foam, the injection dose of cobalt ions is 1×10 17 ions·cm -2 , the energy of the low-energy ion beam is 20 keV, to obtain a catalyst, recorded as NF-1mgCNT-1E17Co.

[0134] Example 9

[0135] A method for loading a catalyst by ion implantation: (1) carbon nanotubes (multi-walled carbon nanotubes, purity > 95%, length 0.5-2 μm, diameter < 8 nm, Xianfeng Nanometer), isopropyl alcohol and Nafion solution with a mass concentration of 5% are ultrasonically treated at room temperature under a power of 1200 W for 1 h in a ratio of 1 mg:185 μL:15 μL to obtain a mixed slurry;

[0136] (2) cut the nickel foam (thickness 1.6 mm, surface density 350 g / m 2) cutting into 1*1 cm 2 , sequentially using acetone, ethanol and deionized water, respectively, under ultrasonic treatment at room temperature for 30 min, under 1200 W power, vacuum drying at 0.1 Pa and 70℃ for 10 h, then the mixed slurry obtained in step (1) is drop-coated on the surface of the cleaned and dried nickel foam by using a pipette, vacuum drying at 0.1 Pa and 70℃ for 10 h, to obtain the nickel foam loaded with carbon nanotubes, wherein the mass ratio of the carbon nanotubes to the surface area of the nickel foam is 1 mg:1 cm 2 ;

[0137] (3) in the ion implanter, iron ion implantation is performed on the surface of the nickel foam loaded with carbon nanotubes in step (2), under vacuum condition of 1×10 -3 Pa, low-energy ion beam is implanted into the surface of the nickel foam loaded with carbon nanotubes, the implantation dose of the iron ions is 2.5×10 17 ions·cm -2 , and the energy of the low-energy ion beam is 20 keV, to obtain a catalyst, denoted as NF-1mgCNT-2.5E17Fe.

[0138] Application Example

[0139] The catalysts prepared in Examples 1-9 and commercial Pt / C are used for electrochemical decomposition of water to produce hydrogen, using a three-electrode system, wherein the catalysts prepared in Examples 1-9 and the commercial Pt / C are working electrodes, the counter electrode is a platinum sheet electrode, the reference electrode is Ag / AgCl immersed in saturated KCl solution, and the electrolyte is 1 mol / L KOH, LSV and CV measurements are performed in the potential range of-0.9-0.2 V relative to the standard hydrogen electrode, and the scan rates are 5 and 100 mV / s, respectively. The alternating current impedance measurement is performed under the same configuration, at a potential of 10 mA / cm 2 . -1 5

[0140] The catalysts prepared in Examples 1-9 and the commercial Pt / C are used for hydrogen evolution reaction in the reduction reaction of electrolytic water, and sweep CV (cyclic voltammogram), LSV (linear voltammogram), EIS (electrochemical impedance spectrum), C dl double-layer capacitance, and the fitted Tafel slope, etc. are performed, wherein CV is for a sufficient activation of the sample, LSV is for the overpotential at a certain current value, and 10 mA·cm -2 ​​The overpotential is compared with the value of the overpotential at the time, and during the actual electrolysis cell reaction, the actual potential of the cathode is lower than the theoretical potential, and the actual potential of the anode is higher than the theoretical potential. The voltage value is called overpotential, and the loss comes from electrochemical polarization and concentration difference polarization; the Tafel slope is usually fitted from the LSV curve, which is used to describe the relationship between the potential and the current density. The value of the Tafel slope represents the change of the potential when the current increases or decreases by 10 times. The smaller the value is, the faster the reaction kinetics of water electrolysis OER or HER is, and the better the catalytic activity is; EIS is used to characterize the impedance characteristics of the catalyst in various aspects through the change relationship between the alternating current impedance and the frequency. From the electrochemical impedance spectrum, the solution resistance (R s ) and the charge transfer resistance (R ct ) in the HER or OER process can be obtained, so as to analyze the electrochemical performance of the catalyst. The intercept of the front end of the semicircle with the X axis represents R s , which can be used to correct the polarization curve and compensate for the voltage loss caused by the solution resistance. The radius of the semicircle represents R ct , and the smaller the value is, the stronger the electron transport ability of the catalyst is, and the faster the kinetics process is; the electrochemical active area is the effective area participating in the electrochemical reaction. Generally, the electrode reaction includes a Faraday process and a non-Faraday process. The Faraday process is a process in which oxidation and reduction reactions occur on the electrode and charge transfer between the electrode and the solution interface. The non-Faraday process does not have oxidation and reduction reactions, and is due to the adsorption or desorption process and the charging and discharging of the double-layer at the electrode and solution interface, and causes current flow. The study of electrochemical active area (ECSA) is based on the principle of electrochemical double-layer capacitance (C dl ) in the non-Faraday process, and the ECSA is proportional to C dl , which can be compared by the C dl value of the catalyst. The cyclic voltammetry (CV) test is carried out at different scan rates with 0.1 V as the voltage window, and then the straight line of the relationship between the scan rate and the current density is fitted, and the slope of the straight line is C dl .

[0141] The LSV, Tafel, EIS and C dl curves of the catalyst prepared in Example 1 and the commercial Pt / C catalyst in the electrochemical decomposition of water hydrogen evolution reaction are shown in Figures 2-5 , respectively. The Pt content of the catalyst prepared in Example 1 is 5wt% by inductively coupled plasma emission spectrometer (ICP) test result, and the Pt content of the commercial Pt / C catalyst is 20wt%. It can be seen from Figures 2-5 that the dosage of platinum ion implantation is 2.5x10 17 ions·cm-2 Its catalytic performance is superior to that of commercial Pt / C, reflecting its lower overpotential and representing its excellent catalytic performance. Meanwhile, its Tafel slope value (46.85 mV dec) is also superior. -1 (lower than commercial Pt / C (47.24mV dec)) -1 The smaller radius of the EIS impedance spectrum compared to commercial Pt / C reflects its rapid reaction kinetics. Its C... dl The value (249.95mF / cm) 2 The ratio is greater than that of commercial Pt / C (235.6 mF / cm). 2 This reflects its larger electrochemical active area.

[0142] The X-ray photoelectron spectroscopy (XPS) spectrum of the catalyst prepared in Example 1 is as follows: Figure 6 As shown, for Figure 6 The X-ray photoelectron spectrum of Pt peaks is shown in the figure after spectral decomposition. Figure 7 As shown. From Figures 6-7 The data shows the content and valence state of Pt. Zero-valence Pt is almost nonexistent, while divalent Pt is abundant. Pt may be associated with S. 2- After bonding, it exhibits a +2 valence.

[0143] The L3-side X-ray absorption near-side structure spectrum (XANES) of Pt in the catalyst prepared in Example 1 is as follows: Figure 8 As shown, through Figure 8 The peak value before the middle edge indicates that the valence state of the platinum single atom (Pt-SA) is between 0 and 4. Figure 8 Perform a transformation in R space to obtain Figure 9 . Figure 9 The structure fitting results show that Pt in the intermediate valence state between 0 and 4 exists in the form of Pt-S bonds. At the same time, no obvious Pt-Pt bonds appear in the R space transformation of the sample Pt-SA-MoS2, which further illustrates the single-atom existence of Pt. Figure 8 Wavelet transform diagram as shown Figure 10 As shown. Figure 10 By displaying the coordinate bond lengths, the types of coordinating atoms can be visually identified. From Figures 8-10 As can be seen from the data, after Pt was injected using molybdenum disulfide as a support, no obvious Pt-Pt bonds were observed in the synchrotron radiation spectrum, but obvious Pt-S bonds were observed. This indicates that the catalyst exists in the form of single atoms or few atoms in clusters, which has a larger specific surface area and thus higher catalytic activity.

[0144] Aberration-corrected high-resolution transmission electron microscope image of the catalyst prepared in Example 1 is shown below. Figure 11 As shown, throughFigure 11 The brightness of the middle atoms reveals the single-atom existence of Pt. The elemental EDS mapping diagram of the catalyst prepared in Example 1 is shown below. Figure 12 As shown. From Figure 12 As can be seen, Pt, S, and Mo elements are uniformly distributed in the catalyst.

[0145] The LSV and Tafel curves of the electrochemical water splitting and hydrogen evolution reaction of the catalysts prepared in Examples 2-4 are shown below. Figures 13-14 As shown. From Figures 13-14 It can be seen that ion implantation of electrocatalyst metal ions is a universal method, and different supports and implanted ions can be selected, resulting in various combinations. The Tafel slope values ​​are as follows: Example 2 (1 mg Gr-5.0 Pt) is 100.43 mV dec. -1 Example 3 (1 mg MoS2-5.0 Fe) had a dec V of 105.17 mV. -1 Example 3 (1 mg CNT-3E16Ni) had a dec V of 390.02 mV. -1 The catalyst with the best catalytic performance is still the one infused with Pt.

[0146] The LSV and Tafel curves of the electrochemical water splitting and hydrogen evolution reaction of the catalysts prepared in Examples 1 and 2 are shown below. Figures 15-16 As shown. From Figures 15-16 As can be seen, the Tafel slope values ​​are as follows: Example 1 (1 mg MoS2-5.0 Pt) is 46.85 mV dec. -1 Example 2 (1 mg Gr-5.0 Pt) had a dec of 100.43 mV. -1 With the same implanted ion Pt and the same implantation dose of 2.5 × 10⁻⁶, 17 ions·cm -2 The performance of MoS2 as a support is better than that of graphene as a support. The main reason is that graphene can provide good conductivity but is catalytically inert. The sulfur atom vacancies and edges of MoS2 itself can play a good catalytic role. Although defect sites are introduced to anchor Pt single atoms during the implantation process, the defects generated can also improve the catalytic activity of MoS2 itself.

[0147] The catalysts prepared in Examples 5-6 for the electrochemical water splitting and hydrogen evolution reaction LSV, Tafel, EIS, and C dl The curves are respectively as follows Figures 17-20 As shown. From Figures 17-20 It can be seen that the Tafel slope values ​​are as follows: Example 5 (NF-1mgCNT-3E16Pt) is 69.63mV dec -1Example 6 (NF-1mgCNT-3E16Mo) had a dec rate of 35.86 mV. -1 C dl The values ​​were as follows: Example 5 (NF-1 mg CNT-3 E16 Pt) was 460.9 mF / cm. 2

[0148] Example 6 (NF-1 mg CNT-3E16Mo) had a concentration of 296.87 mF / cm³. 2 Implanting ions onto nickel foam coated with 1 mg CNTs resulted in optimal catalytic performance with minimal dosage of Mo ions. The lowest Tafel slope also confirmed faster reaction kinetics than commercial Pt / C. The Ni-Mo alloy promotes the HER reaction, and the electron cloud density of the metallic bond formed by their electronic structures is favorable for the adsorption and desorption of hydrogen ions.

[0149] The catalysts prepared in Examples 7-9 for the electrochemical water splitting and oxygen evolution reaction LSV, Tafel, EIS, and C dl The curves are respectively as follows Figures 21-24 As shown. From Figures 21-24 It can be seen that the Tafel slope values ​​are as follows: Example 7 (NF-1mgCNT-1E17Fe) is 56.45mV dec -1 Example 8 (NF-1mgCNT-1E17Mo) had a dec rate of 80.21 mV. -1 Example 9 (NF-1mgCNT-2.5E17Fe) had a dec V of 46.57 mV. -1 C dl The values ​​were as follows: Example 7 (NF-1 mg CNT-1 E17 Fe) was 137.5 mF / cm. 2 Example 8 (NF-1 mg CNT-1 E17 Mo) had a concentration of 157.93 mF / cm³. 2 Example 9 (NF-1 mg CNT-2.5E17Fe) had a concentration of 264.33 mF / cm³. 2 Inject 2.5×10 17 ions·cm -2 Fe ions have the greatest promoting effect on the OER reaction, and Ni-Fe alloys promote the OER reaction, with a 10 mA·cm⁻¹ concentration. -2 The overpotential at this point is 254 mV, which is better than that of RuO2 (270 mV). In addition, its smallest Tafel slope reflects its fastest reaction kinetics, its smallest EIS radius reflects its smallest charge transfer resistance, and its largest double-layer capacitance reflects its largest electrochemical active area, representing the largest number of active sites.

[0150] Figure 25 A target disk is placed in a process cavity of an ion implanter for ion implantation to a current collector. Figure 25 As can be seen from the above, the method provided by the present application can be used for mass production.

[0151] In summary, the catalyst prepared by the present application has excellent catalytic performance even at a low catalyst loading amount, and has strong scalability in the selection of current collectors, carriers and ion species for implantation, and is a very universal catalyst synthesis and loading method.

[0152] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A method for ion implantation loading a catalyst, comprising the following steps: (1) The carrier material is mixed with a solvent and a binder to obtain a mixed slurry; the carrier material is molybdenum disulfide; (2) The mixed slurry obtained in step (1) is coated onto the current collector to obtain a current collector with a load carrier material; (3) Metal ions are implanted onto the surface of the current collector of the supported material obtained in step (2) to obtain a catalyst; In step (2), the ratio of the mass of the carrier material to the surface area of ​​the current collector in the current collector is (0.5~1.5) mg:1 cm². 2 The metal ions in step (3) are iron ions or platinum ions; the injection dose of the metal ions in step (3) is 1×10⁻⁶. 15 ~5×10 17 ions·cm −2 In step (3), the energy of the low-energy ion beam during metal ion implantation is 5~100keV.

2. The method according to claim 1, characterized in that, In step (1), the ratio of the mass of the carrier material, the volume of the solvent, and the volume of the binder is 1 mg: (180~220) μL: (10~20) μL.

3. The method according to claim 1, characterized in that, The current collector in step (2) includes one of carbon paper, carbon cloth, copper foam, and nickel foam.

4. The method according to claim 1, characterized in that, In step (3), metal ion implantation is performed under vacuum conditions.

5. The catalyst prepared by the ion implantation loading method according to any one of claims 1 to 4.

6. The application of the catalyst according to claim 5 in hydrogen production by water electrolysis.

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