Precious metal nanocluster modified 1T phase catalyst as well as preparation method and application thereof

Abstract

The invention discloses a noble metal nanocluster modified 1T phase catalyst and a preparation method and application thereof, the preparation method comprises the following steps: mixing a transition metal doped sheet 1T phase and / or 1T'phase substrate material with a noble metal salt solution, stirring for reaction, and then carrying out solid-liquid separation and washing to obtain the noble metal nanocluster modified 1T phase catalyst, by limiting the phase shape and morphology of the substrate material and doping the transition metal, the activity of the substrate material is regulated and controlled, the reaction rate of precious metal ions and sulfide or selenide and the like is increased, and the yield of the substrate material is increased under the condition that no medicament is added. And the noble metal nanocluster catalyst with high dispersion, high load and high uniformity can be rapidly prepared at room temperature by a one-step method.

Description

Technical Field

[0001] This invention relates to the field of electrocatalysis technology, and in particular to a noble metal nanocluster modified 1T phase catalyst, its preparation method and application. Background Technology

[0002] Noble metals have wide applications as catalysts in water electrolysis for hydrogen production and electrocatalytic production of organic compounds. However, their scarcity and high attrition characteristics severely hinder their widespread use in catalysis. Atomic catalytic cluster-type noble metal catalysts, on the other hand, can reduce costs and increase efficiency.

[0003] Transition metal sulfides and selenides have advantages such as wide availability, low price, good corrosion resistance, and good conductivity. They can also provide a huge support area for atomic clusters / single atoms. However, the atomic catalytic cluster-type noble metal catalysts prepared using sulfides and selenides as supports have low dispersion, low uniformity, and low loading rate of atomic catalytic clusters, resulting in poor electrochemical performance of noble metal catalysts. In addition, the reaction needs to be completed under high concentration of noble metal solution and long-term heating conditions, which makes the reaction complex and slow.

[0004] Therefore, there is a need to provide a preparation method for noble metal nanoclusters with high dispersion, uniformity, and loading to improve the electrochemical performance of composite catalysts. Summary of the Invention

[0005] In view of this, this application provides a noble metal nanocluster modified 1T phase catalyst, its preparation method and application, to solve the problem of how to improve the dispersion, uniformity and loading of noble metal nanoclusters in the noble metal nanocluster modified 1T phase catalyst.

[0006] To achieve the above technical objectives, this application adopts the following technical solution: In a first aspect, this application provides a method for preparing a noble metal nanocluster modified 1T phase catalyst, characterized by comprising the following steps: mixing a transition metal-doped sheet-like 1T phase and / or 1T' phase substrate material with a noble metal salt solution, stirring and reacting, and then separating the solid and liquid and washing to obtain the noble metal nanocluster modified 1T phase catalyst.

[0007] Preferably, the transition metal includes one or more of Fe, Co, and Ni.

[0008] Preferably, in the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material, the doping amount of the transition metal is 1.8-6.5%.

[0009] Preferably, the precious metal salt includes one or more of the following: precious metal chloride, precious metal nitrate, and precious metal sulfate; the precious metal includes one or more of the following: ruthenium, platinum, iridium, rhodium, and palladium.

[0010] Preferably, the concentration of the noble metal salt solution is 0.01-500 ppm, and the mass ratio of the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material to the noble metal salt is 1-20:1.

[0011] Preferably, the substrate material includes one or more of molybdenum sulfide, molybdenum selenide, vanadium sulfide, sulfides, tungsten selenide, molybdenum telluride, and titanium sulfide.

[0012] Preferably, the method for preparing the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material includes: adding a salt solution of a transition metal to a solution of the lamellar 1T phase and / or 1T' phase substrate material to obtain the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material.

[0013] Preferably, the temperature of the stirring reaction is 20-40℃, and the reaction time is 1-20 min.

[0014] Secondly, this application provides a noble metal nanocluster modified 1T phase catalyst.

[0015] Thirdly, this application provides an application of a noble metal nanocluster modified 1T phase catalyst in the fields of hydrogen production by water electrolysis and electrocatalytic preparation of organic compounds.

[0016] The beneficial effects of this application are as follows: This application regulates the activity of the substrate material by limiting the phase and morphology of the substrate material and doping it with transition metals, thereby accelerating the reaction rate of noble metal ions with sulfides or selenides, etc., and achieving rapid preparation of highly dispersed, highly loaded, and highly uniform noble metal nanocluster catalysts at room temperature in one step without adding any reagents. Attached Figure Description

[0017] Figure 1 This is a transmission electron microscope (TEM) image of 1T-MoS2-Ru; Figure 2 The X-ray diffraction (XRD) and Raman patterns of the catalysts prepared in Comparative Example 1 and Examples 1-3 are shown. Figure 3 The results of HER performance tests of 1T-MoS2-Ru prepared by Comparative Examples 1 and 11, 12 and 7 at different reaction times are shown. Figure 4 The results of HER tests on 1T phase molybdenum disulfide electrocatalysts modified with different noble metal nanoclusters prepared in proportions 1-5 are shown. Figure 5 These are the test results of the composite electrocatalytic HER performance of different metal dopants. Figure 5a shows the LSV curve. Figure 6These are scanning electron microscope (SEM) images of 1T-Fe / MoS2-Ru, 1T-Co / MoS2-Ru, and 1T-Ni / MoS2-Ru; Figure 7 These are transmission electron microscope (TEM) images of 1T-Fe / MoS2-Ru, 1T-Co / MoS2-Ru, and 1T-Ni / MoS2-Ru. Figure 8 HER performance testing of MoSe2 and VS2 before and after ruthenium nanocluster modification; Figure 9 The results show the performance of Fe metal-doped composite electrocatalysts for HER with different doping amounts. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0019] This application provides a method for preparing a noble metal nanocluster modified 1T phase catalyst, characterized by the following steps: mixing a transition metal-doped sheet-like 1T phase and / or 1T' phase substrate material with a noble metal salt solution, stirring and reacting, followed by solid-liquid separation and washing to obtain the noble metal nanocluster modified 1T phase catalyst.

[0020] In this application, the activity of the substrate material is controlled by limiting the phase and morphology of the substrate material and doping with transition metals, thereby accelerating the reaction rate of noble metal ions with sulfides or selenides. The high reaction rate provides more active sites to react synchronously with noble metal ions, increasing the dispersion and loading of noble metals on the substrate. Without adding any reagents, a one-step method is used to rapidly (within 20 min) prepare highly dispersed, highly loaded, and highly uniform noble metal nanocluster catalysts at room temperature.

[0021] The morphology, phase type, and doping of the catalyst simultaneously affect the loading and synergistically enhance the catalytic performance. In this application, the plate-like 1T phase doped with transition metals promotes the nanocluster particle size distribution and noble metal loading of the catalyst. Compared with the prior art, the advantages of the plate-like morphology are its large specific surface area, fast reaction rate, numerous active sites, and large loading. Unlike the reaction system of the 2H phase, which has a very slow reaction rate when immersed in solution and requires the addition of hydrogen peroxide to accelerate the reaction, this application modifies the 2H reaction system by using the 1T phase, which has a fast reaction rate. However, the addition of hydrogen peroxide will directly lead to the decomposition of molybdenum sulfide in the 1T phase. The reason for using transition elements in this application is that doping will cause the dopant element to replace the lattice position of molybdenum. The difference in the extranuclear electrons between the dopant element and molybdenum will lead to a decrease in the MS (chemical bond formed between the dopant element and sulfur) bond length, an increase in the SMS bond angle, and enhanced activity of sulfur atoms. If non-transition metal elements cannot achieve this purpose, it is because the extranuclear electron properties of non-transition elements are significantly different from those of molybdenum atoms and cannot replace molybdenum atoms.

[0022] After stirring the reaction, this application performs solid-liquid separation, then washes the product alternately with ethanol and deionized water, and finally dries it to obtain a noble metal nanocluster modified 1T phase catalyst.

[0023] In some embodiments, the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material includes one or more of the transition metal-doped lamellar 1T phase substrate material and the transition metal-doped lamellar 1T' phase substrate material.

[0024] In some embodiments, the transition metal includes one or more of Fe, Co, and Ni.

[0025] In some embodiments, the amount of transition metal doped in the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material is 1.8-6.5 wt%.

[0026] In this embodiment, too little doping can improve dispersibility, but reduce loading. This is because sulfur atoms bonded to the doped element are highly active, and reducing the doping amount will lead to a decrease in the number of highly active sulfur atoms. Too much doping has little effect on loading, but it results in waste of raw materials.

[0027] In some embodiments, the precious metal salt includes one or more of the precious metal chloride salt, precious metal nitrate salt, and precious metal sulfate salt; the precious metal includes one or more of ruthenium, platinum, iridium, rhodium, and palladium.

[0028] In some embodiments, the concentration of the noble metal salt solution is 0.01-500 ppm, and the mass ratio of the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material to the noble metal salt is 1-20:1; in some embodiments, the amount of noble metal salt solution added is 1-10 ml; in some embodiments, the amount of transition metal-doped lamellar 1T phase and / or 1T' phase substrate material used is 1-50 mg.

[0029] In this embodiment, too much substrate material will lead to increased load, but poorer dispersion and uniformity; while too little substrate material will lead to low load.

[0030] In some embodiments, the substrate material includes one or more of molybdenum sulfide, molybdenum selenide, vanadium sulfide, sulfides, tungsten selenide, molybdenum telluride, titanium sulfide, etc.

[0031] In some embodiments, the preparation method of the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material includes: adding a salt solution of a transition metal to a solution of the lamellar 1T phase and / or 1T' phase substrate material to obtain the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material.

[0032] The 1T phase catalyst was synthesized via a one-step hydrothermal method: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers, and the sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after being alternately washed with ultrapure water and ethanol to obtain 1T-MoS2. 1T-M / MoS2 was prepared by adding M(NO3)x (M = iron, cobalt, nickel) to the solution.

[0033] In some embodiments, the sheet-like 1T phase and / or 1T' phase substrate material includes, but is not limited to, one or more of the following: 1T phase molybdenum sulfide, 1T' phase molybdenum sulfide, 1T phase molybdenum selenide, 1T phase vanadium sulfide, 1T phase tungsten sulfide, 1T phase tungsten selenide, 1T phase molybdenum telluride, and 1T phase titanium sulfide.

[0034] In some embodiments, the temperature of the stirring reaction is 20-40°C, and the reaction time is 1-20 min.

[0035] This application provides a noble metal nanocluster modified 1T phase catalyst.

[0036] Using the method of this application, a 1T phase catalyst modified with noble metal nanoclusters can be prepared within 20 min using only a low concentration (0.01-500 ppm) noble metal salt solution. The 1T phase catalyst modified with noble metal nanoclusters includes a transition metal-doped sheet-like 1T phase and / or 1T' phase substrate material and noble metal nanocluster particles loaded on the transition metal-doped sheet-like 1T phase and / or 1T' phase substrate material. The nanocluster particles are of moderate size (1-1.5 nm) and have high dispersion uniformity (1-1.5 nm accounts for more than 90%), and high noble metal loading rate (more than 7 at.%).

[0037] This application provides the application of a noble metal nanocluster modified 1T phase catalyst in the fields of hydrogen production by water electrolysis and electrocatalytic preparation of organic compounds.

[0038] The following specific embodiments further illustrate this solution.

[0039] Raw material preparation: 6.46 wt% Fe-doped lamellar 1T phase MoS2 was prepared as follows: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, 0.0546 g Fe(NO3)3·9H2O, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers. The sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after alternating washing with ultrapure water and ethanol, and was designated as 1T-Fe / MoS2.

[0040] 1.78 wt% Co-doped flaky 1T-phase MoS2 was prepared as follows: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, 0.02 g Co(NO3)2·6H2O, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers. The sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after alternating washing with ultrapure water and ethanol, and was designated as 1T-Co / MoS2.

[0041] 1.96wt% Ni-doped lamellar 1T-phase MoS2 was prepared as follows: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, 0.02 g Ni(NO3)2·6H2O, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers. The sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after alternating washing with ultrapure water and ethanol, and was denoted as 1T-Ni / MoS2.

[0042] The 2wt% Fe-doped flaky 1T phase MoS2 was prepared as follows: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, 0.018 g Fe(NO3)3·9H2O, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers. The sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after alternating washing with ultrapure water and ethanol, and was designated as 1T-2%Fe / MoS2.

[0043] The preparation method of 8wt% Fe-doped flaky 1T phase MoS2 is as follows: 0.206 g ammonium molybdate tetrahydrate, 0.381 g thiourea, 0.073 g Fe(NO3)3·9H2O, and 0.03 g L-ascorbic acid were dissolved in 30 mL of ultrapure water. The mixed solution was transferred to a 50 mL autoclave lined with 20*20 mm graphite fibers. The sealed autoclave was then reacted at 200°C for 18 hours. The resulting product was dried after being alternately washed with ultrapure water and ethanol, and was designated as 1T-8%Fe / MoS2.

[0044] Example 1 A method for preparing a noble metal nanocluster modified 1T phase catalyst includes the following steps: Six mg of 6 wt% Fe-doped flake-like 1T phase MoS2 (1T-Fe / MoS2) was loaded onto a graphite felt with an area of ​​0.5 × 1 cm and then placed in 5 mL of 200 ppm ruthenium chloride solution. The mixture was stirred until homogeneous and reacted at room temperature (25 °C) for 5 min. The reaction product was filtered, washed alternately with ethanol and deionized water, and then dried to obtain a noble metal nanocluster modified 1T phase catalyst, labeled as 1T-Fe / MoS2-Ru. ICP detection results showed that the ruthenium nanocluster loading was 12.08 wt.%.

[0045] Example 2-3 A method for preparing a noble metal nanocluster modified 1T phase catalyst is described, which is otherwise the same as in Example 1, except that 1T-Fe / MoS2 is replaced with 1T-Co / MoS2 and 1T-Ni / MoS2 in sequence, resulting in 1T-Co / MoS2-Ru and 1T-Ni / MoS2-Ru respectively. ICP detection results show that the ruthenium nanocluster loadings of 1T-Co / MoS2-Ru and 1T-Ni / MoS2-Ru are 8.38 wt.% and 4.65 wt.%, respectively.

[0046] Examples 4-5 A method for preparing a noble metal nanocluster modified 1T phase catalyst is the same as in Example 1, except that 1T-Fe / MoS2 is replaced with 1T-2%Fe / MoS2 and 1T-8%Fe / MoS2 in sequence, resulting in 1T-2%Fe / MoS2-Ru and 1T-8%Fe / MoS2-Ru respectively.

[0047] Comparative Example 1 A method for preparing a noble metal nanocluster modified 1T phase catalyst is described, with other contents being the same as in Example 1, except that 1T-Fe / MoS2 is replaced with undoped plate-like 1T phase MoS2, and the product is designated as 1T-MoS2-Ru. ICP analysis results show that the ruthenium nanocluster loading is 8.54 wt.%.

[0048] Comparative Examples 2-5 A method for preparing a noble metal nanocluster modified 1T phase catalyst is the same as that in Comparative Example 1, except that the noble metal solution is replaced sequentially with rhodium chloride, palladium chloride, platinum chloride, and iridium chloride solutions to obtain 1T-MoS2-Rh, 1T-MoS2-Pd, 1T-MoS2-Pt, and 1T-MoS2-Ir respectively.

[0049] Comparative Examples 6-7 A method for preparing a noble metal nanocluster modified 1T phase catalyst is the same as that in Comparative Example 1, except that the 1T phase MoS2 is replaced with 1T phase molybdenum diselenide and 1T phase vanadium disulfide in sequence to obtain MoSe2-Ru and VS2-Ru respectively.

[0050] Comparative Examples 8-10 A method for preparing a noble metal nanocluster modified 1T phase catalyst is the same as that in Comparative Example 1, except that the reaction times are 1 min, 3 min and 4 min respectively.

[0051] Testing and Evaluation 1. Scanning electron microscopy and transmission electron microscopy tests (Comparative Example 1, Examples 1-3) Figure 1This is a transmission electron microscope (TEM) image of 1T-MoS2-Ru. It can be seen that the 1T-MoS2 modified with Ru nanoclusters is a flower-like structure assembled from sheets. However, a large number of black nanocluster particles are grown on the sheet structure, but their distribution uniformity is poor.

[0052] Figure 6 These are scanning electron microscope (SEM) images of 1T-Fe / MoS2-Ru, 1T-Co / MoS2-Ru, and 1T-Ni / MoS2-Ru. In the image, a is the SEM image of 1T-Fe / MoS2-Ru, b is the SEM image of 1T-Co / MoS2-Ru, and c is the SEM image of 1T-Ni / MoS2-Ru. It can be seen that the catalyst generally presents a plate-like shape, and the morphology varies due to doping.

[0053] Figure 7 These are transmission electron microscopy (TEM) images of 1T-Fe / MoS2-Ru, 1T-Co / MoS2-Ru, and 1T-Ni / MoS2-Ru. In the image, a is the TEM image of 1T-Fe / MoS2-Ru, b is the TEM image of 1T-Co / MoS2-Ru, and c is the TEM image of 1T-Ni / MoS2-Ru. The modification of ruthenium nanoclusters on the nanosheets can be clearly seen. Figure 7 Compared to a, 7b and 7c Figure 7 The nanoclusters in b are the largest. Figure 7 The smallest nanoclusters are found in c. Figure 7 The nanoclusters exhibit moderate density and the highest uniformity of dispersion. Their test data are shown in Table 1.

[0054] Table 1. Results of Dispersion and Uniformity Tests

[0055] 2. X-ray diffraction test Figure 2 The X-ray diffraction (XRD) patterns of the catalysts prepared in Comparative Example 1 and Examples 1-3 are shown below. Figure 2 a) and Raman diagram ( Figure 2 b). XRD analysis of different samples was used to characterize their crystal phase composition, while Raman spectroscopy was used to verify the XRD results from a chemical bonding perspective. Figure 2 As can be seen, there is no significant difference in crystal information between 1T-Fe / MoS2-Ru, 1T-Co / MoS2-Ru, and 1T-Ni / MoS2-Ru and 1T-Fe / MoS2-Ru compared with 1T-phase MoS2. XRD cannot directly detect the information of nanoclusters. Raman results show that the overall structure of the catalyst substrate does not change before and after nanocluster modification.

[0056] 3. Element content test The contents of Mo, S, Fe, Co, Ni, and Ru in the solid fraction of the ruthenium nanocluster modified catalyst obtained by solid-liquid separation (referred to as the final product) and the liquid fraction of the ruthenium nanocluster modified catalyst obtained by solid-liquid separation (referred to as the remaining solution) of the 1T phase substrate material in Comparative Example 1 and Examples 1-3 were tested by ICP method. The test results are shown in Table 2.

[0057] Table 2. Element content in materials at different stages

[0058] As can be seen from Table 1, the content of doped elements in the 1T phase substrate material decreases during the preparation process of this invention. This indicates that the noble metal salt solution causes sulfur atoms around the doped elements to preferentially participate in the reaction and generate noble metal nanoclusters during the preparation process. The comparison of ruthenium content shows that iron doping helps to increase the amount of noble metal nanocluster modification and achieve a high degree of dispersion. The remaining solution after the reaction contains doped elements with a large content, which verifies that the noble metal salt solution causes sulfur atoms around the doped elements to preferentially participate in the reaction and generate noble metal nanoclusters during the preparation process.

[0059] 4. Electrocatalytic performance test 4.1 Overpotential (electrocatalytic activity) test Electrochemical tests were performed on the noble metal nanoclusters modified 1T phase catalysts of Examples 1-5 using an electrochemical workstation (Princeton). Specifically, a three-electrode system was used for the tests, in which the composite electrocatalyst was the working electrode, the graphite rod was the counter electrode, and the mercury / mercury oxide electrode was the reference electrode. Electrochemical performance such as LSV and EIS were measured in 1.0 M KOH electrolyte solution.

[0060] Based on the above linear sweep voltammetry curves, the voltammetry results of 1T phase catalysts modified with different noble metal nanoclusters at 500 mA / cm² were obtained. 2 The overpotentials under high current density are shown in Table 3.

[0061] Table 3 Overpotential test results

[0062] As can be seen from Table 3, at high current density (500 mA / cm²), 2 The noble metal nanoparticle-modified sulfide composite catalyst prepared by this invention has a significantly reduced overpotential. The composite electrocatalyst has excellent electrocatalytic activity in water electrolysis and hydrogen evolution. The obtained catalyst has a small overpotential and a fast mass transfer rate when electrolyzing water at high current density.

[0063] 4.2 LSV and EIS Testing Figure 3The results of HER performance tests of 1T-MoS2-Ru prepared by Comparative Examples 1 and 11, 12 and 7 at different reaction times are shown in the figure. a is the LSV curve; b is the EIS curve. Figure 3 a indicates that 1T-MoS2-Ru reacts for 3 min or 5 min and exhibits the best performance in hydrogen production through water electrolysis. Figure 3 b indicates that 1T-MoS2-Ru reacted for 3 min or 5 min has the minimum mass transfer rate and the minimum internal resistance.

[0064] Figure 4 The results of HER tests on 1T phase molybdenum disulfide electrocatalysts modified with different noble metal nanoclusters prepared in proportions 1-5 are shown in Figure 4a, which shows the LSV curves of 1T phase molybdenum disulfide modified with different noble metal nanoparticles. Figure 4 b shows the EIS curves of composite electrocatalysts modified with different noble metal nanoparticles. It can be seen that 1T phase molybdenum disulfide modified with different noble metal nanoparticles can all improve the hydrogen production performance of water electrolysis, and the optimal hydrogen evolution performance corresponding to different reaction times varies for different composite catalysts.

[0065] Figure 5 The figures show the performance test results of composite electrocatalysts for HER with different metal doping. Figure 5a shows the LSV curve; Figure 5b shows the EIS curve. Figure 5 It can be seen that ruthenium nanoclusters modified with different transition metal doped 1T phase molybdenum disulfide exhibit better water electrolysis performance than undoped molybdenum disulfide, with Fe doping showing the best performance, followed by Co and Ni doping. Figure 8 The HER performance of MoSe2 and VS2 before and after modification with ruthenium nanoclusters is tested. In this paper, 8(a) represents LSV and 8(b) represents EIS. Figure 9 The figures show the HER performance test results of composite electrocatalysts with different Fe metal doping amounts. Figure 9a is the LSV curve; and Figure 9b is the EIS curve.

[0066] In this application, the activity of the substrate material is controlled by limiting the phase and morphology of the substrate material and doping it with transition metals, thereby accelerating the reaction rate of noble metal ions with sulfides or selenides. Under the condition of not adding any reagents, a one-step method is used to rapidly prepare highly dispersed, highly loaded, and highly uniform noble metal nanocluster catalysts at room temperature.

[0067] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a noble metal nanocluster modified 1T phase catalyst, characterized in that, Includes the following steps: The noble metal nanoclusters modified with the 1T phase catalyst are obtained by mixing the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material with a noble metal salt solution, stirring and reacting, followed by solid-liquid separation and washing.

2. The preparation method of the noble metal nanoclusters modified 1T phase catalyst according to claim 1, characterized in that, The transition metals include one or more of Fe, Co, and Ni.

3. The preparation method of the noble metal nanoclusters modified 1T phase catalyst according to claim 1, characterized in that, In the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material, the doping amount of the transition metal is 1.8-6.5%.

4. The preparation method of the noble metal nanoclusters modified 1T phase catalyst according to claim 1, characterized in that, The precious metal salt includes one or more of precious metal chloride salts, precious metal nitrate salts, and precious metal sulfate salts; the precious metal includes one or more of ruthenium, platinum, iridium, rhodium, and palladium.

5. The preparation method of the noble metal nanoclusters modified 1T phase catalyst according to claim 1, characterized in that, The concentration of the noble metal salt solution is 0.01-500 ppm, and the mass ratio of the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material to the noble metal salt is 1-20:

1.

6. The method for preparing a noble metal nanocluster modified 1T phase catalyst according to claim 1, characterized in that, The substrate material includes one or more of the following: molybdenum sulfide, molybdenum selenide, vanadium sulfide, sulfides, tungsten selenide, molybdenum telluride, and titanium sulfide.

7. The method for preparing a noble metal nanocluster modified 1T phase catalyst according to claim 1, characterized in that, The method for preparing the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material includes: adding a salt solution of a transition metal to a solution of the lamellar 1T phase and / or 1T' phase substrate material to obtain the transition metal-doped lamellar 1T phase and / or 1T' phase substrate material.

8. The method for preparing a noble metal nanocluster modified 1T phase catalyst according to claim 1, characterized in that, The temperature of the stirring reaction is 20-40℃, and the reaction time is 1-20 min.

9. A noble metal nanoclusters modified 1T phase catalyst obtained by the preparation method according to any one of claims 1-8.

10. The application of the noble metal nanocluster modified 1T phase catalyst as described in claim 9 in the fields of hydrogen production by water electrolysis and electrocatalytic preparation of organic compounds.

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