A rare earth single atom-noble metal cluster composite catalyst, a preparation method and application thereof

Abstract

The application provides a rare earth single atom-noble metal cluster composite catalyst and a preparation method and application thereof, and belongs to the fields of material science and technology and electrocatalysis. The mass percentage of noble metal in the rare earth single atom-noble metal cluster composite catalyst is 0.28-1.2%, and the mass percentage of the rare earth single atom is 0.02%-0.03%. The noble metal includes ruthenium or rhodium, and the rare earth single atom includes cerium single atom or lanthanum single atom. The composite catalyst simultaneously contains atomically dispersed rare earth single atoms and noble metal clusters with an average size of 1 nm. By introducing atomically dispersed cerium single atoms, the alkaline hydrogen evolution performance of the noble metal cluster catalyst is greatly improved, so that the catalyst can achieve excellent hydrogen production performance when a very low amount of noble metal is used.

Description

Technical Field

[0001] This invention relates to the fields of materials science and technology and electrocatalysis, and in particular to a rare earth single-atom-noble metal cluster composite catalyst, its preparation method and application. Background Technology

[0002] Hydrogen energy is widely recognized as a green energy source capable of addressing resource shortages and environmental pollution, thus green hydrogen production technologies have received significant attention. Currently, hydrogen production technologies through water electrolysis are mainly categorized into alkaline water electrolysis, proton exchange membrane (PEM) water electrolysis, and solid oxide electrolysis. Compared to PEM and solid oxide electrolysis, alkaline water electrolysis offers advantages such as mature technology, ease of operation, and low equipment investment. However, hydrogen evolution in alkaline water electrolysis is limited by low current density and slow electrolysis efficiency. Specifically, under alkaline conditions, there are not a large number of free protons, resulting in slow electrode reaction kinetics. Alkaline cathode hydrogen evolution requires a high potential for water splitting, leading to significant energy waste. Therefore, designing and preparing highly efficient alkaline cathode hydrogen evolution catalysts is crucial.

[0003] Under alkaline conditions, the breaking of bonds in water molecules is the rate-determining step of the entire reaction. Even platinum, with its optimal hydrogen evolution activity, cannot effectively break the H-OH bonds in water molecules. Co-catalytic strategies can effectively optimize water splitting. For example, constructing noble metal-non-noble metal alloys or using transition metal oxides as supports to load noble metal active sites utilizes the oxygen / hydrophilic differences between noble and non-noble metals to optimize water molecule bond breaking and achieve efficient hydrogen evolution through co-catalysis. However, these optimization strategies still require high noble metal loading to achieve excellent alkaline hydrogen evolution performance. Summary of the Invention

[0004] To address the aforementioned issues, this invention provides a rare-earth single-atom-noble-metal cluster composite catalyst, its preparation method, and its application. This composite catalyst simultaneously contains atomically dispersed rare-earth single atoms and noble-metal clusters with an average size of 1 nm. By introducing atomically dispersed cerium single atoms, the alkaline hydrogen evolution performance of the noble-metal cluster catalyst is significantly improved, enabling the catalyst to achieve excellent hydrogen production performance even with extremely low amounts of noble metals.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a rare earth single-atom-noble metal cluster composite catalyst, wherein the mass percentage of noble metal in the rare earth single-atom-noble metal cluster composite catalyst is 0.28-1.2%, and the mass percentage of rare earth single atoms is 0.02-0.03%.

[0007] The precious metals include ruthenium or rhodium;

[0008] The rare earth single atom includes cerium single atom or lanthanum single atom.

[0009] Preferably, the mass percentage of noble metal in the rare earth single-atom-noble metal cluster composite catalyst is 1.0%.

[0010] This invention also provides a method for preparing the rare earth single-atom-noble metal cluster composite catalyst described in the above technical solution, comprising the following steps:

[0011] 1) Mix carbon materials and urea, and calcine them to obtain functionalized carbon carriers;

[0012] 2) Disperse the functionalized carbon support obtained in step 1) in a rare earth salt solution, stir, and dry to obtain a solid. Then, calcine the solid to obtain the calcined product.

[0013] 3) The calcined product obtained in step 2) is etched under acidic conditions and dried to obtain a rare earth single-atom modified carbon support.

[0014] 4) Disperse the rare earth single-atom modified carbon support obtained in step 3) in a noble metal salt solution, stir, and dry to obtain a precipitate. Then, reduce and calcine the precipitate to obtain a rare earth single-atom-noble metal cluster composite catalyst.

[0015] Preferably, the carbon material in step 1) includes activated carbon, carbon black, graphene, carbon nanotubes, or carbon aerogel.

[0016] The mass ratio of the carbon material to urea is 2:3;

[0017] The roasting conditions include a temperature of 300°C and a time of 4 hours.

[0018] Preferably, the rare earth salt in the rare earth salt solution in step 2) includes one or more of cerium nitrate, cerium chloride, cerium sulfate, cerium ammonium nitrate, cerium oxalate, and lanthanum nitrate;

[0019] The mass ratio of the functionalized carbon support to the volume ratio of the rare earth salt solution is 0.1 g: 20 mL.

[0020] The concentration of rare earth salts in the rare earth salt solution is 3.1 g / L.

[0021] Preferably, the conditions for the roasting treatment in step 2) include: roasting at 700°C for 2 hours in a 5% hydrogen-argon mixture.

[0022] Preferably, step 3) acidic conditions include etching at a pH of 1.0 for 2 hours.

[0023] Preferably, the noble metal salt in the noble metal salt solution in step 4) includes one or more of ruthenium chloride, trinitronitrosyl ruthenium, ruthenium acetylacetone, rhodium chloride, and rhodium nitrate;

[0024] The mass ratio of the rare earth single-atom modified carbon support to the volume ratio of the noble metal salt solution is 0.1 g: 20 mL.

[0025] The concentration of the precious metal in the precious metal salt solution is 0.25 g / L.

[0026] Preferably, the conditions for reduction roasting in step 4) include roasting for 2 hours at a temperature of 250-350°C with a 5% hydrogen-argon mixture.

[0027] This invention also provides the application of the rare earth single-atom-noble metal cluster composite catalyst described in the above technical solution in alkaline water electrolysis for hydrogen evolution.

[0028] The beneficial effects of this invention are as follows:

[0029] (1) This invention uses functionalized carbon materials as a carrier to prepare a rare earth single-atom and noble metal cluster composite catalyst by impregnation method. The cluster size is ultra-small. Compared with commercial platinum-carbon catalysts, the obtained composite catalyst exhibits superior electrocatalytic activity and stability in the alkaline water electrolysis hydrogen evolution reaction.

[0030] (2) In the composite catalyst of this invention, single atoms can not only regulate the electronic structure of noble metal clusters, but also optimize the adsorption mode of water molecules at active sites, thus optimizing the reaction pathway and exhibiting superior catalytic activity. The strong interaction between the ultra-small noble metal clusters and the support can effectively suppress problems such as Austrondell ripening and aggregation, exhibiting better stability. In 1M KOH solution, at 10 mA / cm², [the catalyst exhibits better stability]. 2 At the specified current density, the overpotential of the catalyst of this invention is only 26 mV. The noble metal content of the catalyst system is all below 1%, demonstrating strong practical application value. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the embodiments will be briefly described below.

[0032] Figure 1 The XRD test results are for Embodiment 1 and Comparative Example 1 of the present invention.

[0033] Figure 2 The results are HRTEM test results of the catalyst prepared in Example 1 of this invention.

[0034] Figure 3 The AC-TEM test results are for the catalyst prepared in Example 1 of this invention.

[0035] Figure 4 The linear voltammetric polarization curves of Example 1 and Comparative Example 1 of the present invention in 1 mol / L KOH solution are shown.

[0036] Figure 5 The catalyst prepared in Example 1 of this invention operates at 150 mA / cm². 2 Results of chronopotential method test at current density.

[0037] Figure 6 The XRD test results are for each of Embodiment 2 and Comparative Example 2 of the present invention.

[0038] Figure 7 The results are HRTEM test results of the catalyst prepared in Example 2 of this invention.

[0039] Figure 8 The LSV curves of Example 2 and Comparative Example 2 of the present invention in 1 mol / L KOH solution are shown.

[0040] Figure 9 The results are HRTEM test results of the catalyst prepared in Comparative Example 1 of this invention.

[0041] Figure 10 The results are HRTEM test results for the catalyst prepared in Comparative Example 2 of this invention. Detailed Implementation

[0042] This invention provides a rare-earth single-atom-noble-metal cluster composite catalyst, wherein the mass percentage of noble metal in the rare-earth single-atom-noble-metal cluster composite catalyst is 0.28-1.2%, and the mass percentage of rare-earth single atoms is 0.02-0.03%; the noble metal includes ruthenium or rhodium; and the rare-earth single atom includes cerium single atoms or lanthanum single atoms. In this invention, the preferred mass percentage of noble metal in the rare-earth single-atom-noble-metal cluster composite catalyst is 1.0%.

[0043] This invention also provides a method for preparing the rare earth single-atom-noble metal cluster composite catalyst described in the above technical solution, comprising the following steps:

[0044] 1) Mix carbon materials and urea, and calcine them to obtain functionalized carbon carriers;

[0045] 2) Disperse the functionalized carbon support obtained in step 1) in a rare earth salt solution, stir, and dry to obtain a solid. Then, calcine the solid to obtain the calcined product.

[0046] 3) The calcined product obtained in step 2) is etched under acidic conditions and dried to obtain a rare earth single-atom modified carbon support.

[0047] 4) Disperse the rare earth single-atom modified carbon support obtained in step 3) in a noble metal salt solution, stir, and dry to obtain a precipitate. Then, reduce and calcine the precipitate to obtain a rare earth single-atom-noble metal cluster composite catalyst.

[0048] This invention involves mixing and calcining carbon materials and urea to obtain a functionalized carbon carrier. In this invention, the carbon material preferably includes activated carbon, carbon black, graphene, carbon nanotubes, or carbon aerogel; in a specific embodiment, the carbon material is XC-72. In this invention, the mass ratio of the carbon material to urea is preferably 2:3. In this invention, the calcination conditions preferably include a temperature of 300°C and a time of 4 hours. Preferably, after calcination, the mixture is allowed to cool naturally to room temperature, dispersed in sufficient deionized water, and after thorough dispersion, filtered and washed until the filtrate is neutral. The separated solid is then dried at 60°C to obtain the functionalized carbon carrier.

[0049] This invention involves dispersing the obtained functionalized carbon support in a rare earth salt solution, stirring, and drying to obtain a solid. The solid is then calcined to obtain a calcined product. In this invention, the stirring is preferably performed at room temperature for 12 hours, and the drying is preferably performed at 60°C for at least 8 hours to completely remove residual moisture. In this invention, the rare earth salt in the rare earth salt solution preferably includes one or more of cerium nitrate, cerium chloride, cerium sulfate, cerium ammonium nitrate, cerium oxalate, and lanthanum nitrate. In this invention, the mass ratio of the functionalized carbon support to the volume of the rare earth salt solution is preferably 0.1 g:20 mL. In this invention, the concentration of the rare earth salt in the rare earth salt solution is preferably 3.1 g / L. In this invention, the calcination conditions preferably include: calcination at 700°C for 2 hours under a 5% (v / v) hydrogen-argon mixture.

[0050] This invention involves etching the obtained calcined product under acidic conditions and then drying it to obtain a rare-earth single-atom modified carbon support. Preferably, the acidic conditions include etching at pH 1.0 for 2 hours. More preferably, the calcined product is etched in a hydrochloric acid solution with a pH of 1.0.

[0051] This invention involves dispersing a rare-earth single-atom modified carbon support in a noble metal salt solution, stirring, and drying to obtain a precipitate. The precipitate is then subjected to reduction calcination to obtain a rare-earth single-atom-noble metal cluster composite catalyst. In this invention, the stirring is preferably performed at room temperature for 12 hours, and the drying is preferably performed at 60°C for at least 8 hours to completely remove residual moisture. In this invention, the noble metal salt in the noble metal salt solution preferably includes one or more of ruthenium chloride, trinitronitrosylruthenium, ruthenium acetylacetonate, rhodium chloride, and rhodium nitrate. In this invention, the mass ratio of the rare-earth single-atom modified carbon support to the volume of the noble metal salt solution is preferably 0.1 g: 20 mL. In this invention, the concentration of the noble metal in the noble metal salt solution is preferably 0.25 g / L. In this invention, the reduction calcination conditions preferably include calcination treatment at 250–350°C for 2 hours in a 5% hydrogen-argon mixture.

[0052] This invention also provides the application of the rare earth single-atom-noble metal cluster composite catalyst described in the above technical solution in alkaline water electrolysis for hydrogen evolution.

[0053] To further illustrate the present invention, the following detailed description is provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0054] Example 1

[0055] Weigh 3g of urea and 2g of commercially available XC-72, grind and mix them evenly. Transfer the resulting mixture to a crucible and place it in a muffle furnace to calcine at 300℃ for 4 hours. After naturally cooling to room temperature, disperse the calcined mixture in sufficient deionized water. After thorough dispersion, filter and wash until the filtrate is neutral. The separated solid product is dried in a 60℃ constant temperature oven to obtain the functionalized carbon support.

[0056] 2.177 g of Ce(NO3)3·6H2O solid was weighed and dissolved in 10 ml of ultrapure water for later use. 286 μl of cerium nitrate solution was pipetted into 20 ml of ultrapure water and diluted with stirring to obtain a cerium nitrate precursor salt solution with a concentration of 3.1 g / L. Next, 0.1 g of functionalized carbon support was weighed and added to the continuously stirred cerium nitrate precursor salt solution. The mixture was stirred continuously at room temperature for 12 h. After stirring, the mixture was centrifuged and dried in a 60°C oven for at least 8 hours to completely remove residual moisture. After drying, the resulting powder was calcined in a tube furnace for 2 h in a 5% hydrogen-argon mixture at a calcination temperature of 700°C. The calcined product was placed in a hydrochloric acid solution with pH = 1 and stirred at room temperature for 12 h. It was then centrifuged and dried in a 60°C oven to obtain a cerium single-atom modified support.

[0057] 530 μl of a 10 mg / ml RuCl3 solution was added to a beaker containing 10 ml of ultrapure water and stirred continuously. Then, 0.05 g of cerium single-atom modified support was added, and after stirring continuously for 12 hours, the precipitate obtained by centrifugation was dried in a constant temperature oven at 60 °C for at least 8 hours. The resulting black powder was placed in a tube furnace and reduced at 250 °C for 2 hours under a 5% hydrogen-argon mixed atmosphere to obtain the cerium single-atom-ruthenium metal cluster composite catalyst of this invention, named RuCeNC. The mass percentage of ruthenium in the catalyst is 1%, and the mass percentage of cerium in the catalyst is 0.03%. Figure 1 The XRD pattern of the prepared catalyst did not show obvious ruthenium, cerium, or other related phases, indicating that ruthenium and cerium are highly dispersed on the carbon support surface. Furthermore, Figure 2 High-resolution transmission electron microscopy images and Figure 3 Aberration-corrected electron microscopy images show that the ruthenium clusters on the support surface are highly dispersed, with an average size of 1.0 nm.

[0058] 4 mg of the above catalyst was weighed and dispersed in a mixed solution of 375 μl anhydrous ethanol, 125 μl ultrapure water, and 50 μl 5% Nafion solution (total solution volume 550 μl). The solution was sonicated for a certain time to ensure complete dispersion of the active components, resulting in a catalyst slurry. 2.5 μl of this slurry was dropped onto a 3 mm glassy carbon electrode and dried to obtain the working electrode. Electrochemical tests were performed using a three-electrode system in a single-chamber cell. The counter electrode was a graphite electrode, the reference electrode was a mercury oxide electrode filled with 1 M KOH, the working electrode was the aforementioned glassy carbon electrode, and the electrolyte was a 1 M KOH solution. The linear voltammetric polarization curve is shown below. Figure 4 High-current constant-current electrolysis stability test, such as Figure 5 Meanwhile, its performance was compared with that of a 20% commercial platinum-carbon catalyst, and the electrochemical activity is shown in Table 1.

[0059] Example 2

[0060] Functionalized carbon supports were prepared using the same method as in Example 1.

[0061] A 20 mL solution of 3.1 g / L lanthanum nitrate was prepared and stirred continuously. Then, 0.1 g of functionalized carbon support was weighed and added to the continuously stirred lanthanum nitrate precursor salt solution. The mixture was stirred continuously at room temperature for 12 h. After stirring, the mixture was centrifuged and dried in a 60 °C oven for at least 8 hours to completely remove residual moisture. After drying, the resulting powder was calcined in a tube furnace for 2 h in a 5% hydrogen-argon mixture at a temperature of 700 °C. The calcined product was then placed in a hydrochloric acid solution with pH = 1 and stirred at room temperature for 12 h. Subsequently, it was centrifuged and dried in a 60 °C oven to obtain the lanthanum single-atom modified support.

[0062] 530 μl of a 10 mg / ml RuCl3 solution was added to a beaker containing 10 ml of ultrapure water and stirred continuously. Then, 0.05 g of a lanthanum single-atom modified support was added, and the mixture was stirred continuously for 12 hours. The precipitate obtained by centrifugation was dried in a constant temperature oven at 60 °C for at least 8 hours. The resulting black powder was placed in a tube furnace and reduced at 250 °C for 2 hours under a 5% hydrogen-argon mixed atmosphere to obtain the lanthanum single-atom-ruthenium metal cluster composite catalyst of this invention, named RuLaNC. The ruthenium content in the catalyst was 1% by mass, the lanthanum content was 0.02%, and the average size of the Ru clusters on the support was 1.1 nm.

[0063] The lanthanum single-atom-ruthenium metal cluster composite catalyst of this embodiment was used as an alkaline water electrolysis hydrogen production catalyst and electrochemically tested in a three-electrode system (same as in Example 1). The electrochemical activity results are shown in Table 1.

[0064] Example 3

[0065] Functionalized carbon supports were prepared using the same method as in Example 1.

[0066] A cerium single-atom modified support was prepared using the same impregnation method and etching steps as in Example 1.

[0067] 293 μl of 0.05 M RhCl3 solution was added to a beaker containing 10 ml of ultrapure water and stirred continuously. Then, 0.05 g of cerium single-atom modified support was added, and after stirring continuously for 12 hours, the precipitate obtained by centrifugation was dried in a constant temperature oven at 60 °C for at least 8 hours. The resulting black powder was placed in a tube furnace and reduced at 350 °C for 2 hours under a 5% hydrogen-argon mixed atmosphere to obtain the cerium single-atom-rhodium metal cluster composite catalyst of this invention, named RhCeNC. The rhodium content in the catalyst was 0.28% by mass, and the cerium content was 0.03% by mass. Figure 6 The XRD pattern of the prepared catalyst did not show obvious rhodium, cerium, or other related phases, indicating that rhodium and cerium are highly dispersed on the carbon support surface. Furthermore, Figure 7 High-resolution transmission electron microscopy images reveal that the rhodium clusters on the support surface are highly dispersed, with an average size of 1.1 nm.

[0068] The cerium single-atom-rhodium metal cluster composite catalyst of this embodiment was used as an alkaline water electrolysis hydrogen production catalyst and electrochemically tested in a three-electrode system (same as in Example 1). The linear voltammetric polarization curve is shown below. Figure 8 The electrochemical activity results are shown in Table 1.

[0069] Comparative Example 1

[0070] Functionalized carbon supports were prepared using the same method as in Example 1.

[0071] 293 μl of 0.05 M RuCl3 solution was added to a beaker containing 10 ml of ultrapure water and stirred continuously. Then, 0.05 g of functionalized carbon support was added, and the mixture was stirred continuously for 12 hours. The precipitate obtained by centrifugation was dried in a constant temperature oven at 60 °C for at least 8 hours. The resulting black powder was placed in a tube furnace and reduced at 250 °C for 2 hours under a 5% hydrogen-argon mixed atmosphere to obtain the ruthenium metal cluster catalyst of this invention, named RuNC. Figure 1 It can be observed that no obvious ruthenium-related phases appear in the XRD pattern of the prepared catalyst. Figure 9 High-resolution transmission electron microscopy images reveal that the ruthenium clusters on the support surface are highly dispersed, with an average size of 1.3 nm.

[0072] The ruthenium metal cluster catalyst of this embodiment was used as an alkaline water electrolysis hydrogen production catalyst in a three-electrode system for electrochemical testing. The electrochemical activity results are shown in Table 1.

[0073] Comparative Example 2

[0074] Functionalized carbon supports were prepared using the same method as in Example 1.

[0075] 293 μl of a 10 mg / ml RhCl3 solution was added to a beaker containing 10 ml of ultrapure water and stirred continuously. Then, 0.05 g of cerium single-atom modified support was added, and after stirring continuously for 12 hours, the precipitate obtained by centrifugation was dried in a constant temperature oven at 60°C for at least 8 hours. The resulting black powder was placed in a tube furnace and reduced at 350°C for 2 hours under a 5% hydrogen-argon mixed atmosphere to obtain the cerium single-atom-rhodium metal cluster composite catalyst of this invention, named RhCeNC. The rhodium content in the catalyst was 1% by mass. Figure 6 No obvious rhodium-related phases appeared in the XRD pattern of the prepared catalyst. Figure 10 High-resolution transmission electron microscopy images reveal that the rhodium clusters on the support surface are highly dispersed, with an average size of 1.2 nm.

[0076] The rhodium metal cluster catalyst of this embodiment was used as an alkaline water electrolysis hydrogen production catalyst in a three-electrode system for electrochemical testing. The electrochemical activity results are shown in Table 1.

[0077] Table 1. Hydrogen production activity tests of Examples 1-3, Comparative Examples 1-2, and commercial platinum-carbon catalysts in alkaline water electrolysis.

[0078] Serial Number precious metal loading <![CDATA[10mA / cm 2 Overpotential (mV) Example 1 1.0 wt.% 25.4mV Example 2 1.0 wt.% 68.0mV Example 3 0.28 wt.% 16.2mV Comparative Example 1 1.3 wt.% 74.1mV Comparative Example 2 1.0 wt.% 116.8mV Commercial platinum carbon 20wt.% 41.6mV

[0079] Table 1 shows the noble metal content and concentration at 10 mA / cm² in Examples 1-3, Comparative Examples 1-2, and commercial platinum-carbon catalysts. 2A comparison of overpotentials at current densities reveals that the electrocatalytic hydrogen evolution performance is significantly improved when atomically dispersed rare-earth single atoms coexist with noble metal clusters on the substrate. Taking the aforementioned ruthenium-based catalyst as an example, when atomically dispersed cerium single atoms are present on the substrate, only 1.0 wt.% of the noble metal Ru is required to significantly surpass the alkaline electrocatalytic hydrogen evolution performance of 20% commercial PtC; while ruthenium cluster catalysts without single-atom modification struggle to achieve efficient alkaline hydrogen evolution. Therefore, atomically dispersed cerium single atoms can modulate the electronic structure of noble metal clusters to enhance the alkaline electrocatalytic hydrogen evolution performance of noble metals.

[0080] Figure 5 It can be seen that the rare earth single-atom-noble metal cluster catalyst obtained in this invention achieves a performance of 150 mA / cm². 2 It can operate stably for 12 hours under high current constant current electrolysis conditions, while the voltage increase of commercial platinum-carbon catalysts after 12 hours of constant current electrolysis reaches more than 250mV.

[0081] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a rare earth single atom-noble metal cluster composite catalyst, characterized in that, The method comprises the following steps: 1) mixing and calcining a carbon material and urea to obtain a functionalized carbon carrier; 2) dispersing the functionalized carbon carrier obtained in step 1) in a rare earth salt solution, stirring, and drying to obtain a solid, and performing calcination treatment on the solid to obtain a calcination product; 3) performing etching on the calcination product obtained in step 2) under acidic conditions, and drying to obtain a rare earth single atom modified carbon carrier; 4) dispersing the rare earth single atom modified carbon carrier obtained in step 3) in a noble metal salt solution, stirring, and drying to obtain a precipitate, and performing reduction calcination on the precipitate to obtain a rare earth single atom-noble metal cluster composite catalyst; The mass percentage content of the noble metal in the rare earth single atom-noble metal cluster composite catalyst is 0.28-1.2%, and the mass percentage content of the rare earth single atom is 0.02-0.03%. The noble metal includes ruthenium or rhodium. The rare earth single atom includes cerium single atom or lanthanum single atom.

2. The production method according to claim 1, characterized by, The mass percentage content of the noble metal in the rare earth single atom-noble metal cluster composite catalyst is 1.0%.

3. The preparation method according to claim 1, characterized in that, The carbon material in step 1) includes activated carbon, carbon black, graphene, carbon nanotube, or carbon aerogel. The mass ratio of the carbon material to urea is 2:

3. The calcination conditions include a temperature of 300°C and a time of 4h.

4. The method of claim 1, wherein, The rare earth salt in the rare earth salt solution in step 2) includes one or more of cerium nitrate, cerium chloride, cerium sulfate, cerium ammonium nitrate, cerium oxalate, and lanthanum nitrate. The mass of the functionalized carbon carrier to the volume of the rare earth salt solution is 0.1g:20mL. The concentration of the rare earth salt in the rare earth salt solution is 3.1g / L.

5. The preparation method according to claim 1, characterized in that, The calcination treatment conditions in step 2) include calcination treatment under 5% hydrogen-argon mixed gas and at a temperature of 700°C for 2h.

6. The method of claim 1, wherein, The acidic conditions in step 3) include etching at a pH value of 1.0 for 2h.

7. The preparation method according to claim 1, characterized in that, The noble metal salt in the noble metal salt solution in step 4) includes one or more of ruthenium chloride, ruthenium trinitrosyl nitrate, ruthenium acetylacetone, rhodium chloride, and rhodium nitrate. The mass of the rare earth single atom modified carbon carrier to the volume of the noble metal salt solution is 0.1g:20mL. The concentration of the noble metal in the noble metal salt solution is 0.25g / L.

8. The method of claim 1, wherein, The reduction calcination conditions in step 4) include calcination treatment under 5% hydrogen-argon mixed gas and at a temperature of 250-350°C for 2h.

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