Rh monatomic hydrogen evolution catalyst and preparation method and application thereof
By preparing Rh single-atom hydrogen evolution catalysts, and utilizing P-doped carbon material supports and low-temperature annealing technology, the problem of insufficient performance of traditional catalysts under acidic conditions was solved, and a highly efficient electrocatalytic hydrogen production effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUDAN UNIVERSITY
- Filing Date
- 2024-10-15
- Publication Date
- 2026-04-17
AI Technical Summary
In existing electrocatalytic hydrogen production technologies, traditional catalysts have poor performance and are difficult to meet the requirements for efficient hydrogen evolution under acidic conditions. Furthermore, the types of single-atom catalysts are limited and their performance needs to be improved.
Using p-doped carbon materials as a support, a multi-step method was used to prepare Rh single-atom hydrogen evolution catalysts. Magnetic stirring and low-temperature annealing techniques were used to ensure that Rh atoms were uniformly distributed and firmly anchored on the support, thereby inhibiting the formation of nanoparticles and improving catalytic activity.
It achieves efficient hydrogen evolution under acidic conditions, optimizes the environment around Rh atoms to enhance catalytic activity, has a small metal loading to avoid loss of active sites, and has good electrocatalytic water splitting hydrogen production performance.
Smart Images
Figure CN121874833A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalytic hydrogen production technology, and in particular to a Rh single-atom hydrogen evolution catalyst, its preparation method, and its application. Background Technology
[0002] "Green hydrogen" can be produced by electrocatalytic water splitting using electricity generated from renewable energy sources such as wind and solar power, without producing carbon dioxide gas throughout the process. Therefore, electrocatalytic water splitting for hydrogen production is considered the most sustainable hydrogen production technology currently available. However, traditional catalysts used in electrocatalytic hydrogen production technologies have poor performance and cannot meet the needs of practical applications, necessitating the development of highly efficient and stable catalysts.
[0003] Single-atom catalysts are a new class of catalysts, typically exhibiting high catalytic performance and metal atom utilization. However, the types of single-atom catalysts currently used for electrocatalytic hydrogen production are relatively limited, and their performance needs further improvement.
[0004] Patent CN118621348 A discloses a highly efficient ruthenium single-atom / nanoparticle hydrogen evolution catalyst, its preparation method, and its application. This method prepares a highly efficient ruthenium single-atom / nanoparticle hydrogen evolution catalyst, where the ruthenium single atoms provide effective active sites for the hydrogen evolution reaction, enhancing catalytic activity. The unique nitrogen- and phosphorus co-doped carbon structure and the synergistic effect between the ruthenium single-atom / nanoparticles significantly improve the electrocatalytic activity and stability of HER. However, this is a catalyst applicable to hydrogen evolution reactions under alkaline pure water and seawater conditions. Summary of the Invention
[0005] The purpose of this invention is to provide a Rh single-atom hydrogen evolution catalyst, its preparation method and application, to achieve efficient hydrogen evolution under acidic conditions.
[0006] The objective of this invention can be achieved through the following technical solution: a Rh single-atom hydrogen evolution catalyst, using P-doped carbon material as a support and Rh single atoms as active sites.
[0007] A method for preparing the above-mentioned Rh single-atom hydrogen evolution catalyst includes the following steps:
[0008] S1, carbon nanotubes and organophosphorus source are ground and mixed to obtain powder A;
[0009] S2, Powder A is annealed at high temperature, with protective gas introduced throughout the process, to obtain powder B;
[0010] S3, Rh metal salt is dissolved in methanol / water mixed solvent, powder B is added, and the mixture is ultrasonically dispersed to obtain mixed solution C;
[0011] S4, the mixed solution C is magnetically stirred and dried to obtain powder D;
[0012] S5, the powder D is annealed at low temperature, and a reducing gas is introduced throughout the process to obtain the Rh single-atom hydrogen evolution catalyst.
[0013] Preferably, in step S1, the carbon nanotubes are multi-walled nanotubes.
[0014] Preferably, in step S1, the organophosphorus source is triphenylphosphine.
[0015] Preferably, in step S1, the mass ratio of the carbon nanotubes to the organophosphorus source is 1:1-5.
[0016] Preferably, in step S2, powder A is placed in a muffle furnace for high-temperature annealing at a temperature of 650–750°C for 1.5–2.5 hours.
[0017] More preferably, in step S2, the annealing temperature is 700°C and the time is 2 hours.
[0018] Preferably, in step S2, the protective gas is argon.
[0019] Preferably, in step S3, the volume ratio of methanol to water in the methanol / water mixed solvent is 1:1.
[0020] Preferably, in step S3, the ultrasonic dispersion time is 50-70 seconds.
[0021] More preferably, in step S3, the ultrasonic dispersion time is 1 minute.
[0022] Preferably, in step S3, the Rh metal salt is RhCl3·xH2O.
[0023] More preferably, the Rh metal salt is RhCl3·3H2O or RhCl3.
[0024] Preferably, in step S3, the mass ratio of the Rh metal salt to powder B is 1:5-20.
[0025] Preferably, in step S4, the magnetic stirring speed is 450-550 rpm, more preferably 500 rpm, and the time is 6-24 hours.
[0026] Preferably, in step S4, the drying is rotary evaporation drying at a temperature of 30-80°C.
[0027] Preferably, in step S5, powder D is placed in a muffle furnace for low-temperature annealing at a temperature of 110–130°C for 50–70 min.
[0028] More preferably, in step S5, the annealing temperature is 120°C and the time is 1 hour.
[0029] Preferably, in step S5, the reducing gas is an H2 / Ar mixture.
[0030] More preferably, the volume concentration of H2 in the reducing gas is 1-20%, preferably 5%.
[0031] An application of the above-mentioned Rh single-atom hydrogen evolution catalyst is to use the Rh (rhodium) single-atom hydrogen evolution catalyst for efficient hydrogen evolution under acidic conditions.
[0032] The performance of single-atom catalysts is significantly affected by the support environment. Therefore, this invention utilizes heteroatoms to optimize the environment surrounding metal single atoms, thereby altering the electronic properties of the metal single atoms and improving the electrocatalytic hydrogen production performance.
[0033] Compared with the prior art, the present invention has the following beneficial effects:
[0034] 1. The present invention provides a Rh single-atom hydrogen evolution catalyst prepared by a multi-step method. The Rh atoms have an excellent surrounding environment, which enhances the intrinsic catalytic activity and achieves high electrocatalytic hydrogen production performance with a low content.
[0035] 2. The preparation method of this invention is simple, and the conditions and yield are easy to control;
[0036] 3. This invention achieves uniform distribution of Rh atoms on a P-doped carbon material carrier through magnetic stirring, and then through low-temperature annealing, the Rh atoms can be firmly anchored on the P-doped carbon material carrier by reducing gas, thus inhibiting the formation of Rh nanoparticles.
[0037] 4. This invention does not easily lose a large number of active sites, has a small metal loading, and alleviates the problem of metal waste;
[0038] 5. The catalyst of this invention can efficiently generate hydrogen under acidic conditions and has good application prospects in the field of electrocatalytic water splitting for hydrogen production. Attached Figure Description
[0039] Figure 1 This is a TEM image of the Rh single-atom catalyst prepared in Example 1 of the present invention;
[0040] Figure 2 The graph shows the electrocatalytic hydrogen production performance of the Rh single-atom catalyst prepared in Example 1 of this invention and the commercial Pt / C catalyst. Detailed Implementation
[0041] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.
[0042] A method for preparing a Rh single-atom hydrogen evolution catalyst, the method comprising the following steps:
[0043] S1, carbon nanotubes and organophosphorus source are ground in a mortar to obtain uniformly mixed powder A;
[0044] S2, Powder A is placed in a muffle furnace for high-temperature annealing, with protective gas introduced throughout the process, to obtain brown-black powder B;
[0045] S3, Rh metal salt is dissolved in methanol / water mixed solvent, powder B is added, and the mixture is ultrasonically dispersed to obtain mixed solution C;
[0046] S4, the mixed solution C is magnetically stirred and dried to obtain brown-black powder D;
[0047] S5. Place the brown-black powder D in a muffle furnace for low-temperature annealing, and pass a reducing gas throughout the process to obtain the Rh single-atom catalyst.
[0048] The following detailed description is based on specific embodiments.
[0049] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.
[0050] Example 1
[0051] A method for preparing a Rh single-atom hydrogen evolution catalyst includes the following steps:
[0052] S1, grind 0.5g of multi-walled carbon nanotubes and 0.5g of triphenylphosphine in a mortar for 5 minutes to obtain a uniformly mixed powder A;
[0053] S2, Powder A is placed in a muffle furnace and annealed at 700 degrees Celsius for 2 hours, with Ar protective gas introduced throughout the process, to obtain brown-black powder B;
[0054] S3, dissolve 60mg RhCl3·3H2O in a mixed solvent of 10mL methanol and 10mL water, add 0.49g powder B, and disperse by ultrasonication for 1min to obtain mixed solution C;
[0055] S4. Mixed solution C was magnetically stirred at 500 rpm for 6 hours, and then dried by rotary evaporation at 30°C to obtain brown-black powder D.
[0056] S5, the brown-black powder D was placed in a muffle furnace and annealed at 120 degrees Celsius for 1 hour, with H2 / Ar (5%) reducing gas introduced throughout the process, and finally the Rh single-atom catalyst HPNT was obtained.
[0057] Figure 1The TEM image shows the product HPNT, with bright spots representing single Rh atoms.
[0058] Figure 2 The test curves in the figure show the electrocatalytic hydrogen production performance of the product HPNT under acidic conditions. Even at an Rh atomic mass concentration of 0.3%, it still exhibits superior performance compared to commercial Pt / C catalysts.
[0059] Example 2
[0060] A method for preparing a Rh single-atom hydrogen evolution catalyst includes the following steps:
[0061] S1, grind 0.5g of multi-walled carbon nanotubes and 1.5g of triphenylphosphine in a mortar for 5 minutes to obtain a uniformly mixed powder A;
[0062] S2, Powder A is placed in a muffle furnace and annealed at 700 degrees Celsius for 2 hours, with Ar protective gas introduced throughout the process, to obtain brown-black powder B;
[0063] S3, dissolve 60mg RhCl3·3H2O in a mixed solvent of 10mL methanol and 10mL water, add 0.49g powder B, and disperse by ultrasonication for 1min to obtain mixed solution C;
[0064] S4. Mixed solution C was magnetically stirred at 500 rpm for 6 hours, and then dried by rotary evaporation at 30°C to obtain brown-black powder D.
[0065] S5, the brown-black powder D was placed in a muffle furnace and annealed at 120 degrees Celsius for 1 hour, with H2 / Ar (5%) reducing gas introduced throughout the process, and finally the Rh single-atom catalyst HPNT was obtained.
[0066] Example 3
[0067] A method for preparing a Rh single-atom hydrogen evolution catalyst includes the following steps:
[0068] S1, grind 0.5g of multi-walled carbon nanotubes and 2.5g of triphenylphosphine in a mortar for 5 minutes to obtain a uniformly mixed powder A;
[0069] S2, Powder A is placed in a muffle furnace and annealed at 700 degrees Celsius for 2 hours, with Ar protective gas introduced throughout the process, to obtain brown-black powder B;
[0070] S3, dissolve 60mg RhCl3·3H2O in a mixed solvent of 10mL methanol and 10mL water, add 0.49g powder B, and disperse by ultrasonication for 1min to obtain mixed solution C;
[0071] S4. Mixed solution C was magnetically stirred at 500 rpm for 6 hours, and then dried by rotary evaporation at 30°C to obtain brown-black powder D.
[0072] S5, the brown-black powder D was placed in a muffle furnace and annealed at 120 degrees Celsius for 1 hour, with H2 / Ar (5%) reducing gas introduced throughout the process, and finally the Rh single-atom catalyst HPNT was obtained.
[0073] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.
Claims
1. A Rh single-atom hydrogen evolution catalyst, characterized in that, The Rh single-atom hydrogen evolution catalyst uses P-doped carbon material as a support and Rh single atoms as active sites.
2. A method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 1, characterized in that, Includes the following steps: S1, carbon nanotubes and organophosphorus source are ground and mixed to obtain powder A; S2, Powder A is annealed at high temperature, with protective gas introduced throughout the process, to obtain powder B; S3, Rh metal salt is dissolved in methanol / water mixed solvent, powder B is added, and the mixture is ultrasonically dispersed to obtain mixed solution C; S4, Stir the mixed solution C and dry it to obtain powder D; S5, the powder D is annealed at low temperature, and a reducing gas is introduced throughout the process to obtain the Rh single-atom hydrogen evolution catalyst.
3. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S1, the carbon nanotubes are multi-walled nanotubes, and the organophosphorus source is triphenylphosphine.
4. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S1, the mass ratio of the carbon nanotubes to the organophosphorus source is 1:1-5.
5. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S2, powder A is placed in a muffle furnace for high-temperature annealing at a temperature of 650–750°C for 1.5–2.5 hours, with argon as the protective gas.
6. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S3, the volume ratio of methanol to water in the methanol / water mixed solvent is 1:1, and the ultrasonic dispersion time is 50-70s.
7. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S3, the Rh metal salt is RhCl3·xH2O, and the mass ratio of Rh metal salt to powder B is 1:5-20.
8. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S4, the stirring is magnetic stirring, the magnetic stirring speed is 450-550 rpm, and the time is 6-24 hours; In step S4, the drying is rotary evaporation drying at a temperature of 30-80℃.
9. The method for preparing the Rh single-atom hydrogen evolution catalyst according to claim 2, characterized in that, In step S5, powder D is placed in a muffle furnace for low-temperature annealing at a temperature of 110-130°C for 50-70 minutes. In step S5, the reducing gas is an H2 / Ar mixture, and the volume concentration of H2 in the reducing gas is 1-20%.
10. The application of the Rh single-atom hydrogen evolution catalyst according to claim 1, characterized in that, The Rh single-atom hydrogen evolution catalyst was used for hydrogen evolution under acidic conditions.