A low-noble-metal-content electrocatalytic seawater hydrogen production catalyst, a preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUDAN UNIVERSITY
- Filing Date
- 2024-12-13
- Publication Date
- 2026-06-16
AI Technical Summary
Existing precious metal-based catalysts for hydrogen production from seawater suffer from problems such as scarce reserves, high prices, and environmental pollution, while traditional synthesis methods are costly and inefficient.
A solvent-free method was used to prepare an electrocatalyst for hydrogen production from seawater with low precious metal content. The method involves grinding precious metal salts and graphite carbon supports and then annealing them at high temperature in a muffle furnace. The abundant carboxyl functional groups of the graphite carbon support anchor the precious metals and inhibit particle growth. The preparation steps are simple and the cost is low.
It achieves excellent electrocatalytic performance with low precious metal content, reduces metal waste and environmental pollution, lowers preparation costs, and produces catalysts with uniform particle size and high electrochemical activity.
Smart Images
Figure CN122214929A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrocatalytic seawater hydrogen production technology, and in particular relates to an electrocatalytic seawater hydrogen production catalyst with low precious metal content, its preparation method and application. Background Technology
[0002] Hydrogen is an ideal clean energy source and a green energy carrier. Because its consumption process emits no greenhouse gases, hydrogen is receiving increasing attention from countries worldwide. Currently, water electrolysis is considered one of the important pathways for large-scale production of "green hydrogen." Due to the limited freshwater resources, seawater hydrogen production has become an important direction for future hydrogen energy development. Seawater has a complex composition, therefore, catalysts used for electrocatalytic seawater hydrogen production still face a series of challenges in terms of material systems and synthesis methods.
[0003] Noble metal-based catalysts remain the most efficient electrocatalytic hydrogen production catalysts, but their practical application is limited by scarce reserves and high prices. Currently, most methods for synthesizing noble metal-based catalysts are wet processes, such as the sodium borohydride reduction method, which have relatively high costs for solutions and reducing agents, and are prone to wasting precious metals and causing some environmental pollution.
[0004] CN114645292A discloses a PEM electrolysis water hydrogen evolution catalyst with low precious metal content, its preparation method and application. The catalyst is prepared by modifying conductive carbon with elements such as nitrogen and / or phosphorus, and by combining ball milling and inert atmosphere calcination for PEM electrolysis water hydrogen evolution reaction in acidic media. However, the use of nitrogen / phosphorus elements in this method will cause a certain degree of environmental pollution. Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings of the prior art by providing an electrocatalytic seawater hydrogen production catalyst with low precious metal content, its preparation method, and its application. The electrocatalytic seawater hydrogen production catalyst with low precious metal content is prepared by a solvent-free method, which can maintain excellent performance under the condition of low precious metal content. The preparation steps are few, the operation is simple, and the cost is low. The graphite carbon support used has abundant carboxyl functional groups, which can anchor precious metal elements and inhibit the growth of precious metal particles.
[0006] The objective of this invention can be achieved through the following technical solutions:
[0007] In a first aspect, the present invention provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low noble metal content, the preparation method comprising the following steps:
[0008] S1, the precious metal salt and graphite carbon support are ground to obtain a black powder;
[0009] S2, the black powder is placed in a muffle furnace for high-temperature annealing, with protective gas introduced throughout the process, and the catalyst is obtained after cooling.
[0010] Furthermore, in step S1, the mass ratio of the noble metal salt to the graphite carbon support is 1-3:10.
[0011] Furthermore, the graphite carbon support is a carboxylated graphite carbon support.
[0012] Furthermore, in step S1, the graphite carbon support has abundant carboxyl functional groups.
[0013] Furthermore, the precious metal salt is a precious metal chloride salt.
[0014] Further, in step S1, the precious metal salt is one or more of ruthenium chloride, iridium chloride, and rhodium chloride.
[0015] Further, in step S1, the noble metal salt is one or more of RuCl3·xH2O, IrCl3·xH2O, and RhCl3·xH2O.
[0016] Furthermore, in step S1, the grinding is carried out in air for 5-30 minutes.
[0017] Furthermore, the mortar is a ceramic mortar or an agate mortar.
[0018] Furthermore, in step S2, the high-temperature annealing process involves first annealing at 450-500 degrees Celsius for 1 hour, and then annealing at 650-750 degrees Celsius for 2 hours.
[0019] Furthermore, in step S2, the high-temperature annealing process involves first annealing at 475 degrees Celsius for 1 hour, and then annealing at 700 degrees Celsius for 2 hours.
[0020] Further, in step S2, the cooling process involves reducing the temperature of the muffle furnace to room temperature.
[0021] Furthermore, in step S2, the protective gas is argon (Ar).
[0022] In a second aspect, the present invention provides an electrocatalytic seawater hydrogen production catalyst with low noble metal content, obtained by the above preparation method, wherein the noble metal content of the catalyst is 4 wt% N 5 wt%.
[0023] Furthermore, the catalyst particles have a size of approximately 1-4 nm and a uniform particle size distribution.
[0024] In a third aspect, the present invention provides an application of an electrocatalytic seawater hydrogen production catalyst with low precious metal content, wherein the catalyst is obtained by the above preparation method and is used as an electrocatalytic seawater hydrogen production catalyst.
[0025] Compared with the prior art, the present invention has the following advantages:
[0026] (1) This invention provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content. The preparation of the electrocatalytic seawater hydrogen production catalyst with low precious metal content by solvent-free method can reduce the cost of solution and reducing agent, reduce metal waste and certain environmental pollution.
[0027] (2) The present invention provides an electrocatalytic seawater hydrogen production catalyst with low precious metal content, which can maintain excellent performance.
[0028] (3) The present invention provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content, which has fewer preparation steps, is simple to operate, and has a low cost.
[0029] (4) This invention provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content. The graphite carbon support used has abundant carboxyl functional groups, which can effectively anchor precious metal elements and inhibit Austyl ripening and reduce the size of precious metal particles. Attached Figure Description
[0030] Figure 1 This is a TEM image of the catalyst RuDG generated in this invention.
[0031] Figure 2 The electrocatalytic performance curve of RuDG catalyst generated in this invention for hydrogen production from seawater is shown. Detailed Implementation
[0032] 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.
[0033] Unless otherwise specified in this technical solution, the component model, material name, connection structure, control method, algorithm, and other features are considered to be common technical features disclosed in the prior art.
[0034] It should be noted that, in this invention, relational terms such as first and second are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations.
[0035] In the following embodiments, unless otherwise specified, the raw materials or processing techniques are all commercially available materials or conventional processing techniques in the art.
[0036] In the following examples, the carboxylated graphene carbon support used is the Edge-carboxylated graphene nanosheets described in Edge-carboxylated graphene nanosheets via ball milling (Proc.Natl.Acad.Sci.USA109 5588-5593(2012)).
[0037] In the following examples, RuCl3·xH2O is hydrated ruthenium trichloride, CAS number 14898-67-0; IrCl3·xH2O is hydrated iridium trichloride, CAS number 14996-61-3; and RhCl3·xH2O is hydrated rhodium trichloride, CAS number 20765-98-4.
[0038] In the following comparative examples, the titanium mesh aperture is 0.154 mm.
[0039] Example 1
[0040] This embodiment provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low noble metal content. The catalyst is specifically RuDG, and the preparation method includes the following steps:
[0041] S1, 28 mg RuCl3·xH2O and 100 mg carboxyl-rich graphite carbon support were added to an agate mortar and ground for 30 min to obtain a black powder;
[0042] S2, the black powder is placed in a muffle furnace and annealed at 475 degrees Celsius for 1 hour and 700 degrees Celsius for 2 hours in sequence, with Ar protective gas introduced throughout the process. Once the temperature of the muffle furnace drops to room temperature, the catalyst RuDG can be obtained. The noble metal content of the catalyst is about 11 wt%.
[0043] Example 2
[0044] This embodiment provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content, specifically IrDG catalyst.
[0045] The only difference between Example 2 and Example 1 is that:
[0046] In S1, the noble metal salt is 20 mg IrCl3·xH2O, and the resulting catalyst is IrDG. The noble metal content of the catalyst is approximately 11 wt%.
[0047] Example 3
[0048] This embodiment provides a method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content, specifically catalyst RhDG.
[0049] The only difference between Example 3 and Example 1 is that:
[0050] In S1, the noble metal salt is 17 mg RhCl3·xH2O, and the obtained catalyst is RhDG. The noble metal content of the catalyst is about 7 wt%.
[0051] Comparative Example 1
[0052] This comparative example provides a catalyst, which is a commercially available titanium mesh.
[0053] Figure 1 The image shown is a TEM image of the catalyst RuDG in Example 1. The Ru particles are small, around 1-4 nm, and have a uniform particle size distribution.
[0054] Figure 2 The images show the electrocatalytic hydrogen production performance tests of the RuDG catalyst from Example 1 and the Ti mesh catalyst from the comparative example in simulated seawater. The test procedures and conditions were as follows: the electrolyte was a mixed solution of 1.0 M KOH and 0.5 M NaCl, and the scan rate was 5 mV / s. Despite the relatively low Ru content, RuDG still maintained excellent electrocatalytic hydrogen production performance from seawater. Figure 2 The LSV curves of the catalysts shown are as follows: the current density of the RuDG catalyst in Example 1 is approximately 3500 mA cm⁻¹ at 0.9 V (vs RHE). 2 Compared to titanium mesh (where the current density is approximately 0 mA cm⁻¹ at 0.9V (vs RHE)), 2 At 1.5V (vs RHE), the current density is approximately 3500mA cm⁻¹. 2 The catalyst RuDG in Example 1 exhibits high current density and high electrochemical activity when used for electrocatalytic hydrogen production in seawater.
[0055] 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 method for preparing an electrocatalytic seawater hydrogen production catalyst with low precious metal content, characterized in that, The preparation method includes the following steps: S1, the precious metal salt and graphite carbon support are ground to obtain a black powder; S2, the black powder is placed in a muffle furnace for high-temperature annealing, with protective gas introduced throughout the process, and the catalyst is obtained after cooling; In step S1, the mass ratio of the noble metal salt to the graphite carbon support is 1-3:10; The graphite carbon support is a carboxylated graphite carbon support.
2. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 1, characterized in that, The precious metal salt is a precious metal chloride salt.
3. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 2, characterized in that, In step S1, the precious metal salt is one or more of ruthenium chloride, iridium chloride, and rhodium chloride.
4. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 1, characterized in that, In step S1, the grinding is carried out in air for 5-30 minutes.
5. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 1, characterized in that, In step S1, the precious metal salt and graphite carbon support are added to a mortar and ground.
6. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 1, characterized in that, In step S2, the high-temperature annealing process is to first anneal at 450-500 degrees for 1 hour, and then anneal at 650-750 degrees for 2 hours; In step S2, the cooling process involves reducing the temperature of the muffle furnace to room temperature.
7. The method for preparing a low-precious-metal content electrocatalyst for seawater hydrogen production according to claim 1, characterized in that, In step S2, the protective gas is argon.
8. A low-noble-metal content electrocatalyst for seawater hydrogen production, obtained by the preparation method according to any one of claims 1-7, characterized in that, The catalyst contains 4 wt% to 15 wt% of precious metals.
9. The electrocatalyst for hydrogen production from seawater with low precious metal content according to claim 8, characterized in that, The catalyst particles have a size of 1-4 nm.
10. An application of a low-noble-metal-content electrocatalyst for seawater hydrogen production obtained by the preparation method according to any one of claims 1-8, characterized in that, The catalyst was used as an electrocatalytic catalyst for hydrogen production from seawater.