Metal type delafossite electrocatalytic hydrogen evolution catalyst as well as preparation method and application thereof
By epitaxially growing the copper iron ore PdRhO2 film on the substrate, the problems of high electrocatalyst cost and surface inhomogeneity are solved, and high-efficiency electrocatalytic activity and stability are achieved, which are suitable for electrolytic water and hydrogen energy storage.
Patent Information
- Application Number
- CN202510542300.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-28
- Publication Date
- 2025-07-18
AI Technical Summary
The existing electrocatalysts are costly and difficult to quantify catalytic activity. The surface composition of the catalyst in the traditional particle form is uneven, difficult to quantify and test, and complex interaction with the substrate.
Epitaxially grown metal-type copper iron ore PdRhO2 film is used as an electrocatalyst and prepared by spin coating, drying, pyrolysis and annealing on the substrate to form a uniform crystal structure, and the film thickness is regulated to optimize the catalytic performance.
It achieves efficient and long-lasting electrocatalytic activity, significantly reduces overpotential, is suitable for large-scale production, is low-cost, and is suitable for electrolytic water and hydrogen energy storage.
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Figure CN120330769A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of electrocatalytic hydrogen evolution, and particularly to a metal-type chalcopyrite electrocatalytic hydrogen evolution catalyst, a preparation method thereof, and an application thereof. Background Art
[0002] Hydrogen is considered a green energy source that does not emit carbon dioxide during use. The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are two half-reactions of electrocatalytic water splitting, and among them, the hydrogen evolution reaction and the oxygen evolution reaction are effective ways to produce hydrogen. To improve the performance of the hydrogen evolution reaction, various catalysts are studied, and the benchmark catalyst is a platinum (Pt)-based material. However, because the platinum-based material is expensive, it increases the cost of its industrial application.
[0003] Among them, electrocatalytic water splitting for hydrogen production not only has the potential to meet the challenges of global environmental and energy problems, but can also be used as a model for studying other complex heterogeneous catalytic reactions. It is generally believed that an ideal electrocatalyst for the hydrogen evolution reaction should have a low overpotential, a low Tafel slope, and high electrochemical stability. The efficiency of a given catalyst is mainly determined by the first two factors, and these two factors also represent the electron transfer barrier. Further research on the hydrogen evolution process shows that it involves two electron transfer processes: the first is the transfer of electrons from the catalyst surface to the reaction intermediate, which is controlled by the Sabatier principle based on the d-band model, and this principle states that the optimal binding energy of the intermediate is beneficial to the reaction; the second process is the injection of electrons from the substrate into the catalyst and then flowing to the surface.
[0004] Traditional electrocatalysts are usually manufactured in the form of particles, dispersed in an "ink", and drop-coated on the surface of the electrode substrate. This material has a high surface area, resulting in a high reaction rate, but it is challenging to standardize the comparison of the "intrinsic" activity of the material with the active surface area. In addition, these materials may have an uneven surface composition, making it difficult to quantify the tests before and after catalysis, variable crystal phases, and a series of interactions with the substrate. In contrast, epitaxial thin films provide a smooth surface, can be quantitatively characterized by spectroscopic and microscopic techniques, have a uniform crystal structure and crystal orientation, and can change the thickness to control the interaction with the substrate. Summary of the Invention
[0005] Based on this, the purpose of the present invention is to provide a metal-type chalcopyrite electrocatalytic hydrogen evolution catalyst, a preparation method thereof, and an application thereof. This catalyst has excellent electrocatalytic hydrogen evolution (HER) activity and stability, and can be applied to electrolytic water and hydrogen energy storage.
[0006] To achieve the above purpose, the present invention adopts the following technical solutions: The present invention first provides a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst, which comprises a substrate and a metal-type copper iron ore PdRhO2 thin film grown on the substrate.
[0007] As a further improvement of the above solution of the present invention, the substrate is an Al2O3 crystal, a β-Ga2O3 single crystal, a MgO single crystal or a 4H-SiC single crystal.
[0008] As a further improvement of the above solution of the present invention, the thickness of the metal-type copper iron ore PdRhO2 thin film is 10-200 nm.
[0009] The present invention also provides a method for preparing the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst as described above, which comprises the following steps: S1. Stir and mix a palladium salt, a rhodium salt and a solvent to obtain a precursor solution; S2. Spin-coat the precursor solution on a pretreated growth substrate, dry it, pyrolyze it, and anneal it to obtain an electrocatalytic hydrogen evolution catalyst.
[0010] As a further improvement of the above solution of the present invention, in step S1, the palladium salt is one of palladium acetate, palladium sulfate, palladium nitrate, and palladium chloride; the rhodium salt is one of rhodium acetate, rhodium sulfate, rhodium nitrate, and rhodium chloride; And / or, in step S1, the dosages of the palladium source and the rhodium source satisfy that the molar ratio of palladium element to rhodium element is (1-2):(1-2).
[0011] As a further improvement of the above solution of the present invention, in step S1, the solvent is a mixture of nitric acid and ethylene glycol monomethyl ether in a volume ratio of 1:4; the stirring is carried out at a speed of 300-500 revolutions per minute at room temperature for 10-60 minutes; in the precursor solution, the total molar concentration of palladium element and rhodium element is 0.1-1 mol / L.
[0012] As a further improvement of the above solution of the present invention, in step S2, the rotation speed of the spin-coating is 2000-7000 rpm, the spin-coating time is 20-60 seconds, and the spin-coating ambient temperature is 30-60 °C; And / or, the drying is carried out on a hot plate at 90-150 °C for 1-6 minutes; And / or, the pyrolysis is carried out in air at 250-400 °C for 5-30 minutes; And / or, the annealing is carried out in air at 600-950 °C for 10-60 minutes.
[0013] As a further improvement of the above solution of the present invention, step S2 is repeated multiple times to obtain a crystalline metal-type copper iron ore PdRhO2 thin film with a thickness of 30-80 nm.
[0014] The present invention also provides an application of the above-mentioned metal-type copper iron ore electrocatalytic hydrogen evolution catalyst in electrocatalytic hydrogen evolution.
[0015] As a further improvement of the above solution of the present invention, the application adopts a three-electrode test system, and uses 0.5 M sulfuric acid or 1.0 M potassium hydroxide as the electrolyte.
[0016] Compared with the prior art, the present invention has the following beneficial effects: The metal-type copper iron ore electrocatalytic hydrogen evolution catalyst provided by the present invention exhibits ultra-high electrocatalytic hydrogen evolution activity, realizes efficient and durable electrocatalytic activity in the medium, and can be applied to electrolytic water and hydrogen energy storage; the performance of the catalyst can be adjusted by controlling the thickness of the epitaxially grown metal-type copper iron ore PdRhO2 thin film, which significantly reduces the overpotential during the electrocatalytic process. At the same time, the bimetallic combination of Pd and Rh can optimize the catalytic performance through the synergistic regulation of the electronic structure, and has high electrocatalytic application value.
[0017] The preparation method of the metal-type copper iron ore PdRhO2 electrocatalytic hydrogen evolution catalyst provided by the present invention is simple. Based on the chemical solution deposition process in a non-vacuum environment, by preparing a stable precursor solution and then coating the precursor solution on the growth substrate, a large-size and high-quality metal-type copper iron ore PdRhO2 thin film is deposited. It has the advantages of low cost and simple operation. It can not only effectively control the quality and transport properties of the PdRhO2 thin film, but also be suitable for large-scale production, and has good application prospects in the field of metal electrodes.
[0018] When preparing the metal-type copper iron ore PdRhO2 electrocatalytic hydrogen evolution catalyst of the present invention, in the precursor solution, the hydroxyl group (-OH) and methoxy group (-OCH3) in the ethylene glycol methyl ether molecule can form strong hydrogen bond interactions with palladium ions and rhodium ions, thereby significantly improving the dispersion of palladium nitrate and rhodium nitrate in the solvent; in addition, the relatively high dielectric constant of ethylene glycol methyl ether helps to effectively solvate the charged nitrate ions, reduce the electrostatic attraction between ions, and inhibit the agglomeration of palladium nitrate and rhodium nitrate particles; the above interactions make the mixed system of palladium nitrate, rhodium nitrate and ethylene glycol methyl ether have a low free energy, thereby endowing the precursor solution with good stability. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 It is the XRD pattern of the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1 of the present invention; Figure 2 It is the structural schematic diagram of the three-electrode test system involved in the present invention; Figure 3 It is the hydrogen evolution performance diagram of the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1 of the present invention; Figure 4 This is the hydrogen evolution performance diagram of the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 2 of the present invention; Figure 5 This is the hydrogen evolution performance diagram of the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 3 of the present invention. Detailed implementation manners
[0020] For the convenience of understanding the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.
[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.
[0022] Example 1 This example provides a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst, and its preparation method includes the following steps: S1. Add 2 mmol of palladium nitrate and 2 mmol of rhodium nitrate to 10 mL of a solvent (a mixture of nitric acid and ethylene glycol monomethyl ether in a volume ratio of 1:4; the nitric acid is commercially available with a concentration of 68%) and dissolve it, and stir at room temperature for 6 hours to obtain a stable precursor solution; S2. Spin coat the stable precursor solution on the surface of a pretreated Al2O3 substrate. The spin coating speed is 4000 rpm, the spin coating time is 30 seconds, and the spin coating ambient temperature is 45°C; after spin coating into a film, place the film on a hot plate at 120°C and dry it for 1 minute; after drying, pyrolyze the film in an air atmosphere, the pyrolysis temperature is 350°C, and the pyrolysis time is 10 minutes; after pyrolysis, push it into a tubular furnace and anneal it in air, the annealing temperature is 700°C, and the annealing time is 60 minutes. Repeat the above steps of spin coating, drying, pyrolysis, and annealing 9 times to obtain a PdRhO2 film with a thickness of 65 nm, which is the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst.
[0023] According to the X-ray diffraction test method, under the conditions of a test voltage of 40 kV and a current of 40 mA, use a Philips X'pert PRO X-ray diffractometer with Cu Kα radiation to perform X-ray diffraction characterization on the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst obtained in this example, and obtain the Figure 1 shown XRD pattern. From Figure 1It can be seen that the metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst obtained in this example shows diffraction peaks of the (003), (006), (009), and (0012) crystal planes of the perovskite-type PdRhO2 at positions such as 14.70°, 29.63°, 45.10°, and 61.48°, indicating that the sample obtained in Example 1 is PdRhO2, further reflecting the advantage of the present invention that a metal-type copper-iron ore PdRhO2 thin film catalyst can be prepared simply by a simple operation process.
[0024] Test Example 1 The metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1 was subjected to electrocatalytic hydrogen evolution, specifically as follows: According to the electrochemical linear sweep voltammetry test, at a scanning rate of 5 mV s -1 under the test conditions, using a Chenhua electrochemical workstation 660E, a three-electrode test system (such as Figure 2 ), using the PdRhO2 thin film obtained in Example 1 as the working electrode, a graphite rod as the working electrode, a silver / silver chloride electrode as the reference electrode, and 0.5 M sulfuric acid as the electrolyte, its electrocatalytic hydrogen evolution activity was tested. The hydrogen evolution performance obtained from the test is shown in Figure 3 the polarization curve and stability test in.
[0025] From Figure 3 it can be seen that the metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1 has an overpotential of 45 mV at a current density of 10 mA cm -2 , showing ultra-high electrocatalytic hydrogen evolution activity.
[0026] Taking a current density of 10 mA cm -2 as the initial current, a 72-hour stability test was carried out on the metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1. It was found that after the 72-hour stability test, the performance of the metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst prepared in Example 1 did not show obvious attenuation, showing good electrocatalytic hydrogen evolution stability. Further indicating that the metal-type copper-iron ore PdRhO2 thin film catalyst provided by the present invention has high electrocatalytic application value.
[0027] Example 2 This example presents a metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst, and its preparation method includes the following steps: S1. Add 2 mmol of palladium nitrate and 2 mmol of rhodium nitrate to 10 mL of a solvent (a mixture of nitric acid and ethylene glycol monomethyl ether in a volume ratio of 1:4; nitric acid is commercially available with a concentration of 68%) and dissolve it, and stir at room temperature for 6 hours to obtain a stable precursor solution; S2. Spin-coat the stable precursor solution on the surface of the pretreated Al2O3 substrate at a spin-coating speed of 4000 rpm, a spin-coating time of 30 seconds, and a spin-coating ambient temperature of 45 °C. After spin-coating to form a film, place the film on a hot plate at 120 °C and dry it for 1 minute. Pyrolyze the dried film in an air atmosphere at a pyrolysis temperature of 350 °C and a pyrolysis time of 10 minutes. After pyrolysis, push it into a tube furnace and anneal it in air at an annealing temperature of 700 °C and an annealing time of 60 minutes. Repeat the above steps of spin-coating, drying, pyrolysis, and annealing 4 times to obtain a PdRhO2 film with a thickness of 30 nm, which is the metal-type cuprite electrocatalytic hydrogen evolution catalyst.
[0028] Experimental Example 2 Perform electrocatalytic hydrogen evolution on the metal-type cuprite electrocatalytic hydrogen evolution catalyst prepared in Example 2, specifically: According to the electrochemical linear sweep voltammetry test, under the test conditions of a scanning rate of 5 mV s -1 , using a Chenhua Electrochemical 660E workstation, adopt a three-electrode test system (such as Figure 2 ), use the PdRhO2 film obtained in Example 2 as the working electrode, a graphite rod as the working electrode, a silver / silver chloride electrode as the reference electrode, and select 0.5 M sulfuric acid as the electrolyte to conduct its electrocatalytic hydrogen evolution activity test. The hydrogen evolution performance obtained from the test is shown in Figure 4 the polarization curve and stability test in.
[0029] From Figure 4 it can be seen that the metal-type cuprite electrocatalytic hydrogen evolution catalyst prepared in Example 2 has an overpotential of 161 mV at a current density of 10 mA cm -2 , showing good electrocatalytic hydrogen evolution activity. Further indicating that the metal-type cuprite PdRhO2 film catalyst provided by the present invention has high electrocatalytic application value.
[0030] Example 3 This example proposes a metal-type cuprite electrocatalytic hydrogen evolution catalyst, and its preparation method includes the following steps: S1. Add 2 mmol of palladium nitrate and 2 mmol of rhodium nitrate to 10 mL of a solvent (a mixture of nitric acid and ethylene glycol methyl ether in a volume ratio of 1:4; nitric acid is commercially available with a concentration of 68%) and dissolve it, and stir at room temperature for 6 hours to obtain a stable precursor solution; S2. Spin-coat the stable precursor solution on the surface of the pretreated Al2O3 substrate at a spin-coating speed of 4000 rpm, a spin-coating time of 30 seconds, and a spin-coating ambient temperature of 45 °C. After spin-coating to form a film, place the film on a hot plate at 120 °C and dry it for 1 minute. Pyrolyze the dried film in an air atmosphere at a pyrolysis temperature of 350 °C and a pyrolysis time of 10 minutes. After pyrolysis, push it into a tubular furnace and anneal it in air at an annealing temperature of 700 °C and an annealing time of 60 minutes. Repeat the above steps of spin-coating, drying, pyrolysis, and annealing 11 times to obtain a PdRhO2 film with a thickness of 75 nm, which is the metal-type cuprite electrocatalytic hydrogen evolution catalyst.
[0031] Test Example 3 Perform electrocatalytic hydrogen evolution on the metal-type cuprite electrocatalytic hydrogen evolution catalyst prepared in Example 3, specifically: According to the electrochemical linear sweep voltammetry test, under the test conditions of a scanning rate of 5 mV s -1 , use the Chenhua Electrochemical 660E workstation and adopt a three-electrode test system (such as Figure 2 ). Use the PdRhO2 film obtained in Example 3 as the working electrode, a graphite rod as the working electrode, and a silver / silver chloride electrode as the reference electrode. Select 0.5 M sulfuric acid as the electrolyte to conduct its electrocatalytic hydrogen evolution activity test. The hydrogen evolution performance obtained from the test is shown in Figure 5 the polarization curve and stability test in.
[0032] From Figure 5 it can be seen that the metal-type cuprite electrocatalytic hydrogen evolution catalyst prepared in Example 3 has an overpotential of 76 mV at a current density of 10 mA cm -2 , showing good electrocatalytic hydrogen evolution activity. Further indicating that the metal-type cuprite PdRhO2 film catalyst provided by the present invention has high electrocatalytic application value.
[0033] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.
[0034] The above-described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent should be subject to the appended claims.
Claims
1. A metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst, characterized in that, It includes a substrate and a metallic copper-iron-oxide PdRhO₂ thin film grown on the substrate.
2. The metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to claim 1, wherein The substrate is an Al₂O₃ crystal, a β-Ga₂O₃ single crystal, a MgO single crystal or a 4H-SiC single crystal.
3. The metal-type copper-iron ore electrocatalytic hydrogen evolution catalyst according to claim 1, characterized in that, The thickness of the metallic copper-iron-oxide PdRhO₂ thin film is 10 - 200 nm.
4. A method for preparing the metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to any one of claims 1-3, characterized in that, It includes the following steps: S1. Stir and mix a palladium salt, a rhodium salt and a solvent to obtain a precursor solution; S2. Spin-coat the precursor solution on a pretreated growth substrate, dry it, pyrolyze it, and anneal it to obtain an electrocatalytic hydrogen evolution catalyst.
5. The method for preparing a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to claim 4, characterized in that, In step S1, the palladium salt is one of palladium acetate, palladium sulfate, palladium nitrate, and palladium chloride; the rhodium salt is one of rhodium acetate, rhodium sulfate, rhodium nitrate, and rhodium chloride; And / or, in step S1, the dosages of the palladium source and the rhodium source satisfy that the molar ratio of palladium element to rhodium element is (1 - 2):(1 - 2).
6. The method for preparing a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to claim 4, characterized in that, In step S1, the solvent is a mixture of nitric acid and ethylene glycol monomethyl ether in a volume ratio of 1:4; the stirring is carried out at a speed of 300 - 500 revolutions per minute at room temperature for 10 - 60 minutes; in the precursor solution, the total molar concentration of palladium element and rhodium element is 0.1 - 1 mol / L.
7. The method for preparing a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to claim 4, characterized in that, In step S2, the rotation speed of the spin-coating is 2000 - 7000 rpm, the spin-coating time is 20 - 60 seconds, and the spin-coating ambient temperature is 30 - 60 °C; And / or, the drying is carried out on a hot plate at 90 - 150 °C for 1 - 6 minutes; And / or, the pyrolysis is carried out in air at 250 - 400 °C for 5 - 30 minutes; And / or, the annealing is carried out in air at 600 - 950 °C for 10 - 60 minutes.
8. The method for preparing a metal-type copper iron ore electrocatalytic hydrogen evolution catalyst according to claim 4, characterized in that, Repeat step S2 multiple times to obtain a crystalline metallic copper-iron-oxide PdRhO₂ thin film with a thickness of 30 - 80 nm.
9. Application of a metallic copper-iron-oxide electrocatalytic hydrogen evolution catalyst as described in any one of claims 1 - 3 in electrocatalytic hydrogen evolution.
10. The application according to claim 9, characterized in that, The application adopts a three-electrode test system with 0.5 M sulfuric acid or 1.0 M potassium hydroxide as the electrolyte.