PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and preparation method thereof
By preparing PtSe2/PtCu heterojunction nanosphere catalysts, the problems of high catalyst cost and low activity in existing water electrolysis hydrogen production have been solved, realizing efficient and low-cost water electrolysis hydrogen production.
Patent Information
- Application Number
- CN202511185121.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-22
- Publication Date
- 2025-12-05
AI Technical Summary
Existing platinum-carbon catalysts are costly and have poor durability in water electrolysis for hydrogen production. The morphology and active sites of transition metal hydrogen evolution electrocatalysts are uncontrollable, resulting in low efficiency in water electrolysis for hydrogen production.
PtSe2/PtCu heterojunction nanospheres were used as catalysts to grow PtCu3 alloy hollow nanospheres via hydrothermal method and then selenized in a tube furnace to form a PtSe2/PtCu heterojunction structure, thereby increasing the active sites and regulating the electronic environment.
This improves the efficiency of the catalyst's active sites, reduces the amount of precious metal Pt used, lowers costs, and increases the efficiency of hydrogen production through water electrolysis.
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Figure CN121065731A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of electrochemical catalysis, and particularly relates to a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and a preparation method thereof. BACKGROUND
[0002] The hydrogen evolution reaction (HER) is a key reaction in the production of hydrogen by water electrolysis, involves multiple chemical kinetic reaction steps such as the adsorption of water molecules, the adsorption and desorption of hydrogen active intermediates, and requires the use of catalysts to reduce the reaction barrier and overpotential. The current commercial HER catalyst is platinum-carbon catalyst, which requires a large amount of scarce noble metal Pt, resulting in high cost. The poor durability and weak corrosion resistance of platinum-carbon catalysts seriously hinder the large-scale application of water electrolysis for hydrogen production. The use of transition metal doping strategy can improve the catalytic efficiency of platinum-based catalysts by utilizing the interaction between transition metals and noble metal elements, and reduce the amount of platinum used. Preparing high-efficiency and low-cost Pt-based electrocatalysts is the key to realizing the overall popularization of water electrolysis for hydrogen production, and is also a key technical problem urgently needed to be solved to promote the industrial development of water electrolysis for hydrogen production catalysts.
[0003] Thanks to the unique sandwiched layered structure and adjustable electronic structure, transition metal chalcogenides have become a new type of hydrogen evolution electrocatalyst. Since electrochemical reactions usually occur on the surface of the catalyst, maximizing the number of active sites in the basal plane of the catalyst and improving the intrinsic activity of the active sites are effective strategies to improve the electrocatalytic performance of transition metal chalcogenide catalysts. However, the existing transition metal hydrogen evolution electrocatalysts have the technical problems of uncontrolled morphology and size, low intrinsic activity of the electrocatalytic hydrogen evolution active site, which leads to a decrease in the yield of water electrolysis for hydrogen production. SUMMARY
[0004] The present application overcomes the shortcomings of the prior art, and provides a new type of transition metal chalcogenide nanosphere electrocatalytic hydrogen evolution catalyst containing PtSe2 / PtCu heterojunction and a preparation method thereof according to strategies including morphology engineering, surface modification and interface engineering. The adsorption and catalytic conversion efficiency of water molecules and active intermediates on the active site are maximized.
[0005] The present application is realized by the following technical solutions: A preparation method of a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst, first growing PtCu3 alloy hollow nanospheres by a hydrothermal method, and then selenizing the PtCu3 alloy hollow nanospheres in a tube furnace to obtain PtSe2 / PtCu nanospheres.
[0006] Preferably, the PtCu3 alloy hollow nanospheres are grown by hydrothermal method, that is, platinum acetylacetonate, copper acetate monohydrate and cetyltrimethylammonium bromide are added into a N,N-dimethylformamide solution, the mixture is uniformly mixed, and then is placed into a high-pressure hydrothermal reactor for sufficient reaction.
[0007] Preferably, the uniform mixing is stirring at 10-25 DEG C for 0.5-3 h.
[0008] Preferably, the solution after stirring and mixing is placed into a high-pressure hydrothermal reactor, and is kept in a blast drying oven for sufficient reaction.
[0009] More preferably, the keeping temperature is 180 DEG C, and the keeping time is 12 h.
[0010] Preferably, the solid-liquid mixture after sufficient reaction is centrifuged and washed for multiple times to obtain black solids, and then the black solids are dried to obtain PtCu3 alloy hollow nanospheres.
[0011] More preferably, the washing solution is a mixed solution of ethanol and water with a volume ratio of 1:2, and the drying method is freeze drying or vacuum drying.
[0012] Preferably, the seleniumization is that selenium powder is placed at the upstream of a tube furnace, the PtCu3 alloy hollow nanospheres are placed at the downstream of the tube furnace, and heating and keeping are performed to realize seleniumization, so as to obtain PtSe2 / PtCu nanospheres.
[0013] More preferably, the temperature at the upstream of the tube furnace is 220 DEG C, the temperature at the downstream of the tube furnace is 400-700 DEG C, and the keeping time is 1-5 h.
[0014] The PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst is prepared by the preparation method of the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst.
[0015] The beneficial effects of the present application relative to the prior art are as follows: The PtSe2 / PtCu nanospheres with a heterojunction structure synthesized by the present application are a kind of efficient electrocatalytic hydrogen evolution catalysts. In the hydrothermal reaction process, cetyltrimethylammonium bromide acts as a reducing agent and a blocking agent, so that the palladium acetylacetonate and the copper acetate are fully reduced, and under the etching action of the acetate ions, the hollow nanosphere structure is formed. Subsequently, in the heating process in the tube furnace, sufficient selenium source and the reduction of H2 ensure the formation of PtSe2, and finally the PtSe2 / PtCu heterojunction nanospheres are obtained.
[0016] Compared with the prior art, in the PtSe2 / PtCu heterojunction nanosphere of the application, the lattice mismatch of the heterojunction interface adjusts the local electronic environment of the active site and the adsorption energy of the intermediate, thereby improving the intrinsic catalytic activity of the active site. At the same time, the incorporation of non-noble metal Cu reduces the amount of noble metal Pt used while improving the activity of the catalyst, thereby reducing the cost of the catalyst.
[0017] In summary, the PtSe2 / PtCu heterojunction nanosphere catalyst prepared by the application has excellent application prospects. The method of the application is easy to operate, and the product is stable, which is conducive to the popularization and application of transition metal chalcogenide hydrogen evolution electrocatalytic materials and hydrogen energy conversion technology. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 Transmission electron microscope image of the PtCu3 hollow nanosphere prepared for Example 1.
[0019] Figure 2 Selected area diffraction pattern of the PtCu3 hollow nanosphere prepared for Example 1.
[0020] Figure 3 Low-magnification transmission electron microscope image of the PtSe2 / PtCu heterojunction nanosphere prepared for Example 1.
[0021] Figure 4 Selected area diffraction pattern of the PtSe2 / PtCu heterojunction nanosphere prepared for Example 1.
[0022] Figure 5 High-resolution transmission electron microscope image of the heterojunction interface of the PtSe2 / PtCu heterojunction nanosphere prepared for Example 1.
[0023] Figure 6 Linear sweep voltammetry (LSV) curve of the PtCu3 alloy and the PtSe2 / PtCu heterojunction nanosphere prepared for Example 1 in a 0.5M H2SO4 electrolyte solution. DETAILED DESCRIPTION
[0024] In order to make the technical problems to be solved by the application, the technical solutions and beneficial effects more clear and explicit, the application is further described in detail in combination with the embodiments and the drawings. It should be understood that the specific embodiments described herein are only used to explain the application and do not limit the application. The technical solutions of the application are described in detail below in combination with the embodiments and the drawings, but the protection scope is not limited thereto. Example 1
[0025] This embodiment proposes a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and a preparation method thereof, which specifically comprises the following steps: Step one, first, 20 mg of acetylacetone platinum, 100 mg of copper acetate monohydrate, 100 mg of cetyltrimethylammonium bromide were added to a solution of 12 mL of N,N-dimethylformamide, stirred at 25°C for 30 minutes.
[0026] Step two, then the above stirring solution was transferred to a 20 mL high pressure reactor, reacted at 180 °C for 12 h.
[0027] Step three, the solid-liquid mixture after reaction was centrifuged to obtain black solid product. The product was washed with a mixture of ethanol and deionized water with a volume ratio of 1:2 for 5 times, and then freeze-dried to obtain PtCu3 alloy hollow nanospheres.
[0028] Step four, the obtained PtCu3 alloy hollow nanospheres were placed in a double-temperature zone tube furnace for selenization: selenium powder was placed upstream of the tube furnace, the temperature was set to 220 °C, and PtCu3 alloy hollow nanospheres were placed downstream of the tube furnace, the temperature was set to 600 °C, after reaction for 2 h, the furnace was cooled down, and PtSe2 / PtCu nanospheres, i.e. PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst, were obtained.
[0029] Figure 1 The transmission electron microscope image of the PtCu3 alloy hollow nanospheres prepared in Example 1, from the figure it can be seen that the prepared PtCu3 alloy morphology is hollow nanospheres.
[0030] Figure 2 The selected area diffraction pattern of the PtCu3 alloy hollow nanospheres prepared in Example 1, from the figure it can be seen that the obtained PtCu3 alloy is a polycrystalline structure.
[0031] Figure 3 The transmission electron microscope image of the PtSe2 / PtCu heterojunction nanospheres prepared in Example 1, from the figure it can be seen that the sample obtained in Example 1 has a nanosphere morphology.
[0032] Figure 4 The selected area diffraction pattern of the PtSe2 / PtCu heterojunction nanospheres prepared in Example 1, from the figure it can be seen that the obtained PtSe2 / PtCu is a polycrystalline structure, and the diffraction rings of PtCu and PtSe2 exist at the same time.
[0033] Figure 5 The high-resolution transmission electron microscope image of the PtSe2 / PtCu nanospheres prepared in Example 1, from the figure it can be seen that there are a large number of heterojunction interfaces in the PtSe2 / PtCu nanospheres prepared in Example 1.
[0034] From the above map, it can be clearly seen that the PtSe2 / PtCu heterojunction nanospheres in this embodiment have a diameter of about 50 nm and contain a large number of heterojunction interfaces. The precise structure regulation at the nanoscale enables the catalyst to not only have a large number of high-efficiency electrocatalytic active sites, but also have a large specific surface area and excellent charge transport capacity, so that the prepared PtSe2 / PtCu heterojunction nanospheres have excellent electrocatalytic hydrogen evolution performance.
[0035] Figure 6 The LSV curves of the PtCu3 alloy and the PtSe2 / PtCu heterojunction nanospheres prepared in Example 1 in a 0.5 M H2SO4 electrolyte solution are shown in the figure. As can be seen from the figure, the overpotential of the PtCu3 alloy is 76 mV and the overpotential of the PtSe2 / PtCu heterojunction nanospheres is 40 mV at an exchange current density of 10 mA cm-2. That is, after seleniumization, the appearance of the heterojunction greatly improves the catalytic performance. -1
[0036] Example 2 This embodiment proposes a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and a preparation method thereof, which specifically comprises the following steps: Step one, first, 10 mg of platinum acetylacetone, 50 mg of copper acetate monohydrate and 100 mg of cetyltrimethylammonium bromide are added to a 12 mL N,N-dimethylformamide solution, and stirred at 15 °C for 30 minutes.
[0037] Step two, then the above stirred solution is transferred to a 20 mL high-pressure reaction kettle, and reacted at 180 °C for 12 h.
[0038] Step three, the solid-liquid mixture after reaction is centrifuged to obtain a black solid product. The product is washed with a mixed solution of ethanol and deionized water in a volume ratio of 1:2 for 5 times, and then freeze-dried to obtain PtCu3 alloy nanospheres.
[0039] Step four, the PtCu3 alloy nanospheres are placed in a double-temperature zone tube furnace for seleniumization. The selenium powder is placed upstream of the tube furnace, the temperature is set to 220 °C, and the PtCu3 alloy nanospheres are placed downstream of the tube furnace, the temperature is set to 500 °C, and the reaction is cooled with the furnace after 2 h to obtain PtSe2 / PtCu nanospheres. Example 3
[0040] This embodiment proposes a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and a preparation method thereof, which specifically comprises the following steps: Step one, first, 10 mg of platinum acetylacetonate, 50 mg of copper acetate monohydrate, 100 mg of cetyltrimethylammonium bromide were added to 12 mL of N,N-dimethylformamide solution, stirred at 20°C for 30 minutes.
[0041] Step two, then the above stirred solution was transferred to a 20 mL high-pressure reactor, and reacted at 180°C for 12 h.
[0042] Step three, the solid-liquid mixture after reaction was centrifuged to obtain black solid product. The product was washed with a mixture of ethanol and deionized water with a volume ratio of 1:2 for 5 times, and then freeze-dried to obtain PtCu3 alloy nanospheres.
[0043] Step four, the obtained PtCu3 alloy nanospheres were placed in a double-temperature zone tube furnace for selenization. The selenium powder was placed upstream of the tube furnace, and the temperature was set to 220°C. The PtCu3 alloy nanospheres were placed downstream of the tube furnace, and the temperature was set to 400°C. After 2h of reaction, the furnace was cooled down to obtain PtSe2 / PtCu nanospheres. Example 4
[0044] The present embodiment provides a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst and a preparation method thereof, specifically the following steps: Step one, first, 10 mg of platinum acetylacetonate, 50 mg of copper acetate monohydrate, 100 mg of cetyltrimethylammonium bromide were added to 12 mL of N,N-dimethylformamide solution, stirred at 20°C for 30 minutes.
[0045] Step two, then the above stirred solution was transferred to a 20 mL high-pressure reactor, and reacted at 180°C for 12 h.
[0046] Step three, the solid-liquid mixture after reaction was centrifuged to obtain black solid product. The product was washed with a mixture of ethanol and deionized water with a volume ratio of 1:2 for 5 times, and then freeze-dried to obtain PtCu3 alloy nanospheres.
[0047] Step four, the obtained PtCu3 alloy nanospheres were placed in a double-temperature zone tube furnace for selenization. The selenium powder was placed upstream of the tube furnace, and the temperature was set to 220°C. The PtCu3 alloy nanospheres were placed downstream of the tube furnace, and the temperature was set to 400°C. After 2h of reaction, the furnace was cooled down to obtain PtSe2 / PtCu nanospheres.
[0048] The above is further detailed description of the present application in combination with specific preferred embodiments, and cannot be deemed as limitation of the specific embodiments of the present application. For those skilled in the art of the present application, without departing from the present application, a number of simple deductions or substitutions can be made, which shall be deemed to belong to the present application, and the patent protection scope is determined by the submitted claims.
Claims
1. A method for preparing a PtSe 2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst, characterized in that, PtCu3 alloy hollow nanospheres are first grown by a hydrothermal method, and then the PtCu3 alloy hollow nanospheres are selenized in a tube furnace to obtain PtSe2 / PtCu nanospheres.
2. The preparation method of the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst according to claim 1, characterized in that, The PtCu3 alloy hollow nanospheres are grown by a hydrothermal method, in which platinum acetylacetonate, copper acetate monohydrate and cetyltrimethylammonium bromide are added to a N,N-dimethylformamide solution, the mixture is uniformly mixed, and then the solution is placed in a high-pressure hydrothermal reactor for reaction.
3. The preparation method of the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst according to claim 2, characterized in that, The uniform mixing is stirring for 0.5h-3h at 10-25℃.
4. The preparation method of the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst according to claim 2, characterized in that, The stirred and mixed solution is placed in a high-pressure hydrothermal reactor for reaction in a forced air drying oven.
5. The method for preparing a PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst according to claim 4, characterized in that, The temperature for the reaction is 180℃, and the reaction time is 12h.
6. The method of claim 2, wherein the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst is prepared by the following steps: (1) preparing a PtSe2 film on a substrate; (2) depositing a PtCu film on the PtSe2 film; and (3) annealing the PtSe2 / PtCu film. The solid-liquid mixture obtained after the reaction is centrifuged and washed multiple times to obtain black solids, and the black solids are dried to obtain PtCu3 alloy hollow nanospheres.
7. The method of claim 6, wherein the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst is prepared by the following steps: (1) preparing a PtSe2 film on a substrate; (2) depositing a PtCu film on the PtSe2 film; and (3) annealing the PtSe2 / PtCu film. The washing liquid is a mixed solution of ethanol and water in a volume ratio of 1:2, and the drying method is freeze-drying or vacuum drying.
8. The method of claim 1, wherein the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst is prepared by the following steps: (1) preparing a PtSe2 film on a substrate; (2) depositing a PtCu film on the PtSe2 film; and (3) annealing the PtSe2 / PtCu film. The selenization is placing selenium powder upstream of a tube furnace, placing PtCu3 alloy hollow nanospheres downstream of the tube furnace, heating and keeping warm for selenization to obtain PtSe2 / PtCu nanospheres.
9. The preparation method of the PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst according to claim 8, characterized in that, The temperature upstream of the tube furnace is 220℃, and the temperature downstream of the tube furnace is 400-700℃; the keeping warm time is 1-5h.
10. A PtSe2 / PtCu heterojunction hydrogen evolution reaction electrocatalyst prepared by the method of any one of claims 1-9.