With zinc and palladium bimetallic vacancies Pd v FeCoNiZn v Preparation method and application of LDH high entropy catalytic material

Abstract

The present invention discloses a preparation method and application of a Pd v FeCoNiZn v LDH high-entropy catalytic material. Palladium chloride is dispersed in absolute ethanol to obtain solution A; ferric chloride hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, ammonium fluoride and urea are added to deionized water, and then mixed with solution A to obtain solution B; nickel foam is placed in solution B for hydrothermal reaction to obtain nickel foam loaded with PdFeCoNiZn LDH; then it is placed in an alkaline solution and heated to react to obtain a flower-shaped Pd v FeCoNiZn v LDH high-entropy catalytic material assembled by nanosheets with abundant zinc and palladium bimetallic vacancies. The high-entropy catalytic material prepared by the present invention exhibits a fast mass transfer rate and reaction kinetics in electrocatalytic HER, and thus shows excellent electrocatalytic activity and stability, and can be used as an electrocatalytic water splitting hydrogen evolution catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation and application of water splitting hydrogen electrocatalyst, and specifically relates to a catalyst having zinc and palladium bimetallic vacancies Pd v FeCoNiZn v Preparation method and application of LDH high entropy catalytic material. Background Art

[0002] At present, hydrogen, as a clean energy, has attracted more and more attention due to its multiple advantages such as high energy density, broad application prospects and environmental protection. Electrocatalytic water splitting technology, as a low-cost method suitable for industrial-scale hydrogen production, has gradually become the focus of research and application. Hydrogen evolution reaction (HER) plays a unique role as the key half-reaction of water splitting. In order to accelerate the HER process, the development and design of catalytic materials with low overpotential and excellent stability has become a hot topic in this research field. However, HER electrocatalysts are still dominated by precious metal platinum (Pt)-based catalysts, but their high cost, scarcity and poor electrocatalytic durability limit their large-scale industrial application. Therefore, the development of low-cost catalysts with high catalytic activity and excellent durability has become an important task in the study of electrocatalytic water splitting HER.

[0003] In recent years, high entropy materials (HEMs) have gradually attracted widespread attention from researchers as an emerging research field. HEMs refer to materials composed of five or more main elements in equal atomic ratios (where the equiatomic limit is relaxed to about 5at.% to 35at.%), including one anion corresponding to multiple cations (such as oxides, hydroxides, fluorides and carbides) and multiple anions and cations. HEMs have complex elemental compositions, and the complex combination of elements can affect the macroscopic and microscopic structures of the materials, giving the catalysts unique properties. Layered hydroxides (LDHs) have more special properties due to their adjustable electronic structure and morphology, and have potential applications in the field of electrocatalysis. However, hydroxides undergo reconstruction in electrochemistry, which can seriously affect their catalytic durability and catalytic activity. Therefore, effective strategies are urgently needed to regulate the electrocatalytic activity and durability of high entropy LDH materials to solve the above technical problems. Summary of the invention

[0004] The technical problem solved by the present invention is to provide a zinc and palladium bimetallic vacancy Pd v FeCoNiZn v Preparation method of LDH high entropy catalytic material, the method prepared zinc, palladium bimetallic vacancy Pd v FeCoNiZn vLDH high entropy catalytic materials exhibit faster mass transfer rate and reaction kinetics in electrocatalytic HER, and thus exhibit excellent electrocatalytic activity and stability. v FeCoNiZn v The overpotential of LDH high entropy catalytic material as HER catalyst is significantly lower than that of PdFeCoNiZn LDH electrocatalyst without metal vacancies and FeCoNiZn LDH electrocatalyst, and is also better than the currently reported HER electrocatalysts.

[0005] The present invention aims to construct a high-entropy layered hydroxide structure in response to the technical problems existing in existing hydroxides. High-entropy materials can significantly improve the stability of traditional layered hydroxides due to their unique "entropy effect". In order to reduce costs and maintain catalytic performance, the present invention introduces palladium (Pd), which is cheaper than platinum (Pt), as a precious metal element. On the one hand, Pd belongs to the same family as Pt and has similar electronic structures and similar performances; on the other hand, Pd's lower first ionization energy makes it easier to transfer electrons as an electron donor, by providing electrons to high-valent transition metal elements to reduce their valence states and increase electron density, thereby inhibiting hydroxide reconstruction and further improving structural stability. In addition, partial etching of Zn and Pd bimetallic elements in an alkaline environment can produce cation vacancies. These vacancies not only retain unpaired electrons and optimize the electronic structure of the metal sites on the catalyst surface, but also provide more active sites, ultimately achieving a Pd with zinc and palladium bimetallic vacancies. v FeCoNiZn v LDH high entropy catalytic material for efficient electrocatalytic hydrogen evolution.

[0006] The present invention adopts the following technical solution to solve the above technical problems, with zinc and palladium bimetallic vacancies Pd v FeCoNiZn v The preparation method of LDH high entropy catalytic material comprises the following specific steps:

[0007] Step S1: dispersing palladium chloride in anhydrous ethanol to obtain solution A;

[0008] Step S2: adding ferric chloride hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, ammonium fluoride and urea to deionized water, mixing well, and then continuing to mix well with the solution A obtained in step S1 to obtain solution B;

[0009] Step S3: placing the nickel foam in the solution B obtained in step S2 and reacting under a hydrothermal condition of 110-120° C. for 4-8 hours, and washing and drying after the reaction to obtain the nickel foam loaded with PdFeCoNiZn LDH;

[0010] Step S4: placing the nickel foam loaded with PdFeCoNiZn LDH obtained in step S3 in an alkaline solution and heating the solution at 60-80°C for 1.5-3h. After the reaction, washing with deionized water and drying the solution to obtain a flower-like Pd nanosheet self-assembled with abundant zinc and palladium bimetallic vacancies. v FeCoNiZn v LDH high entropy catalytic material.

[0011] Furthermore, the mass ratio of the palladium chloride described in step S1 to the ferric chloride hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, urea, and ammonium fluoride described in step S2 is 1.0~1.5:2.5~3.0:6.0~7.0:6.0~7.0:1.0~1.5:8.0~8.5:13.0~14.0; the volume ratio of the anhydrous ethanol described in step S1 to the deionized water described in step S2 is 1:2~3.

[0012] Furthermore, the average particle size of the PdFeCoNiZn LDH in step S3 is 5-9 μm; v FeCoNiZn v The average particle size of LDH high entropy catalytic material is 5~9μm.

[0013] Furthermore, the alkaline solution in step S4 is a sodium hydroxide solution or a potassium hydroxide solution.

[0014] The present invention has zinc and palladium bimetallic vacancies Pd v FeCoNiZn v Application of LDH high entropy catalytic materials in electrocatalytic water splitting hydrogen release catalysts.

[0015] Compared with the prior art, the present invention has the following advantages and beneficial effects: the present invention synthesizes Pd with excellent electrocatalytic activity and rich zinc and palladium double vacancies by two-step water bath heating v FeCoNiZn v LDH high entropy catalytic material, cation vacancies regulate the catalytic performance of the catalytic material, this method is simple and easy. v FeCoNiZn vWhen the LDH high entropy catalytic material is used as an electrocatalyst for electrocatalysis HER, Pd transfers electrons as an electron donor, and reduces the valence state by supplying electrons to high-valent transition metal elements, increases the electron density, stabilizes the metal valence state, inhibits hydroxide reconstruction, and thus improves structural stability. Cationic vacancies are generated by partially etching away zinc and palladium bimetallic elements in an alkaline environment. These vacancies not only retain unpaired electrons, optimize the electronic structure of the metal sites on the catalyst surface, but also provide more active sites. Compared with the separate PdFeCoNiZn LDH electrocatalyst and FeCoNiZn LDH electrocatalyst, the Pd prepared by the present invention v FeCoNiZn v LDH high entropy catalytic materials exhibit excellent electrochemical performance as HER electrocatalysts at 10 mA cm -2 The electrocatalytic hydrogen evolution overpotential at the current density is 11mV±5mV, which is much higher than that of PdFeCoNiZn LDH electrocatalyst (31mV±6mV) and FeCoNiZn LDH electrocatalyst (195mV±5mV). v FeCoNiZn v LDH high entropy catalytic material at 100 mA cm -2 The Pd prepared by the present invention can maintain excellent stability for 350 hours under high current density and has almost no current decay without current. v FeCoNiZn v The HER overpotential of LDH high entropy catalytic materials is also better than that of currently reported HER electrocatalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Pd prepared in Example 1 and Comparative Examples 1-2 of the present invention v FeCoNiZn v X-ray diffraction patterns of LDH, PdFeCoNiZn LDH, and FeCoNiZn LDH materials.

[0017] Figure 2 Pd obtained in Example 1 and Comparative Example 1 of the present invention v FeCoNiZn v X-ray photoelectron surface metal atomic ratio maps of LDH and PdFeCoNiZn LDH materials.

[0018] Figure 3 Pd prepared in Example 1 and Comparative Examples 1-2 of the present invention v FeCoNiZn v Field emission scanning electron microscope images of LDH, PdFeCoNiZn LDH, and FeCoNiZn LDH materials.

[0019] Figure 4 Pd prepared in Example 1 and Comparative Examples 1-2 of the present invention v FeCoNiZn v Raman spectra of LDH, PdFeCoNiZn LDH, and FeCoNiZn LDH materials.

[0020] Figure 5 Pd obtained in Example 1 and Comparative Example 1 of the present invention v FeCoNiZn v Electron paramagnetic resonance spectra of LDH and PdFeCoNiZn LDH materials.

[0021] Figure 6 Pd prepared in Example 1 and Comparative Examples 1-2 of the present invention v FeCoNiZn v Linear scan cyclic voltammetry spectra of LDH, PdFeCoNiZn LDH, and FeCoNiZn LDH materials.

[0022] Figure 7 Pd prepared in Example 1 and Comparative Examples 1-2 of the present invention v FeCoNiZn v Tafel dynamics and double-layer capacitance spectra of LDH, PdFeCoNiZn LDH, and FeCoNiZn LDH materials.

[0023] Figure 8 The Pd prepared in Example 1 of the present invention v FeCoNiZn v Stability test chart of LDH material.

[0024] Fig. 9 The Pd prepared in Example 1 of the present invention v FeCoNiZn v Linear scan cyclic voltammetry spectrum of total hydrolysis of LDH material. DETAILED DESCRIPTION

[0025] The above contents of the present invention are further described in detail below through examples, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples, and all technologies implemented based on the above contents of the present invention belong to the scope of the present invention. Example 1

[0026] Step S1: weigh 0.0300 g of palladium chloride and disperse it in 10 mL of anhydrous ethanol to obtain a palladium chloride suspension;

[0027] Step S2: weigh 0.0830 g of ferric chloride hexahydrate, 0.2030 g of cobalt nitrate, 0.2030 g of nickel nitrate, 0.0240 g of zinc nitrate hexahydrate, 0.2550 g of urea, and 0.3950 g of ammonium fluoride, and dissolve them in 20 mL of deionized water to obtain a mixed solution, and then add the palladium chloride suspension obtained in step S1 to the mixed solution and mix well;

[0028] Step S3: adding nickel foam to the mixed solution obtained in step S2 and transferring the mixture to a stainless steel autoclave lined with polytetrafluoroethylene, heating the mixture to 120° C. for reaction for 6 hours, and then washing and drying the nickel foam to obtain nickel foam loaded with PdFeCoNiZn LDH;

[0029] Step S4: The nickel foam loaded with PdFeCoNiZn LDH obtained in step S3 was placed in a 4 M KOH solution and heated in a water bath at 60°C for 3 h. The sample was then taken out, washed with deionized water, and dried to obtain a flower-like Pd with abundant zinc and palladium bimetallic vacancies. v FeCoNiZn v LDH high entropy electrocatalyst.

[0030] from Figure 1 It can be seen that Pd v FeCoNiZn v Characteristic diffraction peaks of LDH and hexagonal Ni6Fe2(CO3)(OH) 16 4H2O (JCPDS card No. 26-1286), further confirming that Pd v FeCoNiZn v The successful synthesis of LDH high entropy electrocatalyst. Figure 2 After alkaline etching, Pd v FeCoNiZn v The significant decrease in the atomic percentage of Pd and Zn in LDH confirms the successful formation of bimetallic vacancies. Figure 3 Pd synthesized by a simple two-step water bath method can be observed in the ac v FeCoNiZn v The LDH high entropy electrocatalyst is a flower-like structure self-assembled from nanosheets with an average particle size of 8 μm, which is similar to the PdFeCoNiZn in Comparative Example 1. The comparison of the morphology and structure of LDH electrocatalysts shows that the Pd v FeCoNiZn v The overall morphology of the LDH high-entropy electrocatalyst was not destroyed. Figure 4 The Raman spectrum shows that at 447 cm -1 and 542cm -1There are typical LDH characteristic peaks near 600cm, which correspond to the vibration of M-OH and MO bonds, respectively. -1 The obvious characteristic peaks near are related to the cation vacancies in the LDH framework. Figure 5 It can be seen that at g = 2.0038 and 2.0164, two cation vacancy signals appear, which correspond to Pd vacancies and Zn vacancies, respectively. These vacancies can improve the electron density around the metal elements and enhance the Pd v FeCoNiZn v The number of active sites on the surface of LDH high entropy electrocatalyst is more conducive to the subsequent generation of hydrogen. Figure 6 It can be seen that when the current density is 10 mA cm -2 The over potential is 6mV. Figure 7 The Tafel kinetic spectrum of a shows that Pd v FeCoNiZn v The Tafel slope value of the LDH high entropy electrocatalyst is 40.8 mV dec -1 , which are much lower than those of the synthesized catalyst materials without vacancies. Figure 7 The double layer capacitance spectrum of Pd can be seen in b. v FeCoNiZn v The value of LDH high entropy electrocatalyst is 12.12 mF cm -2 , much higher than PdFeCoNiZn LDH electrocatalyst (5.44 mF cm -2 ) and FeCoNiZn LDH (0.55 mF cm -2 ), indicating that in an alkaline environment, the partial etching of palladium and zinc ions to generate cation vacancies provides more active sites on the LDH surface. Figure 8 You can see Pd v FeCoNiZn v Stability of LDH high-entropy electrocatalyst at 100 mA cm -2 The high current density can run for 350h without obvious current decay. v FeCoNiZn v Excellent HER performance of LDH high entropy electrocatalysts using RuO2 as anode and Pd v FeCoNiZn v The LDH high entropy electrocatalyst was used as the cathode to assemble a full water splitting system for linear cyclic voltammetry test. Fig. 9 It can be seen that this system reaches 10mA cm -2The current density only requires a full hydrolysis potential of 1.56 V, showing relatively good full hydrolysis performance. v FeCoNiZn v The HER overpotential of LDH high-entropy electrocatalyst is superior to that of the currently reported high-entropy electrocatalysts.

[0031] Table 1 is the zinc and palladium bimetallic vacancies Pd prepared in Example 1 v FeCoNiZn v Comparison of electrochemical performance between LDH high entropy electrocatalysts and currently reported HER electrocatalysts:

[0032] Table 1

[0033] name electrode Overpotential(mV) <![CDATA[Tafel (mV dec –1 )]]> Related Literature <![CDATA[Pd v FeCoNiZn v LDH]]> nickel foam 6 (η10) 40.6 The present invention Ru−RuSi / C glassy carbon 27 (η10) 27.0 [1] <![CDATA[Ni3S2 / NiO]]> Carbon paper 95 (η10) [2] RuNi / NC glassy carbon 12 (η10) 30.9 [3] <![CDATA[a-Ru@GNL 500 ]]> Carbon paper 23 (η10) 49.0 [4] <![CDATA[Ni3Sn2NiSnO x ]]> nickel foam 14 (η10) 68.8 [5] PdP glassy carbon 30 (η10) [6] PtMoPdRhNi NCs glassy carbon 10 (η10) 25.9 [7] <![CDATA[Ru–Sn / SnO2NS]]> glassy carbon 12 (η10) 22.7 [8] <![CDATA[Co-1T-MoS2-bpe]]> Carbon paper 118 (η10) 83.0 [9] IrMo-CBC glassy carbon 12 (η10) 28.06

[10]

[0034] Related Literature:

[0035] [1] Hou Liqiang, Li Zijian, Jaing Haeseong. et al. PartiallyInterstitial Silicon-Implanted Ruthenium as an Efficient Electrocatalyst for Alkaline Hydrogen Evolution[J]. Angewandte Chemie, 2024: e202423756.

[0036] [2] Ding Xingyu, Liu Da, Zhao Pengju. et al. Dynamic restructuring ofnickel sulfides for electrocatalytic hydrogen evolution reaction[J]. NatureCommunications, 2024, 15:5336.

[0037] [3] Zhang Linjie, Hu Haihui, Sun Chen. et al. Bimetallic nanoalloysplanted on super-hydrophilic carbon nanocages featuring tip-intensifiedhydrogen evolution electrocatalysis[J]. Nature Communications, 2024, 15:7179.

[0038] [4] Karim Golammasud, Patra Amalika, Deb Sujit. et al. TransientElectro-Graphitization of MOFs Affecting the Crystallization of RutheniumNanoclusters for Highly Efficient Hydrogen Evolution[J]. Advanced FunctionalMaterials, 2024, 34: 2315460。

[0039] [5] Wang Xiaomei, Long Guifa, Liu Bo. et al. Rationally Modulatingthe Functions of Ni3Sn2-NiSnOx Nanocomposite Electrocatalysts towardsEnhanced Hydrogen Evolution Reaction[J]. Angewandte Chemie, 2023, 62:e202301562。

[0040] [6] Liu Yihong, Hsieh Chia-Jui, Hsu Liang-Ching. et al. Towardcontrollable and predictable synthesis of high-entropy alloy nanocrystals[J].Science Advances, 2023, 9: 19。

[0041] [7] Wei Min, Sun Yuyan, Zhang Junyu. et al. High-Entropy Alloynanocrystal assembled by nanosheets with d-d electron interaction forHydrogen Evolution Reaction[J]. Energy&Environmental Science, 2023, 16: 4009-4019。

[0042] [8] Yan Zhentong, Tao Shi, Wang Juan. et al. Unlocking EfficientAlkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a NovelHydroxyl Spillover Effect[J]. Advanced Materials, 2024, 36: 2411942.

[0043] [9] Liu Haijun, Zhang Shuo, Chai Yongming. et al. Ligand Modulation of Active Sites to Promote Cobalt-Doped 1T-MoS2 Electrocatalytic HydrogenEvolution in Alkaline Media[J]. Angewandte Chemie, 2023, 62: e202313845.

[0044]

[10] Xiao Xin, Li Zheng, Xiong Ying et al. IrMo Nanocluster-DopedPorous Carbon Electrocatalysts Derived from Cucurbit[6]uril Boost EfficientAlkaline Hydrogen Evolution[J]. Journal of the American Chemical Society, 2023, 145: 16548–16556.

[0045] Comparative Example 1

[0046] Step S1: weigh 0.0300 g of palladium chloride and disperse it in 10 mL of anhydrous ethanol to obtain a palladium chloride suspension;

[0047] Step S2: weigh 0.0830 g of ferric chloride hexahydrate, 0.2030 g of cobalt nitrate, 0.2030 g of nickel nitrate, 0.0240 g of zinc nitrate hexahydrate, 0.2550 g of urea, and 0.3950 g of ammonium fluoride, and dissolve them in 20 mL of deionized water to obtain a mixed solution, and then add the palladium chloride suspension obtained in step S1 to the mixed solution and mix well;

[0048] Step S3: Add nickel foam to the mixed solution obtained in step S2 and transfer to a stainless steel autoclave lined with polytetrafluoroethylene, heat to 120° C. and react for 6 hours, then wash and dry the nickel foam to obtain nickel foam loaded with PdFeCoNiZn LDH.

[0049] from Figure 1 It can be seen that the characteristic diffraction peaks of PdFeCoNiZn LDH and the hexagonal phase of Ni6Fe2(CO3)(OH) 16 4H2O(JCPDS card No. 26-1286). Figure 2 It can be seen that the metal atomic ratios of PdFeCoNiZn LDH are: Fe 22.46%, Ni 41.08%, Pd 4.91%, Zn 9.25%, Co 22.31%. Figure 3 In the middle DF, it can be observed that the synthesized PdFeCoNiZn LDH is a flower-like structure self-assembled by nanosheets with an average particle size of 8 μm. Figure 4 The Raman spectrum shows that at 447 cm -1 and 542cm -1 The characteristic peaks nearby correspond to the vibration of M-OH and MO bonds. From the linear cyclic voltammetry Figure 6 It can be seen that when the current density is 10 mA cm -2 When the overpotential is 26mV, Figure 7 The Tafel kinetic spectrum in a shows that the Tafel slope of PdFeCoNiZn LDH is 97.9 mV dec -1 , Figure 7 The double layer capacitance spectrum in (b) shows that the double layer capacitance of PdFeCoNiZn LDH is 5.44 mF cm -2 .

[0050] Comparative Example 2

[0051] Step S1: weigh 0.0830 g of ferric chloride hexahydrate, 0.2030 g of cobalt nitrate, 0.2030 g of nickel nitrate, 0.0240 g of zinc nitrate hexahydrate, 0.2550 g of urea, and 0.3950 g of ammonium fluoride and dissolve them in 20 mL of deionized water to obtain a mixed solution;

[0052] Step S2: Add nickel foam to the mixed solution obtained in step S1 and transfer to a stainless steel autoclave lined with polytetrafluoroethylene, heat to 120° C. and react for 6 hours, then wash and dry the nickel foam to obtain nickel foam loaded with FeCoNiZn LDH.

[0053] from Figure 1 It can be seen that the characteristic diffraction peaks of FeCoNiZn LDH and the hexagonal phase of Ni6Fe2(CO3)(OH)16 4H2O(JCPDS card No. 26-1286). Figure 3 It can be observed that the synthesized FeCoNiZn LDH is a flower-like structure self-assembled by nanosheets with an average particle size of 10 μm. Figure 4 The Raman spectrum shows that at 447 cm -1 and 542cm -1 The characteristic peaks nearby correspond to the vibration of M-OH and MO bonds. From the linear cyclic voltammetry Figure 6 It can be seen that when the current density is 10 mA cm -2 The overpotential is 190mV. Figure 7 The Tafel kinetic spectrum of a shows that the Tafel slope value of FeCoNiZn LDH is 159.8mVdec -1 , Figure 7 The double layer capacitance spectrum in b shows that the double layer capacitance of FeCoNiZn LDH is 0.55 mF cm -2 .

[0054] The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of protection of the present invention.

Claims

1. Has zinc and palladium bimetallic vacancies Pd v FeCoNiZn v The preparation method of LDH high entropy catalytic material is characterized in that The specific steps are: Step S1: dispersing palladium chloride in anhydrous ethanol to obtain solution A; Step S2: adding ferric chloride hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, ammonium fluoride and urea to deionized water, mixing evenly, and then continuing to mix evenly with the solution A obtained in step S1 to obtain solution B, wherein the mass ratio of the palladium chloride in step S1 to the ferric chloride hexahydrate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, urea and ammonium fluoride in step S2 is 1.0-1.5:2.5-3.0:6.0-7.0:6.0-7.0:1.0-1.5:8.0-8.5:13.0-14.0; Step S3: placing the nickel foam in the solution B obtained in step S2 and reacting under a hydrothermal condition of 110-120° C. for 4-8 hours, and washing and drying after the reaction to obtain the nickel foam loaded with PdFeCoNiZn LDH; Step S4: placing the nickel foam loaded with PdFeCoNiZn LDH obtained in step S3 in an alkaline solution and heating the solution at 60-80°C for 1.5-3h. After the reaction, washing with deionized water and drying the solution to obtain a flower-like Pd nanosheet self-assembled with abundant zinc and palladium bimetallic vacancies. v FeCoNiZn v LDH high entropy catalytic material.

2. The zinc and palladium bimetallic vacancy Pd according to claim 1 v FeCoNiZn v The preparation method of LDH high entropy catalytic material is characterized by: The volume ratio of the anhydrous ethanol in step S1 to the deionized water in step S2 is 1:2-3.

3. The zinc and palladium bimetallic vacancy Pd according to claim 1 v FeCoNiZn v The preparation method of LDH high entropy catalytic material is characterized by: The average particle size of the PdFeCoNiZn LDH in step S3 is 5 to 9 μm; the Pd v FeCoNiZn v The average particle size of the LDH high entropy catalytic material is 5 to 9 μm.

4. The zinc and palladium bimetallic vacancy Pd according to claim 1 v FeCoNiZn v The preparation method of LDH high entropy catalytic material is characterized by: The alkaline solution in step S4 is a sodium hydroxide solution or a potassium hydroxide solution.

5. The Pd having zinc and palladium bimetallic vacancies prepared by the method according to any one of claims 1 to 4 v FeCoNiZn v Application of LDH high entropy catalytic materials in electrocatalytic water splitting hydrogen release catalysts.

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