Electrolysis water hydrogen production catalyst, preparation method and application thereof

Abstract

The present application relates to the technical field of hydrogen production by water electrolysis, and particularly relates to a hydrogen production catalyst for water electrolysis, a preparation method and application thereof. The present application provides a preparation method of a hydrogen production catalyst for water electrolysis, comprising the following steps: mixing an ethanol aqueous dispersion of palladium, a metal precursor dispersion and an ethanol solution of 1-naphthol, and performing a solvothermal reaction to obtain the hydrogen production catalyst for water electrolysis; the hydrogen production catalyst for water electrolysis is an alloy hydride of metallic palladium. The preparation method is simple in operation, low in cost, and friendly to the environment, and the hydrogen production catalyst for water electrolysis prepared by the method has high electrocatalytic performance.

Description

Technical Field

[0001] This invention relates to the field of water electrolysis for hydrogen production technology, and in particular to a catalyst for water electrolysis for hydrogen production, its preparation method, and its application. Background Technology

[0002] Hydrogen energy, as a low-carbon and highly efficient clean energy source, plays a crucial role in global energy transition and addressing climate change. In particular, hydrogen production through water electrolysis, powered by renewable energy sources—known as green hydrogen—does not emit greenhouse gases and is therefore widely considered a key pathway to achieving carbon neutrality. Since the efficiency and cost of hydrogen production through water electrolysis largely depend on the catalyst used, highly efficient catalysts can significantly reduce overpotential during electrolysis, thereby improving energy conversion efficiency and achieving highly efficient water electrolysis for hydrogen production.

[0003] Palladium metal is an ideal alternative to platinum due to its low cost, platinum-like catalytic activity, good stability, and relatively abundant resources, especially in the field of hydrogen production through water electrolysis. However, the strong bond between palladium and hydrogen makes hydrogen desorption difficult, leading to stability issues during water electrolysis. Metal alloy hydrides prepared using palladium as a precursor can effectively improve the adsorption free energy of the catalyst, thereby optimizing the adsorption energy of intermediate products and ultimately enhancing the performance of hydrogen production through water electrolysis. However, the synthesis of palladium-containing alloy hydrides faces challenges such as complex processes, high raw material costs, and the potential environmental impact of certain raw materials. Summary of the Invention

[0004] The purpose of this invention is to provide a water electrolysis hydrogen production catalyst, its preparation method and application. The preparation method is simple to operate, low in cost and environmentally friendly, and the prepared water electrolysis hydrogen production catalyst has high electrocatalytic performance.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a catalyst for hydrogen production through water electrolysis, comprising the following steps:

[0007] The palladium ethanol aqueous dispersion, the metal precursor dispersion, and the 1-naphthol ethanol solution were mixed and subjected to a solvothermal reaction to obtain the electrolytic water hydrogen production catalyst.

[0008] The catalyst for hydrogen production through water electrolysis is an alloy hydride of metallic palladium.

[0009] Preferably, the palladium in the palladium ethanol aqueous dispersion is nano-palladium;

[0010] The microstructure of the palladium nanoparticles includes one or more of the following: nanoparticles, nanowires, nanotubes, nanodendritic crystals, nanoflowers, nanorods, and nanostars.

[0011] The concentration of the palladium aqueous dispersion in ethanol is 50–200 mg / L.

[0012] Preferably, the metal precursor in the metal precursor dispersion includes one or more of ruthenium trichloride, copper chloride dihydrate, ferric chloride hexahydrate, nickel chloride, zinc chloride, and cobalt chloride hexahydrate;

[0013] The concentration of the metal precursor dispersion is 0.01–0.1 mol / L.

[0014] Preferably, the concentration of the 1-naphthol ethanol solution is 0.1 to 1 mol / L.

[0015] Preferably, the ratio of palladium to metal precursor dispersion in the palladium ethanol aqueous dispersion is (1-10) mg: (0.01-1) mL.

[0016] Preferably, the volume ratio of the metal precursor dispersion to the ethanol solution of 1-naphthol is (0.01-1):(0.3-0.7).

[0017] Preferably, the temperature of the solvothermal reaction is 100–240°C, and the time is 1–36 h.

[0018] Preferably, after the solvothermal reaction is completed, the process further includes sequential centrifugation, washing, and drying.

[0019] The present invention also provides an electrolytic hydrogen production catalyst for water electrolysis prepared by the preparation method described above, wherein the electrolytic hydrogen production catalyst for water electrolysis is a metal alloy hydride;

[0020] The metal alloy hydride includes a palladium crystal and doped metal atoms and hydrogen atoms embedded in the palladium crystal structure.

[0021] This invention also provides the application of the electrolytic hydrogen production catalyst described in the above technical solution in the field of water electrolysis hydrogen production.

[0022] This invention provides a method for preparing a catalyst for hydrogen production through water electrolysis, comprising the following steps: mixing an ethanol-water dispersion of palladium, a metal precursor dispersion, and an ethanol solution of 1-naphthol, and carrying out a solvothermal reaction to obtain the catalyst; the catalyst is an alloy hydride of metallic palladium. This invention uses palladium as a substrate and prepares a metal alloy hydride catalyst through a one-step solvothermal reaction by doping with metal elements, ensuring the effective introduction of metal atoms and hydrogen atoms, increasing the active sites on the palladium surface, expanding the electron transfer channels, and improving electrochemical activity; simultaneously, the preparation method, through a one-step solvothermal reaction, is simple to operate, environmentally friendly, non-toxic, and uses low-cost raw materials. Attached Figure Description

[0023] Figure 1 The images shown are TEM and EDS images of the ruthenium-palladium alloy hydride described in Example 1.

[0024] Figure 2 XPS images of the ruthenium-palladium alloy hydride described in Example 1 and the ruthenium-palladium alloy described in Comparative Example 1;

[0025] Figure 3 The images show the XRD patterns of the ruthenium-palladium alloy hydride described in Example 1, the ruthenium-palladium alloy described in Comparative Example 1, and the ruthenium hydride described in Comparative Example 2.

[0026] Figure 4 Linear sweep voltammetry (LSV) curves of the ruthenium-palladium alloy hydride of Example 1, the ruthenium-palladium alloy of Comparative Example 1, and the palladium hydride of Comparative Example 2 during water electrolysis hydrogen production tests.

[0027] Figure 5 Linear sweep voltammetry (LSV) curves of the ruthenium-palladium alloy hydride described in Example 2, the ruthenium-palladium alloy hydride described in Example 3, the ruthenium-palladium alloy hydride described in Example 4, and the copper-palladium alloy hydride described in Example 5 during water electrolysis hydrogen production tests. Detailed Implementation

[0028] This invention provides a method for preparing a catalyst for hydrogen production through water electrolysis, comprising the following steps:

[0029] The palladium ethanol aqueous dispersion, the metal precursor dispersion, and the 1-naphthol ethanol solution were mixed and subjected to a solvothermal reaction to obtain the electrolytic hydrogen production catalyst.

[0030] The catalyst for hydrogen production through water electrolysis is an alloy hydride of metallic palladium.

[0031] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0032] In this invention, the palladium in the palladium ethanol aqueous dispersion is preferably nano-palladium; the microstructure of the nano-palladium preferably includes one or more of nanoparticles, nanowires, nanotubes, nanodendritic crystals, nanoflowers, nanorods, and nanostars; when the microstructure of the nano-palladium is two or more of the above-mentioned specific selections, this invention does not have any special limitation on the ratio of the nano-palladium with the above-mentioned specific microstructures, and they can be mixed in any ratio. In this invention, the solvent in the palladium ethanol aqueous dispersion is preferably an aqueous ethanol solution; the concentration of ethanol in the aqueous ethanol solution is 50 vol%. In this invention, the concentration of the palladium ethanol aqueous dispersion is preferably 50-200 mg / L, more preferably 100-150 mg / L. In this invention, the palladium ethanol aqueous dispersion is preferably dispersed by adding palladium to a solvent; this invention does not have any special limitation on the dispersion process, and a process well known to those skilled in the art can be used. In an embodiment of this invention, the concentration of the palladium ethanol aqueous dispersion can be 125 mg / L. The microstructure of the palladium in the palladium ethanol aqueous dispersion is nanodendritic crystals. In an embodiment of the present invention, the palladium in the palladium ethanol aqueous dispersion can be prepared by adding 0.5 mL of a 0.05 mol / L palladium acetate acetic acid solution to 3 mL of water, adding 0.5 mL of a 0.5 mol / L 1-naphthol ethanol solution, reacting in a water bath at 60°C for 2 h, washing 6 times by centrifugation with ethanol, and freeze-drying for 24 h to obtain palladium with a microstructure of nano-dendritic crystals.

[0033] In this invention, the metal precursor in the metal precursor dispersion preferably includes one or more of ruthenium trichloride, copper chloride dihydrate, ferric chloride hexahydrate, nickel chloride, zinc chloride, and cobalt chloride hexahydrate. When the metal precursor is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned specific substances. In this invention, the solvent in the metal precursor dispersion is deionized water. In this invention, the concentration of the metal precursor dispersion is preferably 0.01–0.1 mol / L, more preferably 0.03–0.06 mol / L. In an embodiment of this invention, the concentration of the metal precursor dispersion can be 0.05 mol / L; the metal precursor in the metal precursor dispersion can be copper chloride dihydrate, ruthenium trichloride, nickel chloride, ferric chloride hexahydrate, zinc chloride, or cobalt chloride hexahydrate.

[0034] In this invention, the concentration of the 1-naphthol ethanol solution is preferably 0.1–1 mol / L, more preferably 0.3–0.7 mol / L. In an embodiment of this invention, the concentration of the 1-naphthol ethanol solution can be 0.5 mol / L. In this invention, the role of 1-naphthol in the 1-naphthol ethanol solution is as a reducing agent to reduce metal ions to elemental metals.

[0035] In this invention, the preferred ratio of palladium to metal precursor dispersion in the palladium ethanol aqueous dispersion is (1-10) mg:(0.01-1) mL, more preferably (3-6) mg:(0.01-0.5) mL. In embodiments of this invention, the preferred ratio of palladium to metal precursor dispersion in the palladium ethanol aqueous dispersion is 4 mg:0.1 mL, 4 mg:0.01 mL, or 4 mg:0.4 mL.

[0036] In this invention, the volume ratio of the metal precursor dispersion to the ethanol solution of 1-naphthol is preferably (0.01–1):(0.3–0.7), more preferably (0.01–0.5):(0.4–0.6). In embodiments of this invention, the volume ratio of the metal precursor dispersion to the ethanol solution of 1-naphthol can be 0.1:0.5, 0.01:0.5, or 0.4:0.5.

[0037] In this invention, the mixing of the palladium ethanol aqueous dispersion, the metal precursor dispersion, and the 1-naphthol ethanol solution is preferably carried out by sequentially adding the metal precursor dispersion and the 1-naphthol ethanol solution to the palladium ethanol aqueous dispersion. This invention does not impose any particular limitation on the method of addition; any method well-known to those skilled in the art can be used.

[0038] In this invention, the temperature of the solvothermal reaction is preferably 100–240°C, more preferably 150–200°C; the time is preferably 1–36 h, more preferably 12–20 h. In embodiments of this invention, the temperature of the solvothermal reaction can be 100°C, 200°C, or 240°C; the time can be 12 h, 1 h, or 36 h.

[0039] After the solvothermal reaction is completed, the present invention preferably includes sequential centrifugal washing and drying. The present invention does not impose any special limitations on the centrifugal washing process; any process well-known to those skilled in the art can be used. In the present invention, the washing is preferably performed six times with ethanol. In the present invention, the drying method is preferably freeze-drying. The present invention does not impose any special limitations on the freeze-drying process; any process well-known to those skilled in the art can be used. In an embodiment of the present invention, the freeze-drying time can be 24 hours.

[0040] The present invention also provides an electrolytic hydrogen production catalyst for water electrolysis prepared by the preparation method described above, wherein the electrolytic hydrogen production catalyst for water electrolysis is a metal alloy hydride;

[0041] The metal alloy hydride includes a palladium crystal and doped metal atoms and hydrogen atoms embedded in the palladium crystal structure.

[0042] In an embodiment of the present invention, the molar ratio of the doped metal atoms to the palladium crystal can be 7:67.

[0043] In this invention, the doped metal atoms preferably include one or more of ruthenium, copper, iron, nickel, zinc and cobalt. When the doped metal atoms are two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the specific ratio of the doped metal atoms, and they can be mixed in any ratio.

[0044] This invention also provides the application of the electrolytic hydrogen production catalyst described in the above technical solution in the field of water electrolysis hydrogen production.

[0045] In this invention, the method of application preferably includes:

[0046] The present invention mixes the electrolytic hydrogen production catalyst and conductive carbon powder described in the above technical solution, and then adds isopropanol, deionized water and Nafion solution with a mass concentration of 5% to obtain ink.

[0047] In this invention, the mass ratio of the water electrolysis hydrogen production catalyst to the conductive carbon powder is preferably 1:1; the volume ratio of the isopropanol, deionized water, and Nafion solution is preferably 6:3:1. In this invention, the concentration of the water electrolysis hydrogen production catalyst in the ink is preferably 1–5 g / L, more preferably 2 g / L.

[0048] After obtaining the ink, the present invention adds the ink dropwise onto a glassy carbon electrode and then electrolyzes it in a potassium hydroxide solution.

[0049] In this invention, the amount of liquid added is preferably 8 to 15 μL, more preferably 9 to 10 μL.

[0050] In this invention, the concentration of the potassium hydroxide solution is preferably 1 mol / L.

[0051] In this invention, all electrochemical measurements were performed in a standard three-electrode electrochemical cell at room temperature using a CHI 660E workstation (CH Instruments, Shanghai Chenhua Co., Ltd.). A graphite rod was used as the auxiliary electrode, and a saturated calomel electrode (SCE) was used as the reference electrode. A glassy carbon electrode (3 mm in diameter) loaded with ink for hydrogen evolution through water electrolysis catalyst was used as the working electrode. The hydrogen evolution reaction (HER) was studied in a N2-saturated 1.0 M KOH solution at a scan rate of 5 mV / s. All electrode potentials are referenced relative to the reversible hydrogen electrode (RHE). In our electrochemical testing system at 1.0 M KOH, E(RHE) = E(SCE) + 1.068 V.

[0052] The following detailed description, in conjunction with embodiments, illustrates the electrolytic hydrogen production catalyst for water electrolysis provided by the present invention, its preparation method, and its application. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0053] Example 1

[0054] 0.5 mL of 0.05 mol / L palladium acetate was added to 3 mL of water, followed by 0.5 mL of 0.5 mol / L ethanol solution of 1-naphthol. The mixture was then reacted in a water bath at 60 °C for 2 h. After the reaction was completed, the mixture was washed 6 times by centrifugation with ethanol and then freeze-dried for 24 h to obtain palladium nanodendritic crystals.

[0055] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h. After centrifugation and washing 6 times with ethanol, the mixture was freeze-dried for 24 h to obtain ruthenium-palladium alloy hydride (molar ratio of ruthenium to palladium was 7:67, and molar ratio of hydrogen to palladium was 3:7).

[0056] Since the proportions of each element in the experimental sample differ from the feeding ratio, the actual sample should be used as the standard. The element proportions of the sample are only provided in Example 1 and will not be provided again in subsequent examples.

[0057] The ruthenium-palladium alloy hydride was subjected to TEM and EDS tests, and the test results are as follows: Figure 1 As shown, (a, b) are EDS images of ruthenium-palladium alloy hydride, (c) are TEM images of ruthenium-palladium alloy hydride, and (d) are TEM images of palladium nanodendritic structures; Figure 1 It can be seen that the morphology of the ruthenium-palladium alloy hydride is nano-dendritic, and EDS testing shows that the atomic ratio of ruthenium atoms to palladium atoms in the ruthenium-palladium alloy hydride is 1:9.

[0058] Example 2

[0059] Palladium nanodendritic crystals were prepared according to Example 1;

[0060] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.01 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain ruthenium palladium alloy hydride.

[0061] Example 3

[0062] Palladium nanodendritic crystals were prepared according to Example 1;

[0063] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.4 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain ruthenium palladium alloy hydride.

[0064] Example 4

[0065] Palladium nanodendritic crystals were prepared according to Example 1;

[0066] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 240 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain ruthenium palladium alloy hydride.

[0067] Example 5

[0068] Palladium nanodendritic crystals were prepared according to Example 1;

[0069] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 1 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain ruthenium palladium alloy hydride.

[0070] Example 6

[0071] Palladium nanodendritic crystals were prepared according to Example 1;

[0072] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L ruthenium trichloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 36 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain ruthenium palladium alloy hydride.

[0073] Example 7

[0074] Palladium nanodendritic crystals were prepared according to Example 1;

[0075] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L copper chloride dihydrate solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain copper palladium alloy hydride.

[0076] Example 8

[0077] Palladium nanodendritic crystals were prepared according to Example 1;

[0078] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L nickel chloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain nickel-palladium alloy hydride.

[0079] Example 9

[0080] Palladium nanodendritic crystals were prepared according to Example 1;

[0081] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L ferric chloride hexahydrate solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain the iron-palladium alloy hydride.

[0082] Example 10

[0083] Palladium nanodendritic crystals were prepared according to Example 1;

[0084] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L zinc chloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain zinc-palladium alloy hydride.

[0085] Example 11

[0086] Palladium nanodendritic crystals were prepared according to Example 1;

[0087] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, followed by the addition of 0.1 mL of 0.05 mol / L cobalt chloride hexahydrate solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. The mixture was then solvothermal reacted at 200 °C for 12 h, washed 6 times by centrifugation with ethanol, and freeze-dried for 24 h to obtain cobalt palladium alloy hydride.

[0088] Comparative Example 1

[0089] Palladium nanodendritic crystals were prepared according to Example 1;

[0090] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of benzyl alcohol solution (benzyl alcohol was analytical grade, ≥99%), followed by the addition of 0.1 mL of 0.05 mol / L ruthenium chloride solution and 0.5 mL of 0.5 mol / L 1-naphthol ethanol solution. After a solvothermal reaction at 200 °C for 12 h, the mixture was washed 6 times by centrifugation with ethanol and freeze-dried for 24 h to obtain a ruthenium-palladium alloy.

[0091] XPS tests were performed on the ruthenium-palladium alloy hydride described in Example 1 and the ruthenium-palladium alloy described in Comparative Example 1. The test results are as follows: Figure 2 As shown, by Figure 2 It can be seen that the valence band of ruthenium-palladium alloy hydrides narrows significantly, proving the formation of metal alloy hydrides.

[0092] Comparative Example 2

[0093] Palladium nanodendritic crystals were prepared according to Example 1;

[0094] 4 mg of palladium nanodendritic crystals were dispersed in 32 mL of 50% ethanol aqueous solution, and then reacted at 200 °C for 12 h. After centrifugation and washing with ethanol 6 times, the mixture was freeze-dried for 24 h to obtain palladium hydride.

[0095] XRD tests were performed on the ruthenium-palladium alloy hydride of Example 1, the ruthenium-palladium alloy of Comparative Example 1, and the palladium hydride of Comparative Example 2. The test results are as follows: Figure 3 As shown, by Figure 3 It can be seen that the strongest diffraction peak of the ruthenium-palladium alloy hydride shifts to the left compared to the strongest diffraction peak of the ruthenium-palladium alloy, which is caused by lattice expansion. At the same time, it shifts to the right compared to the strongest diffraction peak of the palladium hydride. The results indicate the effective synthesis of metal hydrides.

[0096] Application Example 1

[0097] Hydrogen production tests were conducted on the ruthenium-palladium alloy hydride described in Example 1 and the ruthenium-palladium alloy described in Comparative Example 1 using water electrolysis. The tests were performed at room temperature using a standard three-electrode system and a CHI 660E workstation (CH Instruments, Shanghai Chenhua Co., Ltd.). The ruthenium-palladium alloy hydride described in Example 1, the ruthenium-palladium alloy described in Comparative Example 1, and the palladium hydride described in Comparative Example 2 were mixed with conductive carbon powder at a mass ratio of 1:1. Isopropanol, water, and Nafion solution (5 wt.%) were added in a volume ratio of 6:3:1 to obtain ink (the concentration of the water electrolysis hydrogen production catalyst in the ink was 2 g / L). 10 μL of the ink was dropped onto a glassy carbon electrode (d = 3 mm). Using the glassy carbon electrode as the working electrode, a graphite rod as the counter electrode, and a saturated calomel reference electrode as the reference electrode, water electrolysis hydrogen production was tested in a 1 mol / L potassium hydroxide solution. The hydrogen evolution reaction (HER) was studied in a N2-saturated 1.0 M KOH solution at a scan rate of 5 mV / s. All electrode potentials are referenced relative to the reversible hydrogen electrode (RHE). In our electrochemical testing system at 1.0 M KOH, E(RHE) = E(SCE) + 1.068 V.

[0098] Overpotential (η) refers to the portion of the actual voltage exceeding the theoretical voltage required to achieve a certain current density in an electrocatalytic or photoelectrocatalytic reaction. The overpotential value obtained by LSV measurement is one of the key indicators for evaluating the performance of water electrolysis hydrogen production catalysts. Theoretically, for the hydrogen evolution reaction, the closer the overpotential is to 0V, the better the performance of the water electrolysis hydrogen production catalyst. Typically, to facilitate comparison of the electrocatalytic activity of different materials, we use a 10 mA cm⁻¹... -2 At the current density, the reversible hydrogen potential (RHE) is converted for comparison. Figure 4 The test results for linear sweep voltammetry (LSV) are derived from... Figure 4 It can be seen that at 10mA·cm -2 At the same time, the overpotentials of the ruthenium-palladium alloy described in Comparative Example 1 and the palladium hydride of Comparative Example 2 were 33 mV and 56 mV, respectively, while the overpotential of the ruthenium-palladium alloy hydride described in Example 1 was 25 mV. The results show that the introduction of hydrogen atoms and ruthenium atoms can significantly improve the hydrogen production activity of the ruthenium-palladium alloy hydride in water electrolysis.

[0099] Application Example 2

[0100] Electrolysis of water to produce hydrogen was tested on the ruthenium-palladium alloy hydride described in Example 2, Example 3, Example 4, and Example 7. The test procedure was the same as in Application Example 1, and the test results are as follows: Figure 5As shown (the ruthenium palladium alloy hydride of Example 2, the ruthenium palladium alloy hydride of Example 3, the ruthenium palladium alloy hydride of Example 4, and the copper palladium alloy hydride of Example 7 at 10 mA·cm⁻¹), -2 The overpotential at the location is shown in Table 1. Figure 5 As shown in Table 1, the catalytic performance of the ruthenium-palladium alloy hydride can be significantly improved by adding 0.1 mL of 0.05 mol / L ruthenium trichloride and carrying out a solvothermal reaction at 200 °C. In contrast, the overpotential of the copper-palladium alloy hydride in Example 7 is significantly higher than that of the ruthenium-palladium alloy hydride at the same current density. This result indicates that the ruthenium-palladium alloy hydride has superior performance compared to the copper-palladium alloy hydride in terms of catalytic activity.

[0101] Table 1 shows the ruthenium-palladium alloy hydride of Example 2, Example 3, Example 4, and Example 7, and the copper-palladium alloy hydride at 10 mA·cm⁻¹. -2 Overpotential at the location.

[0102] Example Example 2 Example 3 Example 4 Example 7 Overpotential (mV) 33 46 35 49

[0103] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing a catalyst for hydrogen production by electrolysis of water, characterized by, The method comprises the following steps: mixing an ethanol aqueous dispersion of palladium, a metal precursor dispersion and an ethanol solution of 1-naphthol to perform a solvothermal reaction to obtain the water electrolysis hydrogen production catalyst; the water electrolysis hydrogen production catalyst is a metal alloy hydride of palladium; the palladium in the ethanol aqueous dispersion of palladium is nano-palladium; the metal precursor in the metal precursor dispersion comprises one or more of ruthenium trichloride, copper dichloride dihydrate, iron chloride hexahydrate, nickel chloride, zinc chloride and cobalt chloride hexahydrate; the water electrolysis hydrogen production catalyst is a metal alloy hydride; the metal alloy hydride comprises palladium crystals and doped metal atoms and hydrogen atoms embedded into the structure of the palladium crystals.

2. The production method according to claim 1, wherein the micro-morphology of the nano-palladium comprises one or more of nanoparticles, nanowires, nanotubes, nanodendrites, nanoflowers, nanorods and nanostars; the concentration of the ethanol aqueous dispersion of palladium is 50-200 mg / L.

3. The production method according to claim 1, wherein the concentration of the metal precursor dispersion is 0.01-0.1 mol / L.

4. The production method according to claim 1, wherein the concentration of the ethanol solution of 1-naphthol is 0.1-1 mol / L.

5. The production method according to any one of claims 1 to 4, wherein the ratio of the amount of palladium in the ethanol aqueous dispersion of palladium to the amount of the metal precursor dispersion is (1-10) mg:(0.01-1) mL.

6. The production method according to claim 5, wherein the volume ratio of the metal precursor dispersion to the ethanol solution of 1-naphthol is (0.01-1):(0.3-0.7).

7. The production method according to claim 6, wherein the temperature of the solvothermal reaction is 100-240℃ and the time is 1-36 h.

8. The production method according to claim 7, wherein after the solvothermal reaction is completed, centrifugal washing and drying are sequentially performed.

9. The hydrogen production catalyst prepared by the method according to any one of claims 1 to 8, characterized in that, the water electrolysis hydrogen production catalyst is a metal alloy hydride; the metal alloy hydride comprises palladium crystals and doped metal atoms and hydrogen atoms embedded into the structure of the palladium crystals.

10. The water electrolysis hydrogen production catalyst of claim 9 is applied in the field of hydrogen production by water electrolysis.

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