Preparation method and application of wood-derived carbon supported metal sulfide catalyst with modified hierarchical pore structure

Abstract

The invention discloses a preparation method and application of a wood-derived carbon supported metal sulfide catalyst with a modified hierarchical pore structure, relates to a preparation method and application of a hydrogen evolution catalyst, and aims to solve the technical problems that the electrochemical performance of the existing molybdenum disulfide and nickel-based sulfide catalyst is low, and the density of active sites of a wood-derived carbon carrier is low. The method comprises the following steps: immersing wood chips into a mixed solution of H3PO4 and ZnCl2, stirring, and carbonizing in a tubular furnace to obtain wood derived carbon with a modified hierarchical pore structure; and carrying out hydrothermal reaction on the modified wood-derived carbon and a mixed solution of sodium molybdate, nickel nitrate and thiourea to obtain the modified hierarchical pore structure wood-derived carbon supported metal sulfide catalyst. When hydrogen is produced by electrolyzing water in an alkaline electrolyte, the overpotential current density can reach 10mAcm <-2 > only by 101-157mV. The method can be used in the field of water electrolysis hydrogen production.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a hydrogen evolution catalyst, belonging to the technical field of electrocatalytic hydrogen evolution. Background Art

[0002] As the material foundation for sustainable development, energy plays a crucial role in the global development process. At present, the overconsumption of fossil fuels is becoming increasingly severe, and the development of renewable clean energy has become an urgent task. Hydrogen energy, with its significant advantages of high energy density and clean combustion products, is recognized as a highly potential new energy source. Among various hydrogen production methods, water electrolysis is a relatively common one. And electrode catalytic materials play an important role in improving the hydrogen evolution efficiency and reducing the hydrogen production cost. In recent years, many research teams have carried out in-depth exploration on transition metal compounds. Molybdenum disulfide (MoS2), with its unique structural characteristics and suitable hydrogen evolution free energy, is regarded as a highly potential alternative material for noble metal catalysts. MoS2 has a layered structure, which endows it with some special physical and chemical properties and theoretically provides a certain basis for the hydrogen evolution reaction. However, MoS2 exposes many drawbacks in practical applications. Nickel-based sulfides are a kind of inexpensive materials with a wide range of sources and diverse structures. Although there is a significant gap between nickel-based sulfides and platinum-based catalysts. But the metal characteristics it possesses enable it to achieve rapid electron transfer, which is of great significance in the catalytic process. In recent years, a large number of studies have revealed an important phenomenon: when nickel sulfide is combined with other active materials, electron rearrangement will occur in the system. This change at the electron level can effectively improve the activity of the catalyst. Wood-derived carbon is widely used to load active components for preparing self-supporting electrode materials. However, the chemical composition of natural wood is extremely complex. In the harsh process of high-temperature carbonization, the connectivity of the pore structure inside the wood is poor, and there is a serious problem of pore blockage, resulting in a low density of active sites. It is difficult to achieve the coordination and unity among conductivity, long-term stability, and function in the entire wood framework structure. Summary of the Invention

[0003] The present invention aims to solve the technical problems of low electrochemical performance of existing molybdenum disulfide and nickel-based sulfide catalysts and low density of active sites on wood-derived carbon carriers. The present invention constructs a highly efficient hydrogen evolution catalyst with a MoS2 / NiS2 hierarchical nanostructure on modified wood-derived carbon with a hierarchical pore structure. The preparation process is simple, the cost is low, and the electrochemical performance is excellent.

[0004] The preparation method of the modified wood-derived carbon supported metal sulfide catalyst of the present invention comprises the following steps:

[0005] 1. Cut natural beech wood into wood chips, wash and dry them, then immerse them in a mixed aqueous solution of H3PO4 and ZnCl2, stir, and then dry.

[0006] 2. Place the wood chips treated in step 1 in a tubular furnace and carbonize them under a nitrogen atmosphere.

[0007] 3. Put the carbonized material into hydrochloric acid to remove Zn ions, then rinse it with ethanol and deionized water, and then dry it to obtain modified hierarchical porous structure wood-derived carbon, denoted as PZnMC.

[0008] 4. Add the modified hierarchical porous structure wood-derived carbon to a mixed solution of sodium molybdate, nickel nitrate and thiourea, then transfer it to a high-pressure reaction kettle, heat it to 100 - 220 °C and keep it for 10 - 24 h for hydrothermal reaction, and then wash the obtained product with water and dry it to obtain a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst, denoted as MoS2 / NiS2@PZnMC, which is a composite structure with nanosheets supported on wood-derived carbon.

[0009] Furthermore, the length of the wood chips described in step 1 is 2 cm, the width is 1.5 cm, and the thickness is 3 mm.

[0010] Furthermore, in the mixed aqueous solution of H3PO4 and ZnCl2 described in step 1, the concentration of H3PO4 is 2 - 8 mol / L, and the concentration of ZnCl2 is 2 - 8 mol / L.

[0011] Furthermore, the stirring time described in step 1 is 5 - 24 h.

[0012] Furthermore, for the drying in step 1, the temperature is 60 - 120 °C, and the drying time is 5 - 12 h.

[0013] Furthermore, for the carbonization in step 2, the carbonization temperature is 300 - 1000 °C, and the carbonization time is 2 - 12 h.

[0014] Furthermore, the concentration of hydrochloric acid described in step 3 is 2 - 8 mol / L.

[0015] Furthermore, the preparation method of the mixed solution of sodium molybdate, nickel nitrate and thiourea described in step 4: First, dissolve 0.1 - 8 mmol of sodium molybdate and 0.1 - 8 mmol of thiourea in 5 - 25 mL of deionized water and ultrasonically disperse to obtain solution A; dissolve 0.1 - 8 mmol of nickel nitrate in 5 - 25 mL of deionized water to obtain solution B; then mix solution A and solution B and ultrasonically disperse for 10 - 30 min to obtain the mixed solution of sodium molybdate, nickel nitrate and thiourea.

[0016] The application of the modified hierarchically porous structure wood-derived carbon supported metal sulfide catalyst prepared by the above method is to use this catalyst as an electrode material for hydrogen production by electrolyzing water.

[0017] The modified hierarchically porous structure wood-derived carbon supported metal sulfide catalyst of the present invention has the following beneficial effects:

[0018] (1) An efficient hydrogen evolution catalyst with a hierarchical nanostructure of MoS2 / NiS2 is constructed on H3PO4+ZnCl2 modified wood-derived carbon, and its preparation method is hydrothermal synthesis, which is simple and easy to operate, and environmentally friendly and pollution-free.

[0019] (2) Natural beech wood is activated by ZnCl2 and H3PO4, increasing the pores of the wood and forming a hierarchically porous structure containing micropores-mesopores-macropores. The micropores among them can conduct rapid electron-ion transport, and the mesopores and macropores spatially limit the growth of MoS2 / NiS2. The smaller active substances can expose more catalytic sites, and the unique interconnected pore structure inside the catalyst can prevent the shedding of active substances during the persistent electrocatalysis process, improving the material stability. Therefore, the pore regulation of the conductive substrate wood-derived carbon of the present invention improves the hydrogen evolution performance.

[0020] (3) The synergistic effect between the two components adjusts their surface adsorption properties through interfacial electron coupling and promotes excellent activity and high stability for HER.

[0021] (4) The synthesized laminated heterocomposite MoS2 / NiS2@MC catalyst has a larger specific surface area, exposes more active sites, improves the conductivity, and its hydrogen evolution performance is far superior to that of single-component catalysts.

[0022] (5) The modified hierarchically porous structure wood-derived carbon supported metal sulfide catalyst of the present invention only requires an overpotential of 101-157 mV in an alkaline electrolyte to reach a current density of 10 mA cm -2 . It can be used in the field of hydrogen production by electrolyzing water. Description of the Drawings

[0023] Figure 1 are the optical pictures of natural beech wood, PZnMC, PMC, ZnMC, and NC in the examples.

[0024] Figure 2 are the XRD patterns of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, NiS2@PZnMC, and PZnMC in the examples.

[0025] Figure 3 are the Raman spectra of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, and NiS2@PZnMC in the examples.

[0026] Figure 4 SEM images of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, and NiS2@PZnMC in the examples.

[0027] Figure 5 N2 adsorption-desorption isotherms and pore size distribution curves of MoS2 / NiS2@PZnMC-1, MoS2 / NiS2@ZnMC, MoS2 / NiS2@PMC, and MoS2 / NiS2@NC in the examples;

[0028] Figure 6 N2 adsorption-desorption isotherms and pore size distribution curves of MoS2 / NiS2@PZnMC-1, NiS2@PZnMC, and MoS2@PZnMC in the examples;

[0029] Figure 7 LSV curves of the catalysts prepared in Examples 1-5.

[0030] Figure 8 Overpotential diagrams of the catalysts prepared in Examples 1-5 at different current densities.

[0031] Figure 9 LSV curves of the catalyst prepared in Example 1, the catalysts prepared in Comparative Examples 1-5, NC, and 20% Pt / C.

[0032] Figure 10 Overpotential diagrams of the catalyst prepared in Example 1, the catalysts prepared in Comparative Examples 1-5, NC, and 20% Pt / C. Detailed implementation manners

[0033] The implementation manners of the present invention will be described in detail below in conjunction with the examples.

[0034] Example 1: The preparation method of the modified hierarchically porous wood-derived carbon supported metal sulfide catalyst in this example is carried out according to the following steps:

[0035] I. After cutting natural beech wood into 2 cm × 1.5 cm × 3 mm wood chips, cleaning and drying them, immerse them in a mixed aqueous solution of 50 ml of H3PO4 and ZnCl2 and stir for 12 hours, and then put the treated wood chips into a vacuum environment at 100 °C and dry for 6 hours; the concentrations of H3PO4 and ZnCl2 in the mixed aqueous solution are both 5 mol / L.

[0036] Second, the wood chips processed in Step 1 are placed in a tubular furnace. Under a nitrogen atmosphere, first, the temperature is raised to 350 °C at a rate of 2 °C / min and held for 2 hours. Subsequently, the temperature is raised to 550 °C at a rate of 3 °C / min and held for 2 hours. Finally, the temperature is raised to 900 °C at a rate of 3 °C / min and held for 2 hours.

[0037] Third, the carbonized material is placed in 3 mol / L hydrochloric acid for 6 hours to remove Zn ions. Subsequently, it is repeatedly rinsed 3 times with ethanol and deionized water, and then dried to obtain modified hierarchically porous structure wood-derived carbon activated by H3PO4 and ZnCl2, denoted as PZnMC.

[0038] Fourth, 0.4 mmol of sodium molybdate and 2.5 mmol of thiourea are dissolved in 20 mL of deionized water and ultrasonicated for 20 min. Then, 0.1 mmol of nickel nitrate is dissolved in another 20 mL of deionized water. The two are mixed evenly and ultrasonicated for 15 min to obtain a mixed solution of sodium molybdate, nickel nitrate, and thiourea. The modified hierarchically porous structure wood-derived carbon is added to the mixed solution of sodium molybdate, nickel nitrate, and thiourea, and then transferred to a high-pressure reaction kettle. It is heated to 200 °C and held for 20 h for hydrothermal reaction. Then, the obtained product is washed 3 times with water and dried to obtain a modified hierarchically porous structure wood-derived carbon supported metal sulfide catalyst, denoted as MoS2 / NiS2@PZnMC-1, which is a composite structure with nanosheets supported on wood-derived carbon.

[0039] Example 2: The difference between this example and Example 1 is that in Step 4, the amount of sodium molybdate is 0.3 mmol and the amount of nickel nitrate is 0.2 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as MoS2 / NiS2@PZnMC-2.

[0040] Example 3: The difference between this example and Example 1 is that in Step 4, the amount of sodium molybdate is 0.25 mmol and the amount of nickel nitrate is 0.25 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as MoS2 / NiS2@PZnMC-3.

[0041] Example 4: The difference between this example and Example 1 is that in Step 4, the amount of sodium molybdate is 0.2 mmol and the amount of nickel nitrate is 0.3 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as MoS2 / NiS2@PZnMC-4.

[0042] Example 5: The difference between this example and Example 1 is that in Step 4, the amount of sodium molybdate is 0.1 mmol and the amount of nickel nitrate is 0.4 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as MoS2 / NiS2@PZnMC-5.

[0043] Comparative Example 1: The difference between this comparative example and Example 1 is that the amount of sodium molybdate in Step 4 is 0 mmol, and the amount of nickel nitrate is 0.5 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as NiS2@PZnMC.

[0044] Comparative Example 2: The difference between this comparative example and Example 1 is that the amount of sodium molybdate in Step 4 is 0.5 mmol, and the amount of nickel nitrate is 0 mmol. Other steps and parameters are the same as those in Example 1. The obtained catalyst is denoted as MoS2@PZnMC.

[0045] Comparative Example 3: H3PO4 is not added during the wood chip treatment in this comparative example. The difference between this comparative example and Example 1 is the operation in Step 1 as follows: First, cut natural beech wood into wood chips of 2 cm × 1.5 cm × 3 mm, wash and dry them, then immerse them in 50 ml of ZnCl2 solution and stir for 12 hours, and then put the treated wood chips into a vacuum environment at 100 °C and dry for 6 hours; the concentration of the ZnCl2 solution is 5 mol / L; other steps and parameters are the same as those in Example 1. The carbonized wood-derived carbon is denoted as ZnMC, and the obtained catalyst is denoted as MoS2 / NiS2@ZnMC.

[0046] Comparative Example 4: ZnCl2 is not added during the wood chip treatment in this example. The difference between this comparative example and Example 1 is the operation in Step 1 as follows: First, cut natural beech wood into wood chips of 2 cm × 1.5 cm × 3 mm, wash and dry them, then immerse them in 50 ml of H3PO4 and stir for 12 hours, and then put the treated wood chips into a vacuum environment at 100 °C and dry for 6 hours; the concentration of H3PO4 is 5 mol / L; other steps and parameters are the same as those in Example 1. The obtained carbonized wood-derived carbon is denoted as PMC, and the obtained catalyst is denoted as MoS2 / NiS2@PMC.

[0047] Comparative Example 5: Neither H3PO4 nor ZnCl2 is added during the wood chip treatment in this example. The difference between this comparative example and Example 1 is the operation in Step 1 as follows: First, cut natural beech wood into wood chips of 2 cm × 1.5 cm × 3 mm, wash and dry them, and then put them into a vacuum environment at 100 °C and dry for 6 hours; other steps and parameters are the same as those in Example 1. The carbonized wood-derived carbon is denoted as NC, and the prepared catalyst is denoted as MoS2 / NiS2@NC.

[0048] Characterize the electrode materials prepared in Examples 1 to 5 and Comparative Examples 1 to 5: Use X-ray diffraction (XRD) and Raman spectroscopy (Raman) to analyze the crystal structure and possible phase composition of various synthesized catalyst samples, and analyze the specific surface area and pore size distribution of different catalysts through BET tests. Use field emission scanning electron microscopy (SEM) to observe the microstructure and morphology of the electrode materials.

[0049] Figure 1 These are the optical pictures of natural wood, PZnMC, PMC, ZnMC, and NC. By comparison, it can be seen that after carbonization treatment, the sizes of PZnMC, ZnMC, PMC, and NC are all smaller than that of the original log, but the shrinkage of NC is the most obvious. The reason is that more pores and specific surface areas are formed after treatment with H3PO4 and ZnCl2, so the reduced size is smaller.

[0050] Figure 2 These are the XRD patterns of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, NiS2@PZnMC, and PZnMC. Figure 2 It shows that a composite structure of MoS2 and NiS2 is formed in the MoS2 / NiS2@PZnMC-1 sample.

[0051] Figure 3 These are the Raman spectra of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, and NiS2@PZnMC. Figure 3 It further confirms the formation of 2H-phase MoS2 during the hydrothermal process.

[0052] Figure 4 These are the SEM images of MoS2 / NiS2@PZnMC-1, MoS2@PZnMC, and NiS2@PZnMC. Among them, Figure 4 a-c are the SEM images of MoS2 / NiS2@PZnMC-1. It can be seen from the figure that with the help of the hydrothermal method, two different-shaped materials have successfully constructed a flower-like MoS2 / NiS2 heterostructure. This structure presents a unique network morphology, containing a large number of spatial gaps and open channels. The micropores can conduct rapid electron-ion transport, and the mesopores and macropores spatially confine the growth of MoS2 / NiS2. The smaller active substances can expose more catalytic sites, and the unique interconnected pore structure inside the catalyst can prevent the shedding of active substances during the persistent electrocatalysis process, improving the material stability. Figure 4 d-f are the SEM images of MoS2@PZnMC. It can be seen from the figure that under the condition of not adding Ni source, MoS2 is formed by the interweaving and stacking of many nanosheets and grows vertically in a worm-like shape on PZnMC. Figure 4 g-i are the SEM images of NiS2@PZnMC. It can be seen from the figure that under the condition of not adding Mo source, NiS2 presents an irregular blocky structure, and these blocky particles are stacked with each other to form a cluster-like aggregate.

[0053] Figure 5Are the nitrogen adsorption - desorption isotherm curves and pore size distribution diagrams of MoS2 / NiS2@PZnMC - 1, MoS2 / NiS2@ZnMC, MoS2 / NiS2@PMC, and MoS2 / NiS2@NC. Figure 6 Are the nitrogen adsorption - desorption isotherm curves and pore size distribution diagrams of MoS2 / NiS2@PZnMC - 1, NiS2@PZnMC, and MoS2@PZnMC. The test results are shown in Table 1.

[0054] Table 1 Pore volume and specific surface area data of the catalysts

[0055] Example Sample <![CDATA[V pore (cm 3 / g)]]> <![CDATA[S pore (m 2 / g)]]> Example 1 <![CDATA[MoS2 / NiS2@PZnMC-1]]> 0.384 762.807 Comparative Example 3 <![CDATA[MoS2 / NiS2@ZnMC]]> 0.395 1153.286 Comparative Example 4 <![CDATA[MoS2 / NiS2@PMC]]> 0.423 1039.960 Comparative Example 5 <![CDATA[MoS2 / NiS2@NC]]> 0.245 637.081 Comparative Example 1 <![CDATA[NiS2@PZnMC]]> 0.537 917.660 Comparative Example 2 <![CDATA[MoS2@PZnMC]]> 0.267 522.316

[0056] From Figure 5 and Table 1, it can be seen that compared with MoS2 / NiS2@ZnMC, MoS2 / NiS2@PMC, and MoS2 / NiS2@NC, MoS2 / NiS2@PZnMC has the richest pore size distribution and has a hierarchical pore structure containing micropores - mesopores - macropores. From Figure 6 and Table 1, it can be seen that compared with MoS2@PZnMC, the specific surface area, pore volume, and the number of mesopores of MoS2 / NiS2@PZnMC have all increased. The reason is that the combination of MoS2 and NiS2 can optimize the interface and pore size structure through synergistic effects.

[0057] The electrochemical performance of the catalysts prepared in the examples and comparative examples for hydrogen evolution reaction was tested. The electrochemical performance test of the hydrogen evolution reaction was measured in a Chenhua CHI - 760E electrochemical workstation, and the standard three - electrode system was used for the test. In the three - electrode test system, the working electrode is the test electrode material fixed by a platinum electrode clip, the counter electrode uses a graphite rod electrode (with a diameter of about 6 mm) that does not affect the catalytic activity under long - term test conditions, and the reference electrode selects a Hg / HgO electrode with good stability in alkaline solutions. The electrolyte solution system used in the electrochemical test process is 1M KOH (pH≈13.8); the linear sweep voltammetry (LSV) was tested at a rate of 1 mV s -1 and the measured data have all been compensated for 95% current impedance (IR).

[0058] Figure 7 Are the LSV curves of the catalysts prepared in Examples 1 - 5. Figure 8 Are the over - potential diagrams of the catalysts prepared in Examples 1 - 5 at different current densities. The specific over - potentials are shown in Table 2. From Figure 7 and Figure 8 it can be seen that the catalysts prepared in Examples 1 - 5 have low over - potentials at different current densities, indicating that the catalysts prepared by this method have good hydrogen evolution performance.

[0059] Table 2 Overpotential Results of the Catalyst at Different Current Densities

[0060]

[0061] Figure 9 are the LSV curves of the catalyst prepared in Example 1, the catalysts prepared in Comparative Examples 1 - 5, NC, and 20% Pt / C. Figure 10 is the overpotential diagram of the catalyst prepared in Example 1, the catalysts prepared in Comparative Examples 1 - 5, NC, and 20% Pt / C. The specific overpotential values are shown in Table 3. From Figure 9 and Figure 10 it can be seen that compared with the catalysts prepared in Comparative Examples 1 - 5, NC, and 20% Pt / C, except for 20% Pt / C, the catalyst MoS2 / NiS2@PZnMC-1 prepared in Example 1 exhibits the most excellent catalytic activity.

[0062] Table 3 Overpotential Results of the Catalyst at Different Current Densities

[0063]

Claims

1. A preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst, characterized in that, The method comprises the following steps: First, cut natural beech wood into wood chips, wash and dry them, then immerse them in a mixed aqueous solution of H3PO4 and ZnCl2, stir, and then dry; Second, place the wood chips treated in the first step in a tubular furnace and carbonize them under a nitrogen atmosphere; Third, put the carbonized material into hydrochloric acid to remove Zn ions, then rinse it with ethanol and deionized water, and then dry it to obtain modified hierarchical porous structure wood-derived carbon, denoted as PZnMC; Fourth, add the modified hierarchical porous structure wood-derived carbon to a mixed solution of sodium molybdate, nickel nitrate and thiourea, then transfer it to a high-pressure reactor, heat it to 100-220 °C and keep it for 10-24 h for hydrothermal reaction, then wash the obtained product with water and dry it to obtain a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst, denoted as MoS2 / NiS2@PZnMC.

2. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1, characterized in that, In the first step, the length of the wood chips is 2 cm, the width is 1.5 cm, and the thickness is 3 mm.

3. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the first step, the concentration of H3PO4 in the mixed aqueous solution is 2-8 mol / L, and the concentration of ZnCl2 is 2-8 mol / L.

4. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the first step, the stirring time is 5-24 h.

5. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the first step, for drying, the temperature is 60-120 °C and the drying time is 5-12 h.

6. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the second step, for carbonization, the carbonization temperature is 300-1000 °C and the carbonization time is 2-12 h.

7. The preparation method of a modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the third step, the concentration of hydrochloric acid is 2-8 mol / L.

8. The preparation method of a modified hierarchical pore structure wood-derived carbon supported metal sulfide catalyst according to claim 1 or 2, characterized in that, In the fourth step, the preparation method of the mixed solution of sodium molybdate, nickel nitrate and thiourea: First, dissolve 0.1-8 mmol of sodium molybdate and 0.1-8 mmol of thiourea in 5-25 mL of deionized water and ultrasonically disperse to obtain solution A; dissolve 0.1-8 mmol of nickel nitrate in 5-25 mL of deionized water to obtain solution B; then mix solution A and solution B and ultrasonically disperse for 10-30 min to obtain the mixed solution of sodium molybdate, nickel nitrate and thiourea.

9. Use of the modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst prepared by the method according to claim 1, characterized in that This application uses the modified hierarchical porous structure wood-derived carbon supported metal sulfide catalyst as an electrode material for hydrogen production by electrolyzing water.

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