A preparation method of a CoMoP / FeCoS / NF composite catalyst for hydrogen production by full-pH electrolysis of water

Abstract

This invention relates to a method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production through full-pH water electrolysis, belonging to the field of new energy materials technology. The invention addresses the problems of high cost of existing precious metal catalysts and the limited reactivity of non-precious metal catalysts, which are only suitable for alkaline electrolyzers and under acidic or neutral media conditions. The method comprises: 1. Preparation of the FeCoS / NF precursor; 2. Preparation of the CoMoP / FeCoS / NF composite catalyst. This invention is used for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production through full-pH water electrolysis.

Description

Technical Field

[0001] This invention belongs to the field of new energy materials technology. Background Technology

[0002] The excessive consumption of non-renewable energy and the resulting environmental pollution problems necessitate the urgent search for and development of renewable and clean energy sources, among which hydrogen energy is considered one of the most promising clean energy sources of the 21st century. Hydrogen evolution by electrolysis (HER) is considered an environmentally friendly, highly selective, and pollution-free clean production technology. However, since water splitting is a non-spontaneous reaction from a chemical thermodynamic perspective, and the reaction rate is slow, it requires a catalyst to overcome a certain activation potential. Therefore, the development of efficient water electrolysis catalysts is urgent. Currently, efficient electrocatalysts are still mainly based on scarce and expensive precious metals, which is not conducive to the large-scale industrial application of hydrogen evolution by electrolysis. Furthermore, most reported non-precious metal catalysts are only suitable for alkaline electrolyzers, and their reactivity is very limited under acidic or neutral media conditions. However, in practical applications, hydrogen evolution by electrolysis technology places diverse requirements on the pH of the electrolyte solution. Therefore, the development of efficient, stable, low-overpotential, and inexpensive all-pH hydrogen evolution electrocatalysts is imperative. Summary of the Invention

[0003] This invention aims to address the problems of high cost of existing precious metal catalysts and the limited reactivity of non-precious metal catalysts in alkaline electrolyzers under acidic or neutral media conditions. Instead, it provides a method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production through full pH water electrolysis.

[0004] A method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full-pH water electrolysis, comprising the following steps:

[0005] I. Preparation of FeCoS / NF precursor:

[0006] Cobalt, iron, and sulfur sources were uniformly dispersed in ethylene glycol and then ultrasonically treated to obtain a homogeneous and stable mixed solution A. Nickel foam was then immersed in the homogeneous and stable mixed solution A and reacted at a temperature of 150℃~240℃ for 8h~12h. Finally, the mixture was washed and dried to obtain the FeCoS / NF precursor.

[0007] II. Preparation of CoMoP / FeCoS / NF composite catalyst:

[0008] Cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate, and trisodium citrate were uniformly dispersed in deionized water and then stirred to obtain a homogeneous and stable mixed solution B. Using the homogeneous and stable mixed solution B as the electrolyte, FeCoS / NF precursor as the working electrode, carbon rod as the counter electrode, and Ag / AgCl as the reference electrode, the CoMoP / FeCoS / NF composite catalyst was obtained by deposition under constant voltage conditions for 60s to 150s.

[0009] The beneficial effects of this invention are: This invention discloses the preparation of a CoMoP / FeCoS / NF composite catalyst for hydrogen production through all-pH water electrolysis. This catalyst operates at a current density of 10 mA / cm². 2 Under the specified conditions, the overpotentials obtained in alkaline, neutral, and acidic environments were 104 mV, 171 mV, and 27 mV, respectively, demonstrating excellent performance in water electrolysis across all pH levels and maintaining stability for at least 20 hours. The CoMoP / FeCoS / NF composite catalyst prepared in this invention has a simple preparation method, low cost, and catalytic performance comparable to commercial precious metal catalysts, showing promising application prospects in hydrogen production through water electrolysis.

[0010] This invention relates to a method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production through full-pH water electrolysis. Attached Figure Description

[0011] Figure 1 The images show X-ray diffraction (XRD) patterns. 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, and 3 is the NF catalyst prepared in Comparative Experiment 3.

[0012] Figure 2 X-ray photoelectron diffraction (XPS) analysis of the CoMoP / FeCoS / NF composite catalyst prepared in Example 1;

[0013] Figure 3 The images are scanning electron microscope (SEM) images. (a) shows the FeCoS / NF catalyst prepared in Comparative Experiment 1, and (b) shows the CoMoP / FeCoS / NF composite catalyst prepared in Example 1.

[0014] Figure 4 The images are transmission electron microscope (TEM) images of the CoMoP / FeCoS / NF composite catalyst prepared in Example 1. (a) is a scale bar of 500 nm, (b) is a magnified view of (a), (c) is a scale bar of 5 nm, and (d) is a magnified view of (c).

[0015] Figure 5The following are the HER linear sweep voltammetric polarization (LSV) curves and stability test results of the catalysts under alkaline conditions: (a) HER linear sweep voltammetric polarization (LSV) curves, 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3; (b) is the it curve obtained by testing the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE of 0.101V.

[0016] Figure 6 The following are the HER linear sweep voltammetric polarization curves (LSV) and stability test results of the catalysts under neutral conditions: (a) HER linear sweep voltammetric polarization curves (LSV), 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3; (b) is the it curve obtained by testing the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE 0.171V.

[0017] Figure 7 The following are the HER linear sweep voltammetric polarization (LSV) curves and stability test results of the catalysts under acidic conditions. (a) is the HER linear sweep voltammetric polarization (LSV) curve. 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3. (b) is the it curve obtained by testing the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE of 0.027V. Detailed Implementation

[0018] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

[0019] Specific Implementation Method 1: The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production through full pH water electrolysis described in this implementation method is carried out according to the following steps:

[0020] I. Preparation of FeCoS / NF precursor:

[0021] Cobalt, iron, and sulfur sources were uniformly dispersed in ethylene glycol and then ultrasonically treated to obtain a homogeneous and stable mixed solution A. Nickel foam was then immersed in the homogeneous and stable mixed solution A and reacted at a temperature of 150℃~240℃ for 8h~12h. Finally, the mixture was washed and dried to obtain the FeCoS / NF precursor.

[0022] II. Preparation of CoMoP / FeCoS / NF composite catalyst:

[0023] Cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate, and trisodium citrate were uniformly dispersed in deionized water and then stirred to obtain a homogeneous and stable mixed solution B. Using the homogeneous and stable mixed solution B as the electrolyte, FeCoS / NF precursor as the working electrode, carbon rod as the counter electrode, and Ag / AgCl as the reference electrode, the CoMoP / FeCoS / NF composite catalyst was obtained by deposition under constant voltage conditions for 60s to 150s.

[0024] In this embodiment, cobalt, iron, sulfur and ethylene glycol are used as raw materials, and nickel foam is used as a conductive substrate to prepare FeCoS / NF precursor by solvothermal method; the obtained FeCoS / NF precursor is directly used as working electrode to prepare the CoMoP / FeCoS / NF composite catalyst by electrodeposition method.

[0025] The beneficial effects of this embodiment are:

[0026] This embodiment discloses the preparation of a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full-pH water electrolysis. This catalyst operates at a current density of 10 mA / cm². 2 Under the specified conditions, the overpotentials tested in alkaline, neutral, and acidic environments were 104 mV, 171 mV, and 27 mV, respectively, demonstrating excellent performance in water electrolysis across all pH levels and maintaining stability for at least 20 hours. The CoMoP / FeCoS / NF composite catalyst prepared in this embodiment is simple to prepare, low in cost, and exhibits catalytic performance comparable to commercial precious metal catalysts, showing promising application prospects in hydrogen production through water electrolysis.

[0027] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that: the cobalt source in step one is cobalt chloride hexahydrate; the iron source in step one is ferrous sulfate heptahydrate; and the sulfur source in step one is thiourea. Everything else is the same as in Specific Implementation Method One.

[0028] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that: the molar ratio of cobalt source to iron source in step one is 1:(0.5-2); the molar ratio of cobalt source to sulfur source in step one is 1:(1-3); and the molar ratio of cobalt source to ethylene glycol in step one is 1 mmol:(20-50) mL. Everything else is the same as in Specific Implementation Method One or Two.

[0029] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the ultrasonic treatment described in step one is specifically performed at a power of 200W to 500W for 0.5h to 2h. Everything else is the same as in Specific Implementation Methods One to Three.

[0030] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the foamed nickel mentioned in step one is pretreated foamed nickel; the pretreatment is specifically carried out according to the following steps: ① ultrasonically cleaned sequentially with hydrochloric acid, acetone, ethanol, and ultrapure water at concentrations of 2mol / L to 4mol / L; ② repeating step ① 2 to 4 times, and finally drying at a temperature of 50℃ to 60℃ for 6 to 10 hours. The rest is the same as in Specific Implementation Methods One to Four.

[0031] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the washing and drying in step one specifically involves washing with deionized water, followed by drying at a temperature of 50℃~60℃ for 8h~12h. Everything else is the same as in Specific Implementation Methods One to Five.

[0032] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the nickel foam described in step one has a purity of 99.99%, a thickness of 1mm to 2mm, and a pore size of 100PPI to 120PPI. Everything else is the same as in Specific Implementation Methods One to Six.

[0033] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: the mass ratio of cobalt nitrate hexahydrate to sodium hypophosphite in step two is 1:(3-4); the mass ratio of cobalt nitrate hexahydrate to sodium molybdate in step two is 1:(0.5-1.5); the mass ratio of cobalt nitrate hexahydrate to trisodium citrate in step two is 1:(0.5-1); and the mass ratio of cobalt nitrate hexahydrate to deionized water in step two is 1g:(700-1000)mL. Everything else is the same as in Specific Implementation Methods One to Seven.

[0034] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the stirring described in step two is specifically carried out at a rotation speed of 200 r / min to 500 r / min for 0.5 h to 1.5 h. Everything else is the same as in Specific Implementation Methods One to Eight.

[0035] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that: in step two, deposition is performed for 60s to 150s under a constant voltage of -0.5V to -3V. Everything else is the same as in Specific Implementation Methods One to Nine.

[0036] The beneficial effects of the present invention are verified using the following embodiments:

[0037] Example 1:

[0038] A method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full-pH water electrolysis, comprising the following steps:

[0039] I. Preparation of FeCoS / NF precursor:

[0040] 1 mmol cobalt source, 1 mmol iron source and 2 mmol sulfur source were uniformly dispersed in 30 mL ethylene glycol, and then sonicated for 1 h at a power of 300 W to obtain a homogeneous and stable mixed solution A. Nickel foam was vertically immersed in the homogeneous and stable mixed solution A and reacted at a temperature of 200 °C for 12 h. Finally, it was washed and dried to obtain the FeCoS / NF precursor.

[0041] II. Preparation of CoMoP / FeCoS / NF composite catalyst:

[0042] 58 mg of cobalt nitrate hexahydrate, 200 mg of sodium hypophosphite, 62 mg of sodium molybdate, and 50 mg of trisodium citrate were uniformly dispersed in 50 mL of deionized water. The mixture was then stirred at 300 r / min for 1 h to obtain a homogeneous and stable mixed solution B. Using the homogeneous and stable mixed solution B as the electrolyte, FeCoS / NF precursor as the working electrode, carbon rod as the counter electrode, and Ag / AgCl as the reference electrode, the mixture was deposited for 90 s under a constant voltage of -1.0 V to obtain the CoMoP / FeCoS / NF composite catalyst.

[0043] The cobalt source mentioned in step one is cobalt chloride hexahydrate; the iron source mentioned in step one is ferrous sulfate heptahydrate; and the sulfur source mentioned in step one is thiourea.

[0044] The nickel foam mentioned in step one is pretreated nickel foam; the pretreatment is carried out in the following steps: ① ultrasonically cleaned sequentially with hydrochloric acid, acetone, ethanol and ultrapure water at a concentration of 3 mol / L; ② repeat step ① twice, and finally dry at a temperature of 50℃ for 6 hours.

[0045] The nickel foam mentioned in step one has a purity of 99.99%, a pore size of 110 PPI, and a size of 2 cm × 4 cm × 1.5 mm.

[0046] The washing and drying process described in step one specifically involves washing with deionized water and then drying at 50°C for 8 hours.

[0047] Comparative Experiment 1: This comparative experiment differs from Example 1 in that step 2 is omitted, and the FeCoS / NF precursor is used as the FeCoS / NF catalyst. Everything else is the same as in Example 1.

[0048] Comparative Experiment 2: This comparative experiment differs from Example 1 in that step one is omitted, and pretreated nickel foam is used as the working electrode for deposition to obtain the CoMoP / NF composite catalyst. Everything else is the same as in Example 1.

[0049] Comparative Experiment 3: This comparative experiment differs from Example 1 in that steps one and two are omitted, and pretreated nickel foam is used as the NF catalyst. Everything else is the same as in Example 1.

[0050] Figure 1 The images show X-ray diffraction (XRD) patterns. 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, and 3 is the NF catalyst prepared in Comparative Experiment 3. As shown in the figure, the characteristic peaks at 45.0°, 52.2°, and 76.7° correspond to the (111), (200), and (220) crystal planes of NF (JDPDS No. 04-0850), respectively; the characteristic peaks at 31.6°, 38.3°, 47.4°, 50.5°, and 55.6° correspond to the (311), (400), (422), (511), and (440) crystal planes of Co3S4 (JDPDS No. 74-0138), respectively; and the characteristic peaks at 29.9°, 47.8°, and 73.66° correspond to the (311), (511), and (731) crystal planes of Fe3S4 (JDPDS No. 23-1122), respectively. These results demonstrate the successful preparation of the FeCoS / NF composite material. No diffraction peaks of Co, Mo, and P elements were detected. This is because the CoMoP sample deposited on the FeCoS / NF surface by electrodeposition method contained very little CoMoP, which did not reach the detection limit.

[0051] Figure 2The X-ray photoelectron diffraction (XPS) analysis of the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 shows the presence of Co, Mo, P, Fe, S and Ni elements, which proves the successful preparation of the CoMoP / FeCoS / NF composite catalyst.

[0052] Figure 3 Figure 1 shows scanning electron microscopy (SEM) images. (a) shows the FeCoS / NF catalyst prepared in Comparative Experiment 1, and (b) shows the CoMoP / FeCoS / NF composite catalyst prepared in Example 1. As shown in Figure (a), FeCoS nanoparticles are tightly attached to the surface of the three-dimensional nickel foam. After Co-Mo-P electrodeposition on its surface, the morphology of the CoMoP / FeCoS / NF composite catalyst changes significantly. The three-dimensional nanosheet cluster structure and large specific surface area can not only effectively buffer the interaction between the gas and the solid surface and promote gas expulsion during the electrochemical reaction, but also effectively increase the reactive sites, promote sufficient contact between the catalyst and the electrolyte, and accelerate the electron transfer rate. This indicates that the CoMoP / FeCoS / NF composite catalyst has good activity for hydrogen production through water electrolysis.

[0053] Figure 4 The images show transmission electron microscopy (TEM) images of the CoMoP / FeCoS / NF composite catalyst prepared in Example 1. (a) is a magnified view of (a) at a scale bar of 500 nm, (b) is a magnified view of (a), (c) is a magnified view of (c) at a scale bar of 5 nm, and (d) is a magnified view of (c). The core-shell structure of the composite material is clearly visible in Figures (a) and (b). The CoMoP shell is uniformly coated on the surface of the FeCoS nanoparticles, with a thickness of approximately 130 nm. Furthermore, the heterostructure composed of FeCoS and CoMoP is observed in Figure (c), and the resulting electronic coupling effect significantly influences the acceleration of electron migration and the enrichment of electron migration pathways. Additionally, Figure (d) shows the interplanar spacings corresponding to the Co3S4(400) crystal plane, the Fe3S4(400) crystal plane, and the CoMoP(020) crystal plane, which are 0.24 nm, 0.28 nm, and 0.18 nm, respectively. These results correspond one-to-one with XRD, XPS, and SEM, verifying the accuracy of the characterization results.

[0054] Electrochemical performance testing: Electrochemical workstation (CHI760E) was used in a three-electrode system. The catalysts prepared in Examples and Comparative Experiments 1-3 were used as working electrodes, carbon rods as counter electrodes, and silver / silver chloride electrodes (Ag / AgCl) as reference electrodes. 0.5 mol / L H₂SO₄, 1.0 mol / L PBS (pH=7), and 1 mol / L KOH solutions were used as electrolytes under different pH conditions.

[0055] Hydrogen evolution test under alkaline conditions: Figure 5 Figure (a) shows the linear sweep voltammetric polarization (LSV) curves and stability test results of the catalyst under alkaline conditions for HER. 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3. Figure (b) shows the it curve of the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE of 0.101 V. From Figure (a), it can be observed that the CoMoP / FeCoS / NF composite catalyst has the lowest overpotential at the same current density, indicating that the CoMoP / FeCoS / NF composite catalyst exhibits good HER performance under alkaline conditions. This can be attributed to the synergistic effect between the morphology, composition, and dissimilar metal interface effects of the composite material. Specifically, at 10 mA / cm²... 2 At the specified current density, the CoMoP / FeCoS / NF composite catalyst prepared in this example requires an overpotential of 104 mV, which is the lowest among all the prepared catalysts, indicating that it possesses the optimal HER reaction activity. As shown in Figure (b), this catalyst can stably maintain high activity for more than 24 hours without significant degradation, confirming the excellent chemical stability of the CoMoP / FeCoS / NF composite catalyst under alkaline conditions. This can be attributed to the interaction between the sulfide and phosphide, which effectively strengthens the bonding ability between chemical bonds, thereby promoting the chemical stability and durability of the electrocatalyst.

[0056] Hydrogen evolution test under neutral conditions: Figure 6 The figures show the HER linear sweep voltammetric polarization (LSV) curves and stability test results of the catalysts under neutral conditions. (a) is the HER linear sweep voltammetric polarization (LSV) curve, where 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3. (b) is the it curve obtained by testing the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE of 0.171V. As can be seen from the figure, at 10 mA / cm²... 2At the given current density, the overpotentials of each catalyst were 171 mV, 189 mV, 298 mV, and 423 mV, respectively. The CoMoP / FeCoS / NF composite catalyst required the lowest overpotential, indicating that this material still exhibited the best HER reaction activity under neutral conditions. As shown in Figure (b), this catalyst could stably maintain its catalytic activity for more than 24 hours, confirming the excellent chemical stability of the CoMoP / FeCoS / NF composite catalyst under neutral conditions.

[0057] Hydrogen evolution test under acidic conditions: Figure 7 The figures show the HER linear sweep voltammetric polarization (LSV) curves and stability test results of the catalysts under acidic conditions. (a) is the HER linear sweep voltammetric polarization (LSV) curve, where 1 is the CoMoP / FeCoS / NF composite catalyst prepared in Example 1, 2 is the FeCoS / NF catalyst prepared in Comparative Experiment 1, 3 is the CoMoP / NF catalyst prepared in Comparative Experiment 2, and 4 is the NF catalyst prepared in Comparative Experiment 3. (b) is the it curve obtained by testing the CoMoP / FeCoS / NF composite catalyst prepared in Example 1 at a potential relative to RHE of 0.027 V. As can be seen from the figure, at 10 mA / cm²... 2 At the given current density, the overpotentials of each catalyst were 27 mV, 70 mV, 117 mV, and 199 mV, respectively. The CoMoP / FeCoS / NF composite catalyst prepared in Example 1 required the lowest overpotential, indicating that this material exhibited optimal HER reaction activity under acidic conditions. As shown in Figure (b), this catalyst could stably maintain its catalytic activity for more than 20 hours, confirming that the CoMoP / FeCoS / NF composite catalyst possesses excellent chemical stability under acidic conditions.

Claims

1. A method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full-pH water electrolysis, characterized in that... It is done in the following steps: I. Preparation of FeCoS / NF precursor: Cobalt, iron, and sulfur sources were uniformly dispersed in ethylene glycol and then ultrasonically treated to obtain a homogeneous and stable mixed solution A. Nickel foam was then immersed in the homogeneous and stable mixed solution A and reacted at a temperature of 150℃~240℃ for 8h~12h. Finally, the mixture was washed and dried to obtain the FeCoS / NF precursor. II. Preparation of CoMoP / FeCoS / NF composite catalyst: Cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate, and trisodium citrate were uniformly dispersed in deionized water and then stirred to obtain a homogeneous and stable mixed solution B. Using the homogeneous and stable mixed solution B as the electrolyte, FeCoS / NF precursor as the working electrode, carbon rod as the counter electrode, and Ag / AgCl as the reference electrode, the CoMoP / FeCoS / NF composite catalyst was obtained by deposition under constant voltage conditions for 60s to 150s.

2. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production through full pH water electrolysis according to claim 1, characterized in that... The cobalt source mentioned in step one is cobalt chloride hexahydrate; the iron source mentioned in step one is ferrous sulfate heptahydrate; and the sulfur source mentioned in step one is thiourea.

3. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The molar ratio of cobalt source to iron source in step one is 1:(0.5-2); the molar ratio of cobalt source to sulfur source in step one is 1:(1-3); the molar ratio of cobalt source to ethylene glycol in step one is 1 mmol:(20-50) mL.

4. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The ultrasonic treatment described in step one is specifically performed at a power of 200W to 500W for 0.5h to 2h.

5. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The foamed nickel mentioned in step one is pretreated foamed nickel; the pretreatment is specifically carried out according to the following steps: ① ultrasonic cleaning with hydrochloric acid, acetone, ethanol and ultrapure water with a concentration of 2mol / L to 4mol / L in sequence; ② repeat step ① 2 to 4 times, and finally dry at a temperature of 50℃ to 60℃ for 6h to 10h.

6. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The washing and drying process described in step one specifically involves washing with deionized water and then drying at a temperature of 50℃~60℃ for 8h~12h.

7. The method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full pH water electrolysis according to claim 5, characterized in that... The nickel foam mentioned in step one has a purity of 99.99%, a thickness of 1 mm to 2 mm, and a pore size of 100 PPI to 120 PPI.

8. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The mass ratio of cobalt nitrate hexahydrate to sodium hypophosphite in step two is 1:(3-4); the mass ratio of cobalt nitrate hexahydrate to sodium molybdate in step two is 1:(0.5-1.5); the mass ratio of cobalt nitrate hexahydrate to trisodium citrate in step two is 1:(0.5-1); and the mass ratio of cobalt nitrate hexahydrate to deionized water in step two is 1g:(700-1000)mL.

9. The preparation method of the CoMoP / FeCoS / NF composite catalyst for hydrogen production by full pH water electrolysis according to claim 1, characterized in that... The stirring described in step two is specifically carried out at a speed of 200 r / min to 500 r / min for 0.5 h to 1.5 h.

10. The method for preparing a CoMoP / FeCoS / NF composite catalyst for hydrogen production via full pH water electrolysis according to claim 1, characterized in that... In step two, deposition is carried out for 60s to 150s under a constant voltage of -0.5V to -3V.

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