Preparation of three-dimensional heterostructure P-doped CoMo-based composite material and application to electrolyzed water
By synthesizing CoMoP/CoMoO4/ZnCo2O4 nanoflower-like catalysts on copper foam substrates, the problems of high cost of noble metal catalysts and structural instability of non-noble metal catalysts were solved, achieving electrocatalytic water splitting with low overpotential and high stability.
Patent Information
- Application Number
- CN202410612381.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-16
- Publication Date
- 2025-11-18
AI Technical Summary
Existing precious metal catalysts are expensive and scarce, while traditional non-precious metal catalysts such as ZnCo2O4 are structurally unstable, have limited active sites, and low electron transport efficiency during electrocatalytic water splitting, making it difficult to achieve efficient electrocatalytic water splitting.
ZnCo2O4 nanowires were grown in situ on a copper foam substrate, and CoMoP/CoMoO4/ZnCo2O4 nanoflower-like catalysts were synthesized through hydrothermal reaction and gas-phase phosphating. This increased the active sites and improved the electronic structure, forming a three-dimensional heterostructure to enhance catalytic activity and stability.
Electrocatalytic water splitting with low overpotential and high stability was achieved. CoMoP/CoMoO4/ZnCo2O4 had HER and OER overpotentials of 199mV and 290mV, respectively, at a current density of 50mA cm-2, and maintained stability for 60h, which is superior to traditional catalysts.
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Figure CN120967409A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of new energy materials, specifically relating to a method for preparing a CoMoP / CoMoO4 / ZnCo2O4 composite material and its application in electrocatalytic water splitting. Background Technology
[0002] In recent years, the extensive use of traditional fossil fuels has led to increasingly serious energy and environmental problems, urgently requiring the development of a new energy source to replace traditional fossil fuels. Electrochemical water splitting can convert electrical energy into clean and sustainable hydrogen energy. Hydrogen can serve as a highly efficient fuel for powering fuel cells or as a chemical feedstock, helping to reduce fossil fuel consumption, lower carbon emissions, and promote the development of renewable energy. HER and OER are two important reactions in the electrochemical water splitting process, with the OER reaction typically requiring high energy. The preparation of high-performance electrocatalysts is crucial for the realization of electrochemical water splitting. Pt-based and Ir / Ru-based catalysts are commercially efficient electrocatalysts for HER and OER, respectively; however, the high price and scarcity of precious metal catalysts limit their commercial application. Therefore, developing non-precious metal catalysts with high catalytic performance is of great significance.
[0003] Recent studies have shown that many non-noble metal-based catalysts have demonstrated excellent performance, possessing unique electronic structures, good catalytic activity, abundant reserves, and ease of preparation and regulation. Traditional noble metal catalysts are costly and difficult to produce on a large scale; therefore, the emergence of non-noble metal catalysts has significantly reduced production costs and difficulties. Among these, transition metal oxides are particularly promising. Compared to single-transition metal oxides, dual-transition metal oxides exhibit better chemical stability, more readily available active sites, more abundant redox reactions, better ionic conductivity, and corrosion resistance. ZnCo₂O₄, as a dual-transition metal oxide, has also been shown to have excellent electrocatalytic performance; however, its structure is prone to changes during reactions. Therefore, further rational design of the catalyst structure is needed to further improve catalytic activity and stability. Recently, transition metal molybdates have been considered more promising catalysts for water splitting due to their larger specific surface area, favorable crystal structure, and more prominent redox reactions. CoMoO4-based catalysts have attracted considerable attention, primarily due to the significant redox reactions of Co and the excellent electrical conductivity of Mo. The synergistic effect of Co and Mo is beneficial to the catalytic reaction. However, their active sites are limited, electron transport efficiency is low, and stability needs improvement. To overcome these shortcomings, the synthesis strategy of the catalyst needs to be optimized. Combining it with non-metallic elements (such as O, P, S, N, and Se) is an effective strategy to improve its electrochemical performance. Among these, P has high electronegativity, and transition metal phosphides have good catalytic activity and stability, showing broader application prospects in alkaline electrolytes. Therefore, effectively doping P into electrocatalysts can effectively improve the HER and OER reactivity of the catalysts. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing CoMoP / CoMoO4 / ZnCo2O4 composite material and its application in electrocatalytic water splitting. The material exhibits a nanoflower-like structure, thereby increasing the contact area with the electrolyte solution, and has a low overpotential and high stability, thus achieving efficient overall water splitting.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] This invention provides a CoMoP / CoMoO4 / ZnCo2O4 composite material, in which a CoMoP / CoMoO4 / ZnCo2O4 nanoflower array is uniformly grown on the surface of copper foam. The CoMoP / CoMoO4 / ZnCo2O4 nanosheets are approximately 400 nm thick and exhibit a nanoflower-like structure. This unique nanoflower-like structure exposes more active sites on the catalyst. The introduction of phosphorus (P) alters the electronic structure of the catalyst surface, enhancing the charge transfer rate and promoting electron transfer, resulting in excellent OER and HER catalytic activity.
[0007] The present invention also provides a method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material, comprising the following steps:
[0008] (1) Pretreatment of copper foam (CF): Cut the required copper foam substrate into a rectangle of 2cm×5cm, place it in 0.05-0.55g / mL hydrochloric acid and sonicate for 5-15min, then take it out and wash it with water until neutral, and finally sonicate it with anhydrous ethanol for 5-15min to successfully remove the oxide layer on the surface of the copper foam.
[0009] (2) Preparation of ZnCo2O4: Cobalt nitrate hexahydrate, zinc nitrate hexahydrate, ammonium fluoride, and urea were dissolved in a certain amount of deionized water, ultrasonically dissolved, and then magnetically stirred. The mixture was then transferred to a high-pressure reactor, pretreated copper foam was added, and the mixture was heated at 100-140℃ for 3-6 hours. Finally, the sample was washed and dried to obtain ZnCo2O4.
[0010] (3) Preparation of CoMoO4 / ZnCo2O4: Sodium molybdate dihydrate and cobalt nitrate hexahydrate were weighed and dissolved in deionized water. After ultrasonic dissolution, the mixed solution and ZnCo2O4 obtained in step (1) were transferred to a high-pressure reactor and reacted at 120-150℃ under hydrothermal conditions for 3-6 hours. After natural cooling to room temperature, the mixture was washed and dried to obtain CoMoO4 / ZnCo2O4.
[0011] (4) Preparation of CoMoP / CoMoO4 / ZnCo2O4: The CoMoO4 / ZnCo2O4 precursor and sodium hypophosphite powder obtained in step (2) above were placed in two porcelain boats, which were placed upstream and midstream of a tube furnace, respectively. Then, the furnace was heated to 200-500℃ in a N2 atmosphere and held for 0.5-3.5 h, with a heating rate of 3-8℃ / min. -1 The prepared sample is CoMoP / CoMoO4 / ZnCo2O4.
[0012] Further, the mass concentration of the hydrochloric acid aqueous solution in step (1) is 0.05-0.5 g / mL. Preferably, the mass concentration of the hydrochloric acid aqueous solution is 0.05-0.15 g / mL.
[0013] Further, in step (2), the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.005-0.05 g / mL, the mass concentration of the zinc nitrate hexahydrate aqueous solution is 0.003-0.3 g / mL, the mass concentration of the ammonium fluoride aqueous solution is 0-0.01 g / mL, and the mass concentration of the urea aqueous solution is 0.002-0.2 g / mL. Preferably, the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.007-0.01 g / mL, the mass concentration of the zinc nitrate hexahydrate aqueous solution is 0.002-0.005 g / mL, the mass concentration of the ammonium fluoride aqueous solution is 0-0.003 g / mL, and the mass concentration of the urea aqueous solution is 0.004-0.007 g / mL.
[0014] Further, in step (3), the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.003-0.005 g / mL, the mass concentration of the sodium molybdate dihydrate aqueous solution is 0.002-0.005 g / mL, preferably the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.0045-0.0050 g / mL, and the mass concentration of the sodium molybdate dihydrate aqueous solution is 0.00375-0.00450 g / mL.
[0015] Further, in step (4), the mass of sodium hypophosphite powder is 0.3-0.7g. Preferably, the mass of sodium hypophosphite powder is 0.45-0.55g.
[0016] Furthermore, the substrate is a porous copper foam substrate.
[0017] The present invention also provides the application of the CoMoP / CoMoO4 / ZnCo2O4 composite material as a catalyst in electrocatalytic water splitting.
[0018] Compared with the prior art, the beneficial effects of the present invention are:
[0019] 1. This invention prepares a method for in-situ growth of ZnCo2O4 nanowires on a copper foam substrate. Using ZnCo2O4 nanowires as a precursor, a three-dimensional heterostructured CoMoP / CoMoO4 / ZnCo2O4 nanoflower-like catalyst is synthesized via hydrothermal reaction and gas-phase phosphating. The CoMoP / CoMoO4 / ZnCo2O4 catalyst achieves a wavelength of 50 mA cm⁻¹. -2 At a given current density, the overpotential of its HER is 199 mV, and the overpotential of its OER is 290 mV. CoMoP / CoMoO4 / ZnCo2O4, as a bifunctional electrode, requires a voltage of 1.78 V to achieve a 100 mA cm⁻¹ in overall water / seawater splitting.-2 The current density was maintained at a stable level for 60 hours, indicating that the system has good long-term stability for overall water splitting.
[0020] 2. The electrocatalyst possesses a unique three-dimensional flower-like nanostructure. This nanoflower structure increases the number of accessible active sites and enlarges the contact area with the electrolyte solution. The introduction of phosphorus (P) alters the electronic structure of the catalyst surface, thereby enhancing the charge transfer rate of the catalyst.
[0021] 3. The synergistic effect of the transition metal oxide and transition metal phosphide interfaces in this invention improves catalytic activity and stability. Using copper foam as a substrate to prepare a self-supporting catalyst can improve the catalyst's conductivity and charge transfer rate, and also contribute to enhancing its long-term stability. Attached Figure Description
[0022] Figure 1 Example 1: SEM images of CoMoP / CoMoO4 / ZnCo2O4 were prepared.
[0023] Figure 2 Example 1: TEM image of CoMoP / CoMoO4 / ZnCo2O4 prepared.
[0024] Figure 3 Example 1: LSV curves of OER of Co3O4 / ZnCo2O4 (Co∶Mo 1∶0), CoMoO4 / ZnCo2O4 (Co∶Mo 1∶1) and CoMoO4 / ZnCo2O4 (Co∶Mo 1∶2) in 1M KOH solution.
[0025] Figure 4 Example 1: LSV curves of HER of Co3O4 / ZnCo2O4 (Co∶Mo 1∶0), CoMoO4 / ZnCo2O4 (Co∶Mo 1∶1) and CoMoO4 / ZnCo2O4 (Co∶Mo 1∶2) in 1M KOH solution.
[0026] Figure 5 Example 1 shows the LSV curves of OER of CoMoP / CoMoO4 / ZnCo2O4 (0.1g), CoMoP / CoMoO4 / ZnCo2O4 (0.5g) and CoMoP / CoMoO4 / ZnCo2O4 (1g) in 1M KOH solution.
[0027] Figure 6Example 1 shows the LSV curves of HER of CoMoP / CoMoO4 / ZnCo2O4 (0.1g), CoMoP / CoMoO4 / ZnCo2O4 (0.5g) and CoMoP / CoMoO4 / ZnCo2O4 (1g) in 1M KOH solution.
[0028] Figure 7 Example 1: LSV curves of OER of CoMoP / CoMoO4 / ZnCo2O4 and control sample in 1M KOH solution.
[0029] Figure 8 Example 1: LSV curves of the HER of CoMoP / CoMoO4 / ZnCo2O4 and the control sample in 1M KOH solution.
[0030] Figure 9 Tafel slope diagrams of OER of CoMoP / CoMoO4 / ZnCo2O4 and control sample prepared in 1M KOH solution in Example 1.
[0031] Figure 10 Example 1: Tafel slope plots of HER for CoMoP / CoMoO4 / ZnCo2O4 and the control sample in 1M KOH solution.
[0032] Figure 11 Impedance diagrams of OER of CoMoP / CoMoO4 / ZnCo2O4 and the control sample prepared in Example 1 in 1M KOH solution.
[0033] Figure 12 Impedance chromatograms of HER obtained from the preparation of CoMoP / CoMoO4 / ZnCo2O4 and the control sample in 1M KOH solution in Example 1.
[0034] Figure 13 Example 1: LSV curves of CoMoP / CoMoO4 / ZnCo2O4 as anode and cathode for overall water splitting.
[0035] Figure 14 Example 1: The CoMoP / CoMoO4 / ZnCo2O4 prepared were used as anode and cathode respectively for overall water splitting stability testing. Detailed Implementation
[0036] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.
[0037] Example 1: A method for preparing a CoMoP / CoMoO4 / ZnCo2O4 composite material, comprising the following steps:
[0038] (1) Pretreatment of copper foam (CF): Cut the required copper foam substrate into a rectangle of 2cm×5cm, place it in 0.1g / mL hydrochloric acid and sonicate for 10min, then take it out and wash it with water until neutral, and finally sonicate it with anhydrous ethanol for 10min to successfully remove the oxide layer on the surface of the copper foam.
[0039] (2) Dissolve 0.58 g of cobalt nitrate hexahydrate, 0.30 g of zinc nitrate hexahydrate, 0.07 g of ammonium fluoride, and 0.36 g of urea in 70 ml of deionized water. After sonication for 5 min, stir magnetically for 30 min. Then, transfer the mixture to a 100 mL PTFE-lined stainless steel high-pressure reactor, add pretreated copper foam, and heat at 120 °C for 4 h. Finally, rinse the sample with DI water and dry in an oven for 12 h. The prepared sample is ZnCo2O4.
[0040] (3) Dissolve 0.29 g of cobalt nitrate hexahydrate and 0.24 g of sodium molybdate dihydrate in 60 mL of DI water. Stir ultrasonically for 10 min to dissolve, then stir magnetically for 30 min to make the solution more homogeneous. Add the ZnCo2O4 precursor to the above pink solution and transfer it to a 100 mL PTFE-lined stainless steel high-pressure reactor. Heat at 140 °C for 4 h. Finally, rinse the sample with DI water and dry in an oven for 12 h. The prepared sample is CoMoO4 / ZnCo2O4.
[0041] (4) The prepared CoMoO4 / ZnCo2O4 precursor and 0.5g of sodium hypophosphite powder were placed in two porcelain boats, which were then placed upstream and midstream of a tube furnace, respectively. The furnace was then heated to 300℃ in a N2 atmosphere and held for 1 hour at a heating rate of 5℃ / min. -1 The prepared sample is CoMoP / CoMoO4 / ZnCo2O4.
[0042] Figure 1-2 SEM and TEM images of CoMoP / CoMoO4 / ZnCo2O4 are shown. The SEM image reveals a uniform array of nanoflower-like nanosheets (CoMoP / CoMoO4 / ZnCo2O4) growing on a copper foam framework, with intact nanosheet morphology and a thickness of approximately 400 nm. Phosphorus doping of the nanosheets results in the appearance of tiny nanoparticles on the surface, increasing the surface roughness. The TEM image shows the structure of the CoMoP / CoMoO4 / ZnCo2O4 nanoflower clusters, which are composed of numerous nanosheets, consistent with the SEM results.
[0043] Example 2: The ratio of cobalt to molybdenum in step (2) of Example 1 was changed to 1:1 and 1:0, while other conditions remained the same as in Example 1. The results were obtained through LSV testing (…). Figure 3 and Figure 4 The ratio of cobalt to molybdenum affects the material's properties. When the cobalt-molybdenum ratio is 1:1, the material has a smaller overpotential at the same current density.
[0044] Example 3: The amount of phosphating in step (3) of Example 1 was changed (the amount of phosphating was 0.1 g and 1 g), while other conditions were the same as in Example 1, to obtain CoMoP / CoMoO4 / ZnCo2O4 (0.1 g) and CoMoP / CoMoO4 / ZnCo2O4 (1 g). The results were tested by LSV (Laser-Saturated Variation). Figure 5 and Figure 6 Different phosphating amounts affect the material's performance. When the phosphating amount is 0.5g, the overpotential of the material is relatively small at the same current density. Excessive phosphating amount will lead to a larger overpotential.
[0045] Example 4: The CoMoP / CoMoO4 / ZnCo2O4 composite material prepared in Example 1 was used as a catalyst for electrocatalytic water splitting. The main test steps are as follows:
[0046] (1) Electrochemical tests were performed using a three-electrode system. In 1M KOH solution, CoMoP / CoMoO4 / ZnCo2O4 were used as working electrodes, platinum sheet as counter electrode, and mercury / mercury oxide electrode as reference electrode.
[0047] (2) Before testing, the catalyst was subjected to cyclic voltammetry (CV) for 40 cycles to better activate it. During linear sweep voltammetry (LSV), the HER test range was -0.924 to -1.524 V, and the OER test range was 0-1 V. 90% iR compensation was applied during the test, and the scan rate was 5 mV / s. -1 By testing the LSV of different catalysts, the value at 50 mA cm⁻¹ was calculated. -2 The overpotential required for each catalyst at a given current density. A lower overpotential indicates better electrocatalytic performance in hydrogen evolution and oxygen evolution. Figure 7 and Figure 8 The LSV curves of CoMoP / CoMoO4 / ZnCo2O4 and its control sample in 1M KOH for the OER and HER reactions are shown. The figures reveal that at the same current density, the overpotential of CoMoP / CoMoO4 / ZnCo2O4 is lower than that of other catalysts for both the OER and HER reactions, indicating that CoMoP / CoMoO4 / ZnCo2O4 exhibits superior catalytic performance.
[0048] (3) The Tafel slope is calculated using the formula η=a+blgI, combined with the LSV curve through linear transformation. The lower the Tafel slope, the faster the oxygen evolution reaction rate. Figure 9 and Figure 10 The Tafel slope images for the OER and HER processes of CoMoP / CoMoO4 / ZnCo2O4 and the control sample show that, compared to other control samples (excluding commercial catalysts), CoMoP / CoMoO4 / ZnCo2O4 exhibits the smallest Tafel slope (129.74 and 116.44 mV dec). -1 This indicates that it has the fastest reaction kinetics.
[0049] (4) The amplitude potential of the impedance test EIS is 0.05V, the frequency range is 0.01-100kHz, and the measured potential is consistent with the open circuit voltage. Figure 11 and Figure 12 Impedance images of CoMoP / CoMoO4 / ZnCo2O4 and a control sample. From Figure 11 and Figure 12 The results show that CoMoP / CoMoO4 / ZnCo2O4 exhibits the lowest resistance (0.11 and 0.35 Ω) during OER and HER reactions, demonstrating its faster oxygen evolution and hydrogen evolution reaction kinetics.
[0050] (5) The LSV test voltage range for complete hydrolysis is 1-2V. 90% iR compensation is performed during the test, and the scan rate is 5mV / s. -1 Because CoMoP / CoMoO4 / ZnCo2O4 exhibits excellent HER and OER performance in 1M KOH solution, it can serve as a stable and efficient bifunctional electrocatalyst for total water splitting. The CoMoP / CoMoO4 / ZnCo2O4 bifunctional catalyst was used as both the anode and cathode for total water splitting. Figure 13 and Figure 14 As shown, assembling the CoMoP / CoMoO4 / ZnCo2O4‖CoMoP / CoMoO4 / ZnCo2O4 two-electrode system in 1M KOH requires a voltage of 1.78V to reach 100mA cm⁻¹. -2 The current density is better than that of Pt / C‖RuO2 (1.83V), and it can maintain stability for 60 hours.
[0051] 4. In summary, a novel heterostructure self-supporting electrode, CoMoP / CoMoO4 / ZnCo2O4, for total water splitting was prepared. In 1M KOH solution, the current density was 50 mA cm⁻¹. -2 At that time, the HER overpotential of CoMoP / CoMoO4 / ZnCo2O4 was 199 mV, and the Tafel slope was 116.44 mV dec.-1 The overpotential of the OER is 290 mV, and the Tafel slope is 129.74 mVdec. -1 The CoMoP / CoMoO4 / ZnCo2O4 catalyst exhibits good bifunctional electrocatalytic performance under alkaline conditions. When CoMoP / CoMoO4 / ZnCo2O4 are used as the anode and cathode respectively for overall water splitting, a catalytic efficiency of 100 mA / cm² is achieved. -2 At that time, a battery voltage of 1.78V was required, which is better than that of Pt / C‖RuO2 (1.83V), and the stability was maintained for 60h, indicating that the system has good long-term stability for overall water splitting.
[0052] 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 CoMoP / CoMoO4 / ZnCo2O4 composite material, characterized in that: A CoMoP / CoMoO4 / ZnCo2O4 nanosheet array was uniformly grown on the surface of copper foam. The nanosheets were 400 nm thick and exhibited a nanoflower-like structure, which increased the contact area with the electrolyte solution.
2. A method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material according to claim 1, characterized in that: Includes the following steps: (1) Pretreatment of copper foam (CF): Cut the required copper foam substrate into a rectangle of 2cm×5cm, place it in 0.05-0.55g / mL hydrochloric acid and sonicate for 5-15min, then take it out and wash it with water until neutral, and finally sonicate it with anhydrous ethanol for 5-15min to successfully remove the oxide layer on the surface of the copper foam. (2) Preparation of ZnCo2O4: Cobalt nitrate hexahydrate, zinc nitrate hexahydrate, ammonium fluoride, and urea were dissolved in a certain amount of deionized water, ultrasonically dissolved, and then magnetically stirred. The mixture was then transferred to a high-pressure reactor, pretreated copper foam was added, and the mixture was heated at 100-150℃ for 3-6 hours. Finally, the sample was washed and dried to obtain ZnCo2O4. (3) Preparation of CoMoO4 / ZnCo2O4: Weigh sodium molybdate dihydrate and cobalt nitrate hexahydrate and dissolve them in deionized water. After ultrasonic dissolution, transfer the mixed solution together with the ZnCo2O4 obtained in step (1) to a high-pressure reactor and react under hydrothermal conditions at 100-150℃ for 3-6 hours. After naturally cooling to room temperature, wash and dry to obtain CoMoO4 / ZnCo2O4. (4) Preparation of CoMoP / CoMoO4 / ZnCo2O4: The CoMoO4 / ZnCo2O4 precursor and sodium hypophosphite powder obtained in step (2) above were placed in two porcelain boats, which were placed upstream and midstream of a tube furnace, respectively. Then, the furnace was heated to 200-600℃ in a N2 atmosphere and held for 0.5-3.5 h, with a heating rate of 3-8℃ / min. -1 The prepared sample is CoMoP / CoMoO4 / ZnCo2O4.
3. The method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material according to claim 2, characterized in that: Step (1) The mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.005-0.05 g / mL, the mass concentration of the zinc nitrate hexahydrate aqueous solution is 0.002-0.2 g / mL, the mass concentration of the ammonium fluoride aqueous solution is 0-0.01 g / mL, and the mass concentration of the urea aqueous solution is 0.002-0.2 g / mL.
4. The method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material according to claim 2, characterized in that: In step (2), the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.001-0.005 g / mL, and the mass concentration of the sodium molybdate dihydrate aqueous solution is 0.001-0.003 g / mL.
5. The method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material according to claim 2, characterized in that: In step (3), the mass of sodium hypophosphite powder is 0.3-0.7g.
6. The method for preparing the CoMoP / CoMoO4 / ZnCo2O4 composite material according to claim 1, characterized in that: The substrate is a porous copper foam substrate.
7. The application of the CoMoP / CoMoO4 / ZnCo2O4 composite material as an electrocatalyst in the HER reaction according to claim 1.
8. The application of the CoMoP / CoMoO4 / ZnCo2O4 composite material as an electrocatalyst in the OER reaction according to claim 1.
9. The application of the CoMoP / CoMoO4 / ZnCo2O4 composite material as described in claim 1 as an electrocatalyst in the total water splitting reaction.