Non-precious metal catalyst and preparation method thereof

Abstract

The present invention provides a non-precious metal catalyst and a preparation method thereof. The preparation method comprises: preparing a sol, mixing butyl titanate, ammonium fluoride, and ethylene glycol to obtain a sol; preparing a support, first immersing a porous template in the sol, then heating the immersed porous template, and cooling it to obtain a porous titanium dioxide support; preparing a slurry, dissolving basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid, and cobalt nitrate hexahydrate in deionized water to obtain a slurry; and electrodeposition, immersing the porous titanium dioxide support in the slurry and subjecting the porous titanium dioxide support to a constant potential polarization treatment using a three-electrode system to obtain the non-precious metal catalyst. The preparation method provided by the present invention solves the problems of high cost, low catalytic efficiency, and unstable catalytic activity of existing electrocatalysts.

Description

Technical Field

[0001] The present invention relates to the field of new energy technology, and in particular to a non-precious metal catalyst and a preparation method thereof. Background Art

[0002] As the pollution and depletion problems of traditional fuels become increasingly serious, the search for sustainable, environmentally friendly, efficient and clean energy within the entire energy system is the current and future direction of human social development. Among them, water electrolysis hydrogen evolution technology occupies an important position in the storage and use of new energy sources. Currently, the main factors limiting the development and promotion of this technology are the high price and scarce production of precious metal catalysts for industrial use on the market, while current non-precious metal catalysts also have problems such as difficulty in preparation, low conversion efficiency and poor electrode stability. These reasons have led to the current high cost of hydrogen production, severely limiting the large-scale use of water electrolysis hydrogen production technology.

[0003] Therefore, how to solve the problems of high cost, low catalytic efficiency and unstable catalytic activity of existing electrocatalysts needs to be studied urgently. Summary of the Invention

[0004] The purpose of the present invention is to provide a non-precious metal catalyst and a preparation method thereof, so as to solve the problems of high cost, low catalytic efficiency and unstable catalytic activity of existing electrocatalysts.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A method for preparing a non-precious metal catalyst, comprising the following steps:

[0007] Sol preparation: mixing butyl titanate, ammonium fluoride and ethylene glycol to obtain a sol;

[0008] Preparation of the carrier: first, immersing the porous template in the sol, then heating the immersed porous template, and cooling it to obtain a porous titanium dioxide carrier;

[0009] preparing a slurry by dissolving basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid, and cobalt nitrate hexahydrate in deionized water to obtain a slurry;

[0010] Electrodeposition: immersing the porous titanium dioxide support in the slurry, and performing a constant potential polarization treatment on the porous titanium dioxide support through a three-electrode system to obtain the non-precious metal catalyst.

[0011] In some embodiments of the present invention, the porous template is an open-cell polymer reticulated foam.

[0012] In some embodiments of the present invention, the preparation method further comprises, before the carrier preparation step:

[0013] Template cleaning: using hydrochloric acid, acetone, anhydrous ethanol and deionized water to clean the porous template in sequence.

[0014] In some embodiments of the present invention, in the sol preparation step, 0.5-2 g of ammonium fluoride is dissolved in 1.5-3.6 mL of deionized water to obtain an ammonium fluoride aqueous solution, and then the ammonium fluoride aqueous solution is mixed with butyl titanate and ethylene glycol to obtain the sol.

[0015] In some embodiments of the present invention, the sol preparation step further comprises:

[0016] Nitric acid and a complexing agent are added to a mixture of butyl titanate, ammonium fluoride and ethylene glycol, and the mixture is stirred.

[0017] In some embodiments of the present invention, the complexing agent is citric acid.

[0018] In some embodiments of the present invention, in the sol preparation step, the volume ratio of butyl titanate, ammonium fluoride aqueous solution, nitric acid, citric acid, and ethylene glycol is (20-40):(1-3):(1-2):(2-6):(80-120).

[0019] In some embodiments of the present invention, in the sol preparation step, the mixture of butyl titanate, ammonium fluoride and ethylene glycol is placed in an environment of 70 to 90° C. and kept warm for 6 to 24 hours.

[0020] In some embodiments of the present invention, in the carrier preparation step, the porous template is placed in the sol and ultrasonically stirred for 10 to 60 minutes.

[0021] In some embodiments of the present invention, in the carrier preparation step, the porous template that has undergone the immersion treatment is kept warm in an environment of 1100-1300° C. for 1-3 hours.

[0022] In some embodiments of the present invention, in the slurry preparation step, 2 to 6 g of basic nickel carbonate, 2 to 6 g of nickel sulfate hexahydrate, 0.5 to 3 g of nickel chloride hexahydrate, 4 to 8 g of sodium citrate, 1 to 3 g of sodium chloride, 1 to 5 g of boric acid and 0.1 to 5 g of cobalt nitrate hexahydrate are dissolved in 80 to 150 mL of deionized water to obtain the slurry.

[0023] In some embodiments of the present invention, in the slurry preparation step, the pH value of the slurry is adjusted to 9.5-10.5 with ammonia water.

[0024] In some embodiments of the present invention, in the electrodeposition step, the working electrode of the three-electrode system is connected to the porous support, the counter electrode of the three-electrode system is connected to a platinum electrode, and the reference electrode of the three-electrode system is connected to a silver chloride electrode;

[0025] The duration of the constant potential polarization treatment is 0.5 to 3 minutes, and the voltage of the constant potential polarization treatment is 0.1 to 1.2V.

[0026] In order to achieve the above object, the present invention also provides the following technical solutions:

[0027] A non-precious metal catalyst is prepared by the above preparation method.

[0028] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0029] 1. The non-precious metal catalyst and preparation method provided by the present invention solve the problems of high cost, low catalytic efficiency and unstable catalytic activity of existing electrocatalysts. Specifically, the present invention uses butyl titanate as a titanium source, and mixes butyl titanate with ammonium fluoride and ethylene glycol to obtain a sol, and attaches the sol to a porous template with a large surface area to obtain a porous titanium dioxide support. Subsequently, the porous titanium dioxide support is mixed with basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid and cobalt nitrate hexahydrate, and the porous titanium dioxide support is subjected to a constant potential polarization treatment through a three-electrode system to obtain the above-mentioned non-precious metal catalyst with better catalytic rate and stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0031] Figure 1 A flow chart of the steps of a method for preparing a non-precious metal catalyst provided in one embodiment of the present invention;

[0032] Figure 2 This is a scanning electron microscope image of the catalyst prepared in Example 2 of the present invention;

[0033] Figure 3 The X-ray diffraction patterns of the catalysts obtained in Example 2 of the present invention and Comparative Examples 2-3;

[0034] Figure 4 Polarization curves of the catalysts obtained in Example 2 of the present invention and Comparative Examples 1-3;

[0035] Figure 5 This is a 12h constant potential polarization diagram of the catalyst obtained in Example 2 of the present invention;

[0036] Figure 6 Polarization curves of the catalysts obtained in Examples 2 to 5 of the present invention;

[0037] Figure 7 Polarization curves of the catalysts obtained in Example 2 and Examples 6 to 8 of the present invention. DETAILED DESCRIPTION

[0038] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0039] The technical solutions of the present invention provide a non-precious metal catalyst and a method for preparing the same, which are described in detail below. It should be noted that the order in which the following examples are described does not constitute a preferred order for the embodiments of the present invention. Furthermore, the descriptions of each embodiment in the following examples each have their own emphasis. For details not detailed in one embodiment, reference can be made to the relevant descriptions of other embodiments.

[0040] Example 1

[0041] A method for preparing a non-precious metal catalyst comprises the following steps: preparing a sol, mixing butyl titanate, ammonium fluoride and ethylene glycol to obtain a sol; preparing a carrier, first soaking a porous template in the sol, then heating the soaked porous template, and cooling it to obtain a porous titanium dioxide carrier; preparing a slurry, dissolving basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid and cobalt nitrate hexahydrate in deionized water to obtain a slurry; and electrodeposition, immersing the porous titanium dioxide carrier in the slurry and performing a constant potential polarization treatment on the porous titanium dioxide carrier using a three-electrode system to obtain the non-precious metal catalyst.

[0042] The preparation method provided by the present invention solves the problems of high cost, low catalytic efficiency and unstable catalytic activity of existing electrocatalysts. Specifically, the present invention uses butyl titanate as a titanium source, and mixes butyl titanate with ammonium fluoride and ethylene glycol to obtain a sol, and attaches the sol to a porous template with a large surface area to obtain a porous titanium dioxide support. Subsequently, the porous titanium dioxide support is mixed with basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid and cobalt nitrate hexahydrate, and the porous titanium dioxide support is subjected to a constant potential polarization treatment through a three-electrode system to obtain the above-mentioned non-precious metal catalyst with better catalytic rate and stability.

[0043] In some embodiments of the present invention, the porous template is an open-cell polymer reticulated foam. Specifically, the open-cell polymer reticulated foam can be a polypropylene porous template with a pore size between 10 and 50 nm, which is removable by high-temperature calcination. In the present invention, this template serves as a support for the porous titanium dioxide. During the high-temperature calcination process, the porous titanium dioxide is obtained and the support template is removed, leaving only the porous titanium dioxide.

[0044] In some embodiments of the present invention, the preparation method further comprises, before the carrier preparation step, template cleaning, sequentially and respectively using hydrochloric acid, acetone, anhydrous ethanol and deionized water to clean the porous template.

[0045] In some embodiments of the present invention, in the sol preparation step, 0.5-2g of ammonium fluoride is dissolved in 1.5-3.6mL of deionized water to obtain an ammonium fluoride aqueous solution, and then the ammonium fluoride aqueous solution is mixed with butyl titanate and ethylene glycol to obtain the sol. It is understandable that the ratio between ammonium fluoride and deionized water can be adjusted according to actual conditions; for example, the mass of ammonium fluoride can be any one of 0.7g, 1g, 1.2g, 1.5g, 1.75g ​​or 1.9g, and correspondingly, the volume of deionized water can be any one of 1.8mL, 2mL, 2.5mL, 3mL or 3.3mL.

[0046] In some embodiments of the present invention, the sol preparation step further comprises: adding nitric acid and a complexing agent to the mixture of butyl titanate, ammonium fluoride and ethylene glycol, and stirring.

[0047] It is understandable that the above-mentioned complexing agent can be selected and adjusted according to actual needs; in some embodiments of the present invention, the complexing agent is citric acid.

[0048] In some embodiments of the present invention, in the sol preparation step, the volume ratio of butyl titanate, ammonium fluoride aqueous solution, nitric acid, citric acid, and ethylene glycol is (20-40):(1-3):(1-2):(2-6):(80-120). For example, the volume fraction of butyl titanate can be 25, 30, or 35, and correspondingly, the volume fraction of ammonium fluoride aqueous solution can be 1.5, 2, or 2.6, the volume fraction of nitric acid can be 1.2, 1.5, or 1.7, the volume fraction of citric acid can be any one of 2.5, 3, 3.4, 4, 4.5, 5, and 5.5, and the volume fraction of ethylene glycol can be any one of 85, 90, 95, 100, 105, 110, and 115.

[0049] In some embodiments of the present invention, in the sol preparation step, the mixture of butyl titanate, ammonium fluoride, and ethylene glycol is placed in an environment of 70-90° C. and kept warm for 6-24 hours. For example, the holding temperature can be any one of 72° C., 75° C., and 77° C., and the holding time can be any one of 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, or 22 hours.

[0050] In some embodiments of the present invention, in the carrier preparation step, the porous template is placed in the sol and ultrasonically stirred for 10 to 60 minutes. Exemplarily, the stirring time can be any one of 20 minutes, 30 minutes, 40 minutes, and 50 minutes.

[0051] In some embodiments of the present invention, in the carrier preparation step, the soaked porous template is kept in an environment at 1100-1300°C for 1-3 hours. For example, the holding temperature can be any one of 1150°C, 1200°C, or 1250°C, and the holding time can be any one of 1.5 hours, 2 hours, or 2.5 hours.

[0052] In some embodiments of the present invention, in the slurry preparation step, 2 to 6 g of basic nickel carbonate, 2 to 6 g of nickel sulfate hexahydrate, 0.5 to 3 g of nickel chloride hexahydrate, 4 to 8 g of sodium citrate, 1 to 3 g of sodium chloride, 1 to 5 g of boric acid and 0.1 to 5 g of cobalt nitrate hexahydrate are dissolved in 80 to 150 mL of deionized water to obtain the slurry.

[0053] In some embodiments of the present invention, during the slurry preparation step, Co ions, Mo ions, or Fe ions may be added as reagents depending on the requirements of binary alloy ions.

[0054] In some embodiments of the present invention, in the slurry preparation step, the pH value of the slurry is adjusted to 9.5 to 10.5 with aqueous ammonia, illustratively 9.8, 10 or 10.2.

[0055] In some embodiments of the present invention, in the electrodeposition step, the working electrode of the three-electrode system is connected to the porous support, the counter electrode of the three-electrode system is connected to a platinum electrode, and the reference electrode of the three-electrode system is connected to a silver chloride electrode.

[0056] It is understandable that the operating parameters of the above-mentioned three-electrode system can be selected and adjusted according to actual needs; in some embodiments of the present invention, the duration of the constant potential polarization treatment is 0.5 to 3 minutes, and the voltage of the constant potential polarization treatment is 0.1 to 1.2V.

[0057] It is worth noting that the preparation method of the present invention is different from the anodic oxidation and hydrothermal methods in the prior art. Instead, it adopts the sol-gel method and template production, wherein the template is a porous template with a 3D three-dimensional skeleton and a large surface area and a large porosity. In this way, a 3D three-dimensional skeleton structure can be prepared according to the shape of the template. It is also applicable to microspheres, cubes, MOF skeletons, etc., and the template can be selected according to the size of the subsequent deposited particles. During the deposition process, the deposited particles are adjusted by changing the deposition parameters to achieve the maximum nano-deposition area, depositing more active catalytic materials on the skeleton. The composite nano-alloy catalyst prepared thereby achieves low cost, is easy to prepare, and has excellent catalytic rate and hydrogen production efficiency.

[0058] A non-noble metal catalyst is prepared by the above preparation method.

[0059] Example 2

[0060] This embodiment provides a preparation method of a non-precious metal catalyst, which is basically the same as that of Example 1, except that: first, a 1 cm × 5 cm polypropylene porous template is sequentially placed in 100 mL of 1 mol / L hydrochloric acid solution, 100 mL of acetone solution, 100 mL of anhydrous ethanol, and 100 mL of deionized water and ultrasonically cleaned for 10 minutes; then, 1.228 g of ammonium fluoride and 1.43 g of citric acid are weighed and dissolved in 5 mL of deionized water, and 30 mL of butyl titanate, 70 mL of ethylene glycol, and 5 mL of nitric acid are added and stirred continuously, wherein the addition of citric acid plays a role in the The addition of a small amount of nitric acid can accelerate the dissolution and mixing of the substances under the action of a complexing agent; secondly, the mixture is placed in an oven and heated at 80°C for 12 hours to facilitate the formation of a sol state of the mixed liquid; next, the cleaned porous template is placed in the sol and stirred for 30 minutes to allow the template to be fully immersed in the sol; finally, the template is taken out and the excess sol is removed, and the template is placed in a muffle furnace and heated to 1200°C in an air atmosphere and kept warm for 2 hours. The porous polymer template dissolves and disappears at high temperature, and the titanium dioxide skeleton is ensured to be firm and stable. After the product is cooled to room temperature, it is dried and stored, and a porous titanium dioxide carrier is formed.

[0061] Furthermore, first, 4 g of basic nickel carbonate, 4 g of nickel sulfate hexahydrate, 2 g of nickel chloride hexahydrate, 6.4 g of sodium citrate, 2 g of sodium chloride, 3.4 g of boric acid, and 2.328 g of cobalt nitrate hexahydrate were weighed and dissolved in 100 mL of deionized water and stirred thoroughly. Ammonia water was then added dropwise until the pH value of the slurry reached 10 as measured by a pH tester. The slurry was then stirred for 30 minutes using a magnetic stirrer to fully mix the slurry. Then, the sintered support sample was immersed in the slurry and connected to the working electrode of the three-electrode system, with a platinum electrode as the counter electrode and an AgCl electrode as the reference electrode. Constant potential polarization was performed for 1 minute with the voltage set to 0.8 V. After the deposition was completed, the sample was removed, the surface color of the sample deepened, and it was repeatedly rinsed with deionized water and anhydrous ethanol and dried in a drying oven at 60°C for 8 hours. Finally, the micromorphology of the sample was observed by scanning electron microscopy, its phase data was obtained by X-ray diffraction (XRD), and the catalytic performance of the sample was tested by an electrochemical workstation.

[0062] refer to Figure 2 NiCo particles are clustered on the surface of the 3D porous carrier and do not completely cover the open pores. This three-dimensional structure increases the electrochemical surface area of ​​the catalyst and the number of active sites, thereby accelerating the electrolysis of water and significantly improving the catalytic efficiency and the rate of the electrolysis of water.

[0063] Example 3

[0064] This embodiment is basically the same as embodiment 2, except that cobalt nitrate hexahydrate is not included in the slurry preparation step.

[0065] Example 4

[0066] This embodiment is basically the same as embodiment 2, except that 1.746 g of cobalt nitrate hexahydrate is added during the slurry preparation step.

[0067] Example 5

[0068] This embodiment is basically the same as embodiment 2, except that 2.91 g of cobalt nitrate hexahydrate is added during the slurry preparation step.

[0069] Example 6

[0070] This embodiment is basically the same as embodiment 2, with the only difference being that in the electrodeposition step, the voltage of the constant potential treatment is 0.2V.

[0071] Example 7

[0072] This embodiment is basically the same as embodiment 2, with the only difference being that in the electrodeposition step, the voltage of the constant potential treatment is 0.4V.

[0073] Example 8

[0074] This embodiment is basically the same as embodiment 2, with the only difference being that in the electrodeposition step, the voltage of the constant potential treatment is 0.6V.

[0075] Comparative Example 1

[0076] The porous titanium dioxide carrier prepared by the sol-gel method in the prior art is a TiO2 catalyst, and X-ray diffraction detection is performed to obtain the phase data of the catalyst in this example.

[0077] Comparative Example 2

[0078] The method is basically the same as Example 2, except that: a titanium foil is taken, cleaned, and then connected to a three-electrode system for electrophoretic deposition treatment, wherein the deposition electrolyte slurry is a mixture of 4 g of basic nickel carbonate, 4 g of nickel sulfate hexahydrate, 2 g of nickel chloride hexahydrate, 6.4 g of sodium citrate, 2 g of sodium chloride, 3.4 g of boric acid, and 2.328 g of cobalt nitrate hexahydrate dissolved in 100 mL of deionized water; the titanium foil is immersed in the slurry and connected to the working electrode of the three-electrode system, a platinum electrode is used as the counter electrode, and an AgCl electrode is used as the reference electrode. Constant potential polarization is performed for 1 minute, and the voltage is set to 0.8 V to obtain a NiMo-Ti catalyst.

[0079] It is worth noting that the NiMo-Ti catalyst prepared in Comparative Example 2 is prepared using a sheet-like titanium foil material as raw material, while the raw material for preparation in Example 2 is a porous template, which is a three-dimensional nano-skeleton material with abundant pores. Obviously, under the same mass, the surface area of ​​the porous template is much larger than that of the titanium foil, so the surface areas of the catalysts finally prepared are very different. The catalyst prepared in Example 2 has a larger surface area and therefore has a stronger catalytic ability.

[0080] Comparative Example 3

[0081] 10 mg of 40 wt.% Pt / C powder (i.e., the mass ratio of Pt powder to C powder is 2:3) was weighed, added to 15 L of Nafion solution and 600 L of anhydrous ethanol, and ultrasonically vibrated for 10 minutes to form a suspension. The suspension was introduced into a spray gun and sprayed onto a cleaned titanium foil. The spraying was repeated three times to obtain a Pt / Ti catalyst. X-ray diffraction was then performed to obtain the phase data of the catalyst in this example.

[0082] refer to Figure 3 , Figure 3The figures show the physical phases of the four catalysts in Comparative Examples 1-3 and Example 2. The XRD diffraction peaks of the composite structures formed by the three technical means indicate that TiO2 is formed by the gel sol method, and NiCo alloy particles are formed by electrodeposition. Due to the high catalytic activity of the alloy particles and the support of the porous TiO2 carrier, the catalytic ability of the NiCo alloy is further enhanced, forming a highly active catalytic composite material.

[0083] refer to Figure 4 , Figure 4 The catalytic performance of the four catalysts in Comparative Examples 1-3 and Example 2 is shown in FIG. It is worth noting that the difference between the actual reaction potential and the equilibrium potential is defined as the HER overpotential (η), which is considered to be one of the important parameters for evaluating the performance of water splitting catalysts, because a larger reaction overpotential will lead to too low energy conversion efficiency; generally speaking, the current density is 10 mA·cm -2 or 50mA·cm -2 、100mA·cm -2 The overpotential at 100 nm is the benchmark for evaluating catalyst performance. The smaller the overpotential required to obtain a certain current density, the higher the charge transfer rate and the higher the catalytic efficiency. Figure 4 It can be seen intuitively that the catalyst prepared by the preparation method described in Example 2 can obtain a larger current density when a smaller overpotential is applied thereto.

[0084] refer to Figure 5 , Figure 5 It is shown in Figure 2 that the current density of the catalyst prepared in Example 2 does not fluctuate significantly with the increase in the duration of the electrochemical test, thus indicating that the catalyst has good stability and reliability.

[0085] refer to Figure 6 , Figure 6 The electrochemical test curves of the catalysts prepared in Examples 2 to 5 are shown in FIG. Figure 6 Figure 2 shows the polarization curves of samples deposited at different Co ion concentrations. It can be seen that as the Co ion concentration increases, the overpotential required for the catalyst to obtain a certain current density shows a trend of first decreasing and then increasing. When the Co ion concentration is 0.08 M (the mass of cobalt nitrate hexahydrate in Example 2 is 2.328 g), the required overpotential is the smallest, and the catalytic rate of the catalyst is the highest at this time.

[0086] refer to Figure 7 , Figure 7 The electrochemical test curves of the catalysts prepared in Example 2 and Examples 6 to 8 are shown in FIG. ; specifically, Figure 7The polarization curves for different deposition voltages show that the overpotential of each catalyst decreases first and then increases, indicating that the catalytic activity of each catalyst increases with increasing voltage in the deposition voltage range of 0 to 0.8 V. The required overpotential is the smallest when the deposition voltage is 0.8 V (Example 2), indicating that the catalytic rate is the highest at this time.

[0087] The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art who is familiar with the technical field can easily think of changes or replacements within the technical scope disclosed by the present invention, which should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims. In addition, the principle and implementation of the present invention are explained in detail in the specification using specific examples. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. The content of this specification should not be understood as limiting the present invention.

Claims

1. A method for preparing a non-precious metal catalyst, characterized in that: The preparation method comprises the following steps: Sol preparation: mixing butyl titanate, ammonium fluoride and ethylene glycol to obtain a sol; Preparation of the carrier: first, immersing the porous template in the sol, then heating the immersed porous template, and cooling it to obtain a porous titanium dioxide carrier; preparing a slurry by dissolving basic nickel carbonate, nickel sulfate hexahydrate, nickel chloride hexahydrate, sodium citrate, sodium chloride, boric acid, and cobalt nitrate hexahydrate in deionized water to obtain a slurry; Electrodeposition, immersing the porous titanium dioxide support in the slurry and subjecting the porous titanium dioxide support to a constant potential polarization treatment using a three-electrode system, so that NiCo particles are clustered and deposited on the surface of the porous titanium dioxide support to obtain the non-precious metal catalyst; The porous template is an open-cell polymer reticulated foam; In the carrier preparation step, the porous template that has been soaked is kept warm in an environment of 1100-1300° C. for 1-3 hours.

2. The preparation method according to claim 1, characterized in that The preparation method further comprises, before the carrier preparation step: Template cleaning: using hydrochloric acid, acetone, anhydrous ethanol and deionized water to clean the porous template in sequence.

3. The preparation method according to claim 1, characterized in that In the sol preparation step, 0.5-2 g of ammonium fluoride is dissolved in 1.5-3.6 mL of deionized water to obtain an ammonium fluoride aqueous solution, and then the ammonium fluoride aqueous solution is mixed with butyl titanate and ethylene glycol to obtain the sol.

4. The preparation method according to claim 1, characterized in that The sol preparation step also includes: Nitric acid and a complexing agent are added to a mixture of butyl titanate, ammonium fluoride and ethylene glycol, and the mixture is stirred.

5. The preparation method according to claim 4, characterized in that The complexing agent is citric acid.

6. The preparation method according to claim 5, characterized in that In the sol preparation step, the volume ratio of butyl titanate, ammonium fluoride aqueous solution, nitric acid, citric acid and ethylene glycol is (20-40):(1-3):(1-2):(2-6):(80-120).

7. The preparation method according to claim 1, characterized in that In the sol preparation step, a mixture of butyl titanate, ammonium fluoride and ethylene glycol is placed in an environment of 70 to 90° C. and kept warm for 6 to 24 hours.

8. The preparation method according to claim 1, characterized in that In the carrier preparation step, the porous template is placed in the sol and ultrasonically stirred for 10 to 60 minutes.

9. The preparation method according to claim 1, characterized in that In the slurry preparation step, 2-6 g of basic nickel carbonate, 2-6 g of nickel sulfate hexahydrate, 0.5-3 g of nickel chloride hexahydrate, 4-8 g of sodium citrate, 1-3 g of sodium chloride, 1-5 g of boric acid and 0.1-5 g of cobalt nitrate hexahydrate are dissolved in 80-150 mL of deionized water to obtain the slurry.

10. The preparation method according to claim 1 or 9, characterized in that: In the slurry preparation step, the pH value of the slurry is adjusted to 9.5-10.5 with ammonia water.

11. The preparation method according to claim 1, characterized in that In the electrodeposition step, the working electrode of the three-electrode system is connected to the porous support, the counter electrode of the three-electrode system is connected to a platinum electrode, and the reference electrode of the three-electrode system is connected to a silver chloride electrode; The duration of the constant potential polarization treatment is 0.5 to 3 minutes, and the voltage of the constant potential polarization treatment is 0.1 to 1.2V.

12. A non-precious metal catalyst, characterized in that The non-precious metal catalyst is prepared by the preparation method according to any one of claims 1 to 11.

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