Electrocatalytic Materials with a Wide Potential Range for Adapting to the Volatility of Renewable Electricity, Their Preparation Methods and Applications

Abstract

The present invention relates to the technical field of catalytic materials, and in particular to an electrocatalytic material with a wide potential range that can adapt to the fluctuation of renewable electricity, and its preparation method and application. The present invention provides an electrocatalytic material with a wide potential range that can adapt to the fluctuation of renewable electricity, comprising Ni 3+ and Ni 2+ The nickel oxide core layer and the nickel-nitrogen-carbon catalyst shell layer wrapped on the outer surface of the core layer. The present invention provides a wide potential range electrocatalytic material adapted to the volatility of renewable electricity, and its preparation method and application. The composite catalyst of NiOx coated with nickel-nitrogen-carbon catalyst prepared by this method increases the reaction active sites, can achieve high Faraday efficiency of CO2RR in a wide voltage range, achieve highly selective CO production, and inhibit cathode hydrogen evolution reaction (HER). The wide potential performance is very adaptable to the volatility of renewable electricity, and the composite catalytic material provided by the present invention can provide a guarantee for the practical application of renewable electricity-driven CO2RR in the next step.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic materials, and in particular to an electrocatalytic material with a wide potential range that is adaptable to the volatility of renewable electricity, and a preparation method and application thereof. Background Art

[0002] Driven by renewable electricity such as solar energy and wind energy, the carbon dioxide reduction reaction (CO2RR) to produce high-value-added chemicals or fuels at room temperature and pressure is an efficient and green emerging technology that promotes artificial carbon cycle and stores renewable energy.

[0003] Due to the strong stability of CO2 molecules and competition from the hydrogen evolution side reaction, the current conversion efficiency and product selectivity of CO2RR are not high. Among the 16 possible products of CO2RR, carbon monoxide (CO) has a low conversion energy barrier and is a crucial carbon building block in the chemical industry, widely used in the production of chemicals such as Fischer-Tropsch synthesis, acetic acid, and methanol. Therefore, the direct electrocatalytic conversion of CO2 to CO (CO2-to-CO) driven by "green electricity" offers the most practical application prospects.

[0004] However, due to the intermittent and fluctuating nature of renewable electricity, the output voltage is highly unstable, which can easily lead to hydrogen evolution side reactions in the CO2-to-CO process, resulting in reduced CO selectivity / Faraday efficiency and even the generation of other byproducts. Currently, the voltage window for maintaining CO Faradaic efficiency above 90% in most CO2-to-CO processes is only 200-400 mV, which is far from the requirements for mature applications. Therefore, maintaining high CO selectivity over a wide voltage range has become one of the key challenges in the application of CO2RR technology. The development of an efficient, low-cost electrocatalyst for electrochemical CO2-to-CO conversion over a wide potential range is urgent and of great significance for promoting CO2RR technology from the laboratory to mature applications. Summary of the Invention

[0005] The present invention provides a wide-potential-range electrocatalytic material adapted to the volatility of renewable electricity, as well as its preparation method and application. The composite catalyst, a nickel-nitrogen-carbon catalyst coated with NiOx, produced by this method, increases reactive sites, enabling high Faradaic efficiency for CO₂RR over a wide voltage range, highly selective CO production, and suppression of the cathode hydrogen evolution reaction (HER). This wide-potential performance is highly adaptable to the volatility of renewable electricity, and the composite catalytic material provided by the present invention could provide a foundation for the practical application of renewable electricity-driven CO₂RR in the future.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a wide potential range electrocatalytic material adapted to the fluctuation of renewable electricity, including Ni 3+ and Ni 2+ The nickel oxide core layer and the nickel nitrogen carbon catalyst shell layer wrapped on the outer surface of the core layer; the nickel oxide core layer comprises a nickel oxide core layer and a nickel nitrogen carbon catalyst shell layer wrapped on the outer surface of the core layer; the nickel oxide core layer comprises a nickel nitrogen carbon catalyst shell layer and a nickel nitrogen carbon catalyst shell ... 3+ and Ni 2+ The mass of the nickel oxide core layer is 8~35 wt%.

[0008] Preferably, the Ni-containing 3+ and Ni 2+ There is a strong interaction between the core layer of nickel oxide and the shell layer of the nickel nitrogen carbon catalyst.

[0009] Preferably, Ni 3+ and Ni 2+ Nickel oxide is NiOx.

[0010] Contains Ni 3+ and Ni 2+ Nickel oxides (such as NiOx) have two valence states of nickel ions at the same time. This rich oxidation state is more conducive to the adsorption and activation of CO2. In addition, Ni 3+ and Ni 2+ Nickel oxide has a high content of Ni 3+ , and Ni 3+ and Ni 2+ The charge transfer ability between them can act as an "electron reservoir". 3+ and Ni 2+ Nickel oxide has more effective electronic structure regulation and charge transport capabilities.

[0011] The nickel-nitrogen-carbon catalyst (Ni-NC) shell inhibits the Ni-containing 3+ and Ni 2+ Complete reduction of nickel oxide, so that it remains in a partially oxidized state. 3+ and Ni 2+ The nickel oxide and nickel nitrogen carbon catalyst are combined to well regulate the electronic structure and charge transfer ability of the catalyst; in addition, the nickel nitrogen carbon catalyst is combined with Ni 3+ and Ni 2+ The strong interaction at the nickel oxide interface leads to electron transfer from the NiN-C catalyst to the Ni-containing 3+ and Ni 2+ The nickel oxide decreases the d-band center of Ni. This electronic regulation may make the adsorption of *COOH intermediate more stable and promote the CO2RR reaction.

[0012] Based on the above, Ni3+ and Ni 2+ Nickel oxides for the electronic structure regulation of nickel-nitrogen-carbon catalysts, containing Ni 3+ and Ni 2+ The nickel oxide acts as an "electron reservoir," achieving high Faradaic efficiency for CO₂RR over a wide voltage range, enabling highly selective CO production and suppressing the HER side reaction. This wide potential performance is well-suited to the volatility of renewable electricity. The composite catalytic material provided by this invention promises promising applications in renewable electricity-driven CO₂RR.

[0013] The present invention also provides a method for preparing an electrocatalytic material with a wide potential range that adapts to the volatility of renewable electricity, comprising:

[0014] S1. Preparation of Ni 3+ and Ni 2+ of nickel oxide;

[0015] S2. Ni 3+ and Ni 2+ Nickel oxide, zinc source, nickel source and dimethylimidazole are stirred and mixed, and then dried and calcined under an inert atmosphere to obtain an electrocatalytic material with a wide potential range that adapts to the fluctuation of renewable electricity.

[0016] The present invention uses zinc source and dimethylimidazole to obtain Zif8 precursor in a stirring state, and then calcines the Zif8 precursor with a nickel source to obtain a nickel-nitrogen-carbon catalyst. During the calcination process, the nickel-nitrogen-carbon catalyst is wrapped in a Ni-containing 3+ and Ni 2+ The nickel oxide surface is prepared to obtain a wide potential range electrocatalytic material that can adapt to the fluctuation of renewable electricity.

[0017] Preferably, Ni 3+ and Ni 2+ Ni in nickel oxide 3+ The content is 68~72 wt%.

[0018] Preferably, in S1, the nickel source solution is adjusted to pH 9-11, and then dried and calcined to obtain a nickel-containing solution. 3+ and Ni 2+ of nickel oxide.

[0019] Preferably, the nickel source comprises a nickel-containing salt. Preferably, the nickel source comprises nickel nitrate, nickel sulfate or nickel chloride.

[0020] Preferably, the solvent in the nickel source solution is water.

[0021] Preferably, the solution used to adjust the pH is sodium hydroxide solution and / or aqueous ammonia.

[0022] Preferably, the solution used to adjust the pH is 8-10 M sodium hydroxide solution.

[0023] Preferably, the pH is adjusted to 10.

[0024] Preferably, the drying temperature is 60-100° C., and the drying time is 6-10 h.

[0025] Preferably, the calcination temperature is 250-300° C., and the calcination time is 1-3 h.

[0026] Preferably, S2 contains Ni 3+ and Ni 2+ The molar ratio of the nickel oxide, the nickel in the nickel source, and the zinc in the zinc source is 1:(0.02~0.04):(2~5).

[0027] Preferably, Ni 3+ and Ni 2+ The molar ratio of nickel oxide, nickel in the nickel source, and zinc in the zinc source is 1:(0.02~0.04):3.

[0028] Preferably, the zinc source comprises a zinc-containing salt. Preferably, the zinc source comprises zinc nitrate, zinc sulfate, zinc chloride or zinc acetate.

[0029] Preferably, the nickel source comprises a nickel-containing salt. Preferably, the nickel source comprises nickel nitrate, nickel sulfate or nickel chloride.

[0030] Preferably, in S2, dimethylimidazole is mixed in a solvent to obtain a solution A containing Ni 3+ and Ni 2+ The nickel oxide and zinc source are mixed in a solvent to obtain solution B. After solution A and solution B are mixed, the nickel source is added and stirred to mix.

[0031] Preferably, the solvent comprises methanol, ethanol or water.

[0032] Preferably, the stirring is: stirring under an inert atmosphere for 1 to 5 hours, and then stirring for 8 to 10 hours.

[0033] Preferably, the inert atmosphere comprises nitrogen and / or argon.

[0034] Preferably, the calcination temperature is 900-1000° C., and the calcination time is 1-3 h.

[0035] More preferably, the calcination temperature is 900-950° C., and the calcination time is 1-2.5 h.

[0036] Preferably, the heating rate of calcination is 5-10°C / min.

[0037] Preferably, the drying temperature is 60-100° C., and the drying time is 12-24 h.

[0038] Preferably, the inert atmosphere comprises nitrogen and / or argon.

[0039] The present invention also provides an application of a wide potential range electrocatalytic material that adapts to the volatility of renewable electricity in electrocatalytic production of carbon monoxide from carbon dioxide.

[0040] The present invention also provides a carbon dioxide electrocatalytic electrode, comprising an electrocatalytic material with a wide potential range that adapts to the volatility of renewable electricity.

[0041] The present invention also provides a carbon dioxide catalytic reduction device, comprising a carbon dioxide electrocatalytic electrode.

[0042] Therefore, the present invention has the following beneficial effects:

[0043] (1) The present invention utilizes Ni-NC-wrapped NiOx to achieve multiple advantages of active site protection, electronic structure optimization, mass transfer efficiency improvement, and product selectivity regulation through core-shell structure design, especially in inhibiting the HER reaction and improving the CO Faraday efficiency.

[0044] (2) The NiOx@Ni-NC catalyst provided by the present invention has a CO Faradaic efficiency of more than 90% with a voltage window of more than 1200 mV and a current density of up to 400 mA / cm 2 ; Maintain 95% stability for more than 10 hours.

[0045] (3) The present invention selects Ni 3+ and Ni 2+ NiOx with two valence states of nickel ions, this rich oxidation state form is more conducive to the adsorption and activation of CO2, helps to form electron channels and hydrogen bond networks with Ni-NC catalysts, accelerates charge transfer and intermediate conversion; causes electrons to transfer from nickel nitrogen carbon catalyst to Ni-containing 3+ and Ni 2+ The nickel oxide decreases the d-band center of Ni. This electronic regulation may make the adsorption of *COOH intermediate more stable and promote the CO2RR reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a comparison chart of CO Faraday efficiency tested in an H-type cell.

[0047] Figure 2 This is a Faraday efficiency diagram of the catalyst of Example 1 tested in a flow cell;

[0048] Figure 3 is the XRD comparison chart;

[0049] Figure 4 This is a Raman comparison chart;

[0050] Figure 5 This is a linear sweep voltammetry comparison diagram;

[0051] Figure 6 The linear sweep voltammograms of the catalyst of Example 1 tested in an H-type cell under different saturated atmospheres are shown;

[0052] Figure 7 This is a stability diagram of Example 1 tested in an H-type cell;

[0053] Figure 8 The performance diagram of the H-type cell test with different molar ratios of NiOx and zinc nitrate;

[0054] Figure 9 Performance diagram of H-type cell test at different calcination temperatures. DETAILED DESCRIPTION

[0055] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below generally represent only a portion of the present invention, rather than all of the embodiments. Therefore, all other embodiments derived by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0056] All raw materials in this section were purchased. Commercial NiO was purchased from Aladdin with a particle size of less than 30 nm and a purity of 99.5%. Ni powder was purchased from Guangzhou Metal Metallurgy Co., Ltd. with a particle size of 200-300 nm and a purity of 99.9%.

[0057] [Example]

[0058] Example 1

[0059] (1) Preparation of NiOx: Dissolve 0.44 mol Ni(NO3)2·6H2O in 100 mL of deionized water, adjust the pH to 10 with 10 mol / L sodium hydroxide, stir for 5 min, centrifuge twice, and then place in an 80°C oven for 6 h. Then, calcine the sample in a muffle furnace at 270°C for 2 h to obtain NiOx.

[0060] (2) Preparation of composite catalyst: 0.0273 mol dimethylimidazole was dissolved in 25 mL methanol solution, which was recorded as solution A. 0.001 mol NiOx and 0.003 mol Zn(NO3)2·6H2O were dissolved in 88 mL methanol solution (Zn:NiOx=3:1), which was recorded as solution B. A was slowly added to B and stirred evenly. Then 2.5 mL of 10 mmol / L Ni(NO3)2·6H2O solution was added to B. The mixture was stirred for 2 h while passing Ar gas, and then stirred for 8 h and allowed to stand overnight. The mixture was then centrifuged and washed three times and dried in an oven at 60°C. The sample was placed in a tube furnace under N2 atmosphere and calcined at 900°C for 2 h to obtain a composite catalyst. The mass of NiOx in the composite catalyst was 16 wt%. It was recorded as NiOx@Ni-NC.

[0061] Example 2

[0062] This embodiment is basically the same as embodiment 1, except that: in (2), the calcination temperature is 950°C.

[0063] Comparative Example 1

[0064] This comparative example is basically the same as Example 1, except that the addition of NiOx is omitted and the obtained catalyst is recorded as Ni-NC.

[0065] Comparative Example 2

[0066] This comparative example is basically the same as Example 1, except that NiOx is replaced by an equimolar amount of Ni powder, and the resulting catalyst is recorded as Ni powder@Ni-NC.

[0067] Comparative Example 3

[0068] This comparative example is basically the same as Example 1, except that NiOx is replaced by an equal molar amount of commercial NiO, and the obtained catalyst is recorded as NiO@Ni-NC.

[0069] Comparative Example 4

[0070] This comparative example is basically the same as Example 1, except that the addition of NiOx and the addition of 10 mM Ni(NO3)2·6H2O in (2) are omitted, and the resulting catalyst is recorded as NC.

[0071] Comparative Example 5

[0072] Dissolve 0.44 mol Ni(NO3)2·6H2O in 100 mL of deionized water, adjust the pH to 10 with 10 mol / L sodium hydroxide, stir for 5 min, centrifuge twice, and then place in an 80°C oven to dry for 6 h. Then, calcine the sample in a muffle furnace at 270°C for 2 h to obtain NiOx, which is recorded as NiOx.

[0073] Comparative Example 6

[0074] This comparative example is basically the same as Example 1, except that: in (2), the amount of NiOx used is 0.0005 mol; it is recorded as Zn:NiOx=3:0.5.

[0075] Comparative Example 7

[0076] This comparative example is basically the same as Example 1, except that: in (2), the amount of NiOx used is 0.003 mol; it is recorded as Zn:NiOx=3:3.

[0077] Comparative Example 8

[0078] This comparative example is basically the same as Example 1, except that: in (2), the calcination temperature is 850°C.

[0079]

Performance test

[0080] Catalytic Performance Testing: Carbon dioxide electroreduction (CO2RR) measurements were performed on a CHI760E workstation using a three-electrode H-type electrolyzer separated by a Nafion 117 proton exchange membrane. To prepare the working electrode, 5.0 mg of sample was dispersed into 1000 μL of a mixture of 960 μL of ethanol and 40 μL of a 5 wt% Nafion solution, followed by vigorous sonication for 30 minutes to form a uniform, ink-like slurry. This slurry was further dispersed onto a 1.0 cm × 1.0 cm piece of carbon paper (SGL28BC) to serve as the working electrode. The electrode had a geometric catalytic area of 1.0 cm², and the catalyst loading was 1 mg / cm². The reference electrode was a silver / silver chloride (saturated with potassium chloride) electrode, and the counter electrode was a platinum mesh. During CO2RR measurements, each cell compartment was filled with 50 mL of 0.5 mol / L potassium bicarbonate electrolyte (pH 7.2). Carbon dioxide was continuously introduced into the electrolyte at a constant flow rate of 20 standard cubic centimeters per minute (sccm) to maintain saturation, and the electrolyte in the cathode compartment was magnetically stirred during electrolysis. Cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were repeated until steady-state was reached, and data were recorded at a scan rate of 5 millivolts per second. Catalyst performance was measured by potentiostatic testing, where the current curve at a set constant voltage was recorded as a function of time. The Faradaic efficiency of the product was calculated from the resulting current and the ratio of the reaction products detected by gas chromatography.

[0081] CO Faraday efficiency test: The test method is basically the same as the "catalytic performance test", except that the test environment is a flow cell, the anode and cathode chambers of the reaction cell are separated by Sustainion X37-50 Grade RT anion exchange membrane, and the working electrode area is 0.5 × 0.5 cm -2 , the counter electrode was a platinum mesh (1.4 cm × 1.4 cm), the reference electrode was a Hg / HgO electrode (filled with 1 M KOH), and the electrolytes were 1 M KOH and 0.1 M KOH + 0.9 M KCl solutions.

[0082] The catalysts obtained in Example 1 and Comparative Examples 1 to 5 were tested for CO Faraday efficiency. Figure 1 Observation Figure 1As can be seen, Example 1 significantly outperforms Comparative Examples 1-5. The voltage window in which the CO Faradaic efficiency of Example 1 remains above 90% in the H-type cell test reaches 700 mV. At a standard hydrogen potential of -1.1 V, the CO Faradaic efficiency reaches a maximum of approximately 100%. However, the CO Faradaic efficiencies of the catalysts prepared in Comparative Examples 1-3 are significantly lower than those of Example 1. The CO Faradaic efficiencies of the catalysts prepared in Comparative Examples 4-5 are almost zero, with all hydrogen evolution occurring.

[0083] Furthermore, the catalyst of Example 1 was subjected to a CO Faraday efficiency test in a flow cell test, and the electrolyte used was a mixed solution of 0.1 mol / L KOH and 0.9 mol / L KCl. Figure 2 The voltage window in which the CO Faradaic efficiency remains above 90% is shown to be over 1200 mV. The optimal potential is -0.57 V, with a CO Faradaic efficiency of approximately 100%. This demonstrates that the catalyst obtained in Example 1 can be used as an electrocatalyst with a wide potential range to adapt to the fluctuations of renewable electricity.

[0084] The catalysts obtained in Example 1, Comparative Example 1, Comparative Example 3 and Comparative Example 4 were subjected to XRD test, and the results are as follows: Figure 3 As shown. It can be observed that all four catalysts have two weak peaks at 26.2° and 44.0°. These two diffraction peaks correspond to the diffraction peaks of the (002) crystal plane and the (100) crystal plane of graphite carbon, respectively. From XRD, it can be seen that Example 1 (NiOx@Ni-NC) and Comparative Example 3 (NiO@Ni-NC) have obvious peaks of elemental Ni, indicating that most of the nickel oxide clusters have formed elemental Ni after high-temperature calcination. However, because the performance of Example 1 and Comparative Example 3 is different, there may be a part of the nickel oxide clusters that have not been completely reduced to elemental Ni, which further confirms that the NiOx clusters have greatly improved the performance of the catalyst. The XRD of the other two comparative examples shows the peaks of standard Ni-NC and the peak type of NC.

[0085] The catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 3 were subjected to Raman testing, and the results are as follows: Figure 4 As shown in the figure, the D peak and the G peak are the Raman characteristic peaks of the C atomic crystal, at 1350 cm -1 and 1580 cm -1 Nearby, the D peak reflects the carbon defects in the lattice, and the G peak reflects the carbonization degree of the material. D / I G is the intensity ratio of the D peak to the G peak; I D / I G The smaller the value, the higher the degree of graphitization of carbon and the stronger the conductivity; D / IG The larger the value, the more carbon defects there are. D / I G The value is 0.874, while the I D / I G The values were 1.26 and 0.949, respectively. D / I G The smallest, the highest degree of graphitization.

[0086] Furthermore, linear sweep voltammetry tests were performed on Example 1 and Comparative Examples 1 to 5 in a CO2-saturated 0.5 mol / L KHCO3 solution. The results are shown in FIG. Figure 5 As shown in Figure 2 , the catalysts obtained in Comparative Examples 1 to 5 exhibit lower current densities on the LSV curves and poor CO₂RR performance. Example 1 exhibits a lower onset potential and higher current density. This indicates that Example 1 exhibits the greatest electrochemical response and activity toward CO₂. These results demonstrate that NiOx clusters promote CO₂RR performance.

[0087] Figure 6 This is the LSV diagram of Example 1 tested in an H-type cell under different saturated atmospheres. It can be seen that the performance of the NiOx@Ni-NC catalyst under saturated CO2 gas is better than that under Ar gas, with a lower starting potential and higher current density, indicating that the catalyst has excellent CO2RR performance.

[0088] Figure 7 This is the stability diagram of the H-type cell test in Example 1. Long-term catalyst stability is crucial for achieving scale-up. Therefore, the NiOx@Ni-NC catalyst was subjected to a 17-hour constant-potential electrolysis at -0.78 V (vs RHE). Over time, the selectivity of the NiOx@Ni-NC catalyst remained essentially unchanged, with Faradaic efficiency remaining above 95%.

[0089] Figure 8 The performance diagram of the H-type cell test under different molar ratios of NiOx and Zn(NO3)2·6H2O is shown. The three Zn(NO3)2·6H2O:NiOx molar ratios are 6:1, 3:1, and 3:3, respectively, with the optimal molar ratio being 3:1.

[0090] Figure 9 The following graph shows the performance of the NiOx@Ni-NC catalyst tested in an H-type cell at different calcination temperatures. The calcination temperatures for the NiOx@Ni-NC catalyst are 850°C, 900°C, and 950°C, respectively. The performance of the catalyst calcined at 850°C is significantly poorer, while the performance at 900°C and 950°C is relatively close. From an energy-saving perspective, the optimal calcination temperature is 900°C.

Claims

1. An electrocatalytic material with a wide potential range that adapts to the volatility of renewable electricity, characterized in that: Including Ni 3+ and Ni 2+ The nickel oxide core layer and the nickel nitrogen carbon catalyst shell layer wrapped on the outer surface of the core layer; the nickel oxide core layer comprises a nickel oxide core layer and a nickel nitrogen carbon catalyst shell layer wrapped on the outer surface of the core layer; the nickel oxide core layer comprises a nickel nitrogen carbon catalyst shell layer and a nickel nitrogen carbon catalyst shell ... 3+ and Ni 2+ The mass of the nickel oxide core layer is 8~35 wt%.

2. The electrocatalytic material with a wide potential range adapted to the fluctuation of renewable electricity according to claim 1, characterized in that: The Ni-containing 3+ and Ni 2+ There is a strong interaction between the core layer of nickel oxide and the shell layer of the nickel nitrogen carbon catalyst.

3. The method for preparing an electrocatalytic material with a wide potential range that adapts to the fluctuation of renewable electricity according to claim 1 or 2, characterized in that: include: S1. Preparation of Ni 3+ and Ni 2+ of nickel oxide; S2. Ni 3+ and Ni 2+ Nickel oxide, zinc source, nickel source and dimethylimidazole are stirred and mixed, and then dried and calcined under an inert atmosphere to obtain an electrocatalytic material with a wide potential range that adapts to the fluctuation of renewable electricity.

4. The preparation method according to claim 3, wherein In S1, the nickel source solution is adjusted to pH 9-11, and then dried and calcined to obtain a nickel-containing 3+ and Ni 2+ of nickel oxide.

5. The preparation method according to claim 3, wherein S2 contains Ni 3+ and Ni 2+ The molar ratio of nickel oxide, nickel in the nickel source, and zinc in the zinc source is 1:(0.02~0.04):(2~5).

6. The preparation method according to claim 3, wherein In S2, dimethylimidazole is mixed in the solvent to obtain solution A, which contains Ni 3+ and Ni 2+ The nickel oxide and zinc source are mixed in a solvent to obtain solution B. After solution A and solution B are mixed, the nickel source is added and stirred to mix.

7. The preparation method according to claim 3, wherein In S2, the calcination temperature is 900~1000℃, and the calcination time is 1~3 hours.

8. Use of an electrocatalytic material with a wide potential range adapted to renewable power fluctuations as claimed in any one of claims 1 to 2, or an electrocatalytic material with a wide potential range adapted to renewable power fluctuations obtained by the preparation method as claimed in any one of claims 3 to 7, in the electrocatalytic production of carbon monoxide from carbon dioxide.

9. A carbon dioxide electrocatalytic electrode, characterized in that It comprises the electrocatalytic material with a wide potential range that adapts to the fluctuation of renewable power as described in any one of claims 1 to 2, or the electrocatalytic material with a wide potential range that adapts to the fluctuation of renewable power obtained by the preparation method as described in any one of claims 3 to 7.

10. A carbon dioxide catalytic reduction device, characterized in that: Comprising the carbon dioxide electrocatalytic electrode as claimed in claim 9.

Images