Ultrasonic synthesis non-noble metal-based MOF (Metal Organic Framework) catalyst as well as preparation method and application thereof

Abstract

The invention relates to an ultrasonic synthesis non-noble metal-based MOF catalyst and a preparation method and application thereof, the preparation method comprises the following steps: mixing a non-noble metal source, an organic ligand and a solvent to obtain a mixed solution, and ultrasonically synthesizing the non-noble metal-based MOF catalyst, the non-noble metal source comprises a copper source and / or a cerium source; the organic ligand comprises pyromellitic acid. According to the invention, non-noble metal elements and organic ligands are coordinated by adopting an ultrasonic synthesis method, the preparation method is simple, the synthesis time can be remarkably shortened, rapid crystallization of MOF under mild conditions is ensured, and the prepared catalyst has multiple catalytic sites and high catalytic activity. Meanwhile, pyromellitic acid is selected as an organic ligand, has multidentate coordination capability, and can form a stable coordination structure with a non-noble metal source, so that the thermal stability and chemical stability of the catalyst are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, in particular to a non-noble metal-based MOF catalyst, and in particular to an ultrasonically synthesized non-noble metal-based MOF catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, large amounts of carbon dioxide emissions have led to many problems such as global warming and severe weather. In order to address these environmental problems, countries around the world have taken measures. Among them, converting carbon dioxide into high-value-added products through various catalytic methods (thermal catalysis, photocatalysis, and electrocatalysis, etc.) has become one of the important ways to achieve the goal of carbon neutrality. Among them, the electrocatalytic carbon dioxide reduction reaction has significant environmental friendliness, the ability to generate high-value-added products, mild reaction conditions, catalyst diversity and designability, synergy with other technologies, and economic and sustainability advantages.

[0003] However, the controllable and highly selective conversion of carbon dioxide into specific target products remains a major challenge. Therefore, there is an urgent need to develop a catalyst that can efficiently convert carbon dioxide into specific target products.

[0004] CN119082784A discloses the preparation and application of a catalyst for the electrocatalytic reduction of carbon dioxide to ethylene. The preparation steps of the catalyst are as follows: (1) adding a water-soluble copper salt and a manganese salt to deionized water to obtain solution A; dissolving polyvinylpyrrolidone K30 in deionized water to obtain solution B; (2) adding a NaOH solution to solution A to adjust the pH of the solution to 7-9, and then adding solution B dropwise to solution A to obtain a mixed slurry; (3) subjecting the mixed slurry to a hydrothermal reaction at a temperature of 50-120°C for 12-36 hours to obtain a black precipitate and a supernatant; ultrasonically treating the black precipitate and the supernatant to obtain a black solution; centrifuging, washing, and drying to obtain a black powder; and (4) subjecting the black powder to a radio frequency plasma treatment in an O2 atmosphere at a power of 250W for 10 minutes to obtain a CuMnO2-Vo catalyst. This preparation method has many steps, a complex preparation process, low stability, and low selectivity for the specific product ethylene.

[0005] MOFs, due to their unique structural and stability advantages, have become a highly sought-after material in the field of electrocatalysis. Ultrasonic synthesis utilizes the cavitation effect of ultrasound, providing high energy in a short period of time to promote the mixing of reactants and the breaking and forming of chemical bonds. This method can significantly shorten synthesis time, improve reaction efficiency, and achieve rapid crystallization of MOFs under mild conditions.

[0006] The existing technology has the defects of low catalytic selectivity and low stability of catalysts. Therefore, how to prepare carbon dioxide electrocatalysts with high catalytic selectivity and high stability has become a problem that needs to be solved urgently. Summary of the Invention

[0007] To address the above technical problems, the present invention provides an ultrasonically synthesized non-precious metal-based MOF catalyst, its preparation method, and application. The non-precious metal element is coordinated with an organic ligand using ultrasonic synthesis. The preparation method is simple, significantly shortens the synthesis time, and ensures rapid crystallization of the MOF under mild conditions. The prepared catalyst has multiple catalytic sites and high catalytic activity. Furthermore, the present invention selects pyromellitic acid as the organic ligand, which has multidentate coordination ability and can form a stable coordination structure with the non-precious metal source, thereby improving the thermal and chemical stability of the catalyst.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a method for preparing a non-precious metal-based MOF catalyst by ultrasonic synthesis, the preparation method comprising the following steps: mixing a non-precious metal source, an organic ligand and a solvent to obtain a mixed solution, and ultrasonically synthesizing a non-precious metal-based MOF catalyst; the non-precious metal source comprises a copper source and / or a cerium source; and the organic ligand comprises pyromellitic acid.

[0010] The present invention uses ultrasonic synthesis to coordinate non-precious metal elements with organic ligands. This simple preparation method significantly shortens synthesis time and ensures rapid crystallization of the MOF under mild conditions. The resulting catalyst has multiple catalytic sites and high catalytic activity. Furthermore, the present invention uses pyromellitic acid as the organic ligand, which has multidentate coordination capabilities and can form a stable coordination structure with the non-precious metal source, thereby improving the thermal and chemical stability of the catalyst.

[0011] Preferably, the non-noble metal source includes a copper source and a cerium source.

[0012] Preferably, the copper source comprises copper nitrate and / or copper chloride.

[0013] Preferably, the cerium source includes cerium nitrate and / or cerium chloride.

[0014] Preferably, the molar ratio of the copper source to the cerium source is (3-5):1, for example, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0015] Preferably, the molar ratio of the non-noble metal source and the organic ligand is (1-10):(1-10), for example, it can be 1:1, 5:1, 1:5, 10:1 or 1:10, but is not limited to the listed values. Other unlisted values within the numerical range are also applicable, preferably (1-6):(1-6).

[0016] By further limiting the molar ratio of the non-precious metal source to the organic ligand, the present invention can further improve the stability and catalytic activity of the MOF catalyst, thereby increasing the yield of the catalytic product. Within the preferred molar ratio range of the non-precious metal source to the organic ligand, the prepared MOF catalyst exhibits high stability and catalytic activity, as well as high catalytic product yield and Faradaic efficiency.

[0017] Preferably, the solvent comprises N,N-dimethylformamide, ethanol and deionized water.

[0018] Preferably, the volume ratio of N,N-dimethylformamide, ethanol and deionized water is (0.1-3):(0.1-3):(0.1-3), for example, it can be 1:1:1, 0.1:1:3, 0.1:0.1:3, 2:2:3 or 1:1:3, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0019] Preferably, in the mixed solution, the volume of the solvent accounts for 80%-99% of the total volume of the mixed solution, for example, it can be 80%, 85%, 90%, 95% or 99%, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0020] Preferably, the mixed solution further includes a regulator.

[0021] Preferably, the modifier comprises triethylamine.

[0022] Preferably, in the mixed solution, the volume of the regulator accounts for 1%-20% of the total volume of the mixed solution, for example, it can be 1%, 3%, 5%, 10%, 15% or 20%, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0023] Preferably, the ultrasonic frequency of the ultrasonic synthesis is 30 Hz-100 Hz, for example, 30 Hz, 50 Hz, 70 Hz, 90 Hz or 100 Hz, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0024] Preferably, the ultrasonic synthesis ultrasonic time is 2h-8h, for example, 2h, 3h, 4h, 6h, 7h or 8h, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0025] Preferably, the holding temperature of the ultrasonic synthesis is 20°C-30°C, for example, 20°C, 22°C, 24°C, 26°C, 28°C or 30°C, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0026] Preferably, after the ultrasonic synthesis, solid-liquid separation, washing, freezing and drying are carried out in sequence.

[0027] Preferably, the solid-liquid separation comprises centrifugation.

[0028] Preferably, the washing detergent comprises N,N-dimethylformamide and / or ethanol.

[0029] Preferably, the number of washings is 4 to 10 times, for example, 4, 6, 8, 9 or 10 times, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0030] Preferably, the freezing method includes liquid nitrogen freezing and / or refrigerator freezing.

[0031] Preferably, the holding temperature of the liquid nitrogen freezing is -150°C to -20°C, for example, -150°C, -100°C, -50°C, -40°C, -30°C or -20°C, but is not limited to the listed values, and other values not listed within the numerical range are also applicable.

[0032] Preferably, the freezing insulation temperature of the refrigerator is -20℃~-5℃, for example, it can be -20℃, -15℃, -10℃, -8℃, -7℃ or -5℃, but is not limited to the listed values. Other values not listed within the numerical range are also applicable.

[0033] Preferably, the drying method comprises vacuum drying and / or freeze drying.

[0034] Preferably, the insulation temperature of the vacuum drying is 20°C-50°C, for example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0035] Preferably, the freeze-drying insulation temperature is -70°C to -20°C, for example, it can be -70°C, -60°C, -40°C, -40°C, -30°C or -20°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

[0036] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0037] (1) mixing a non-precious metal source, an organic ligand, a solvent and a regulator to obtain a mixed solution; the non-precious metal source comprises a copper source and / or a cerium source, the organic ligand comprises pyromellitic acid, the solvent comprises any one or a combination of at least two of N,N-dimethylformamide, ethanol or deionized water, the regulator comprises triethylamine, the molar ratio of the non-precious metal source to the organic ligand is (1-10):(1-10), and in the mixed solution, the volume of the solvent accounts for 70%-95% of the total volume of the mixed solution, and the volume of the regulator accounts for 3%-20% of the total volume of the mixed solution.

[0038] (2) The mixed liquid is subjected to ultrasonic synthesis at 20°C-30°C, and then solid-liquid separation, washing, freezing and drying are carried out in sequence to obtain the ultrasonically synthesized non-precious metal-based MOF catalyst; the ultrasonic frequency of the ultrasonic synthesis is 30Hz-100Hz, the ultrasonic time of the ultrasonic synthesis is 2h-8h, the solid-liquid separation includes centrifugation, the washing detergent includes N,N-dimethylformamide and / or ethanol, the number of washing times is 4 times-10 times, the freezing method includes liquid nitrogen freezing and / or refrigerator freezing, the freezing insulation temperature is -20°C to -5°C, the drying method includes vacuum drying and / or freeze drying, the vacuum drying insulation temperature is 20°C-50°C, and the freeze drying insulation temperature is -70°C to -20°C.

[0039] In a second aspect, the present invention provides an ultrasonically synthesized non-noble metal-based MOF catalyst, wherein the ultrasonically synthesized non-noble metal-based MOF catalyst is prepared using the preparation method described in the first aspect.

[0040] In a third aspect, the present invention provides an application of the ultrasonically synthesized non-precious metal-based MOF catalyst as described in the second aspect, wherein the ultrasonically synthesized non-precious metal-based MOF catalyst is applied to electrocatalytic carbon dioxide reduction.

[0041] Preferably, the product of the electrocatalytic carbon dioxide reduction includes ethylene.

[0042] Compared with the prior art, the present invention has at least the following beneficial effects:

[0043] (1) The present invention adopts ultrasonic synthesis to coordinate non-precious metal elements with organic ligands. The preparation method is simple, which can significantly shorten the synthesis time and ensure that MOF can be rapidly crystallized under mild conditions. The prepared catalyst has many catalytic sites and high catalytic activity.

[0044] (2) The present invention selects pyromellitic acid as the organic ligand, which has a multidentate coordination ability and can form a stable coordination structure with the non-noble metal source, thereby improving the thermal stability and chemical stability of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 is a SEM image of the catalyst described in Example 1 of the present invention;

[0046] Figure 2 is a SEM image of the catalyst described in Example 2 of the present invention;

[0047] Figure 3 is an AFM image of the catalyst described in Example 1 of the present invention;

[0048] Figure 4 is an AFM image of the catalyst described in Example 2 of the present invention;

[0049] Figure 5 is a schematic diagram of the catalytic product described in Application Example 1 of the present invention;

[0050] Figure 6 Schematic diagram of the catalytic product described in Application Example 2 of the present invention. DETAILED DESCRIPTION

[0051] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0052] Example 1

[0053] This embodiment provides a method for preparing a non-precious metal-based MOF catalyst by ultrasonic synthesis, the preparation method comprising the following steps:

[0054] (1) dissolving 4 molar parts of CuNO3·3H2O, 1 molar part of CeNO3·6H2O, and 10 molar parts of pyromellitic acid in a mixed solvent, adding triethylamine, and mixing uniformly to obtain a mixed solution; in the mixed solution, the volume of the mixed solvent accounts for 90% of the total volume of the mixed solution, and the volume of the triethylamine accounts for 5% of the total volume of the mixed solution, and the mixed solvent includes 1 part by volume of N,N-dimethylformamide, 1 part by volume of ethanol, and 1 part by volume of deionized water;

[0055] (2) The mixed solution is subjected to ultrasonic synthesis at 25° C. for 6 hours, and then centrifuged, washed, liquid nitrogen frozen and freeze-dried in sequence to obtain the ultrasonically synthesized non-precious metal-based MOF catalyst; the ultrasonic synthesis frequency is 100 Hz, the washing includes washing three times with N,N-dimethylformamide and then washing three times with ethanol, and the insulation temperature of the freeze-drying is -60° C.

[0056] Figure 1 is a SEM image of the catalyst described in Example 1 of the present invention, Figure 3This is an AFM image of the catalyst described in Example 1 of the present invention. It can be seen from the image that the catalyst prepared in this example has a nanosheet morphology with a complete sheet structure. The thickness of the nanosheet is about 5 nm and the thickness is uniform.

[0057] Example 2

[0058] This embodiment provides a method for preparing a non-precious metal-based MOF catalyst by ultrasonic synthesis, the preparation method comprising the following steps:

[0059] (1) dissolving 1 mole of CuNO3·6H2O and 6 moles of pyromellitic acid in a mixed solvent, adding triethylamine, and mixing uniformly to obtain a mixed solution; in the mixed solution, the volume of the mixed solvent accounts for 70% of the total volume of the mixed solution, and the volume of the triethylamine accounts for 20% of the total volume of the mixed solution, and the mixed solvent includes 1 part by volume of N,N-dimethylformamide, 1 part by volume of ethanol, and 1 part by volume of deionized water;

[0060] (2) The mixed solution is subjected to ultrasonic synthesis at 20°C for 8 hours, and then centrifuged, washed, frozen in a refrigerator and freeze-dried in sequence to obtain the ultrasonically synthesized non-precious metal-based MOF catalyst; the ultrasonic frequency of the ultrasonic synthesis is 30 Hz, the washing includes washing twice with N,N-dimethylformamide and then washing twice with ethanol, the insulation temperature of the liquid nitrogen freezing is -30°C, and the insulation temperature of the freeze-drying is -30°C.

[0061] Figure 2 is a SEM image of the catalyst described in Example 2 of the present invention, Figure 4 This is an AFM image of the catalyst described in Example 2 of the present invention. It can be seen from the image that the catalyst prepared in this example has a flaky morphology, a complete flaky structure, and uniform size.

[0062] Example 3

[0063] This embodiment provides a method for preparing a non-precious metal-based MOF catalyst by ultrasonic synthesis, the preparation method comprising the following steps:

[0064] (1) dissolving 6 molar parts of CuCl2·6H2O and 1 molar part of pyromellitic acid in a mixed solvent, adding triethylamine, and mixing uniformly to obtain a mixed solution; in the mixed solution, the volume of the mixed solvent accounts for 95% of the total volume of the mixed solution, and the volume of the triethylamine accounts for 3% of the total volume of the mixed solution, and the mixed solvent includes 1 part by volume of N,N-dimethylformamide, 1 part by volume of ethanol, and 1 part by volume of deionized water;

[0065] (2) The mixed solution is subjected to ultrasonic synthesis at 30°C for 2 hours, and then centrifuged, washed, frozen in a refrigerator and freeze-dried in sequence to obtain the ultrasonically synthesized non-precious metal-based MOF catalyst; the ultrasonic frequency of the ultrasonic synthesis is 50 Hz, the washing includes washing with N,N-dimethylformamide five times and then washing with ethanol five times, the insulation temperature of the liquid nitrogen freezing is -20°C, and the insulation temperature of the freeze-drying is -20°C.

[0066] Example 4

[0067] The only difference between this embodiment and embodiment 1 is that, except that 0.5 molar parts of pyromellitic acid are used in step (1), the rest are the same as those in embodiment 1.

[0068] Example 5

[0069] The only difference between this embodiment and embodiment 1 is that, except that 50 molar parts of pyromellitic acid are used in step (1), the rest are the same as those in embodiment 1.

[0070] Example 6

[0071] The only difference between this embodiment and embodiment 1 is that, except that the ultrasonic frequency of the ultrasonic synthesis in step (2) is 25 Hz, the rest is the same as embodiment 1.

[0072] Example 7

[0073] The only difference between this embodiment and embodiment 1 is that, except that the ultrasonic frequency of the ultrasonic synthesis in step (2) is 55 Hz, the rest is the same as embodiment 1.

[0074] Example 8

[0075] The only difference between this embodiment and embodiment 1 is that, except that 4 molar parts of CuNO3·3H2O and 1 molar part of CeNO3·6H2O in step (1) are replaced by 5 molar parts of CuNO3·3H2O, the rest are the same as embodiment 1.

[0076] Example 9

[0077] The only difference between this embodiment and embodiment 1 is that, except that 4 molar parts of CuNO3·3H2O and 1 molar part of CeNO3·6H2O in step (1) are replaced by 5 molar parts of CeNO3·6H2O, the rest are the same as embodiment 1.

[0078] Comparative Example 1

[0079] The only difference between this comparative example and Example 1 is that, except that terephthalic acid is used to replace pyromellitic acid in step (1), the rest is the same as Example 1.

[0080] Application Example 1

[0081] (1) The ultrasonically synthesized non-noble metal-based MOF catalyst described in Example 1, acetylene black, and polyvinylidene fluoride were mixed in a mass ratio of 8:1:1, dispersed in pyrrolidone, and uniformly mixed to obtain a slurry, which was then coated on nickel foam to obtain a catalytic electrode;

[0082] (2) Using 1 mol / L KOH solution as the electrolyte, assembling the catalytic electrode, Hg / HgO reference electrode and nickel foam electrode into a three-electrode, introducing CO2 into the electrolyte for electrolysis, and collecting the first reaction gas; at 2000 mA / cm 2 After running for 1000 h at a current density of , the second reaction gas was collected.

[0083] Figure 5 This is a schematic diagram of the catalytic product of Application Example 1 of the present invention. As can be seen from the figure, at 300mA / cm 2 At a current density of 1.5 GHz, the Faradaic efficiency of ethylene is as high as 93%.

[0084] Application Example 2

[0085] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 2, the rest is the same as application example 1.

[0086] Figure 6 Schematic diagram of the catalytic product of Application Example 2 of the present invention. As can be seen from the figure, at a voltage of -1.4 V vs. RHE, the Faradaic efficiency of ethylene is 50%.

[0087] Application Example 3

[0088] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 3, the rest is the same as application example 1.

[0089] Application Example 4

[0090] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 4, the rest is the same as application example 1.

[0091] Application Example 5

[0092] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 5, the rest is the same as application example 1.

[0093] Application Example 6

[0094] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 6, the rest is the same as application example 1.

[0095] Application Example 7

[0096] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 7, the rest are the same as application example 1.

[0097] Application Example 8

[0098] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 8, the rest are the same as application example 1.

[0099] Application Example 9

[0100] The difference between this application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in Example 9, the rest are the same as application example 1.

[0101] Comparative Application Example 1

[0102] The only difference between this comparative application example and application example 1 is that, except for step (1) using the ultrasonic synthesis of the non-noble metal-based MOF catalyst described in comparative example 1, the rest are the same as application example 1.

[0103] Test Method

[0104] The second reaction gas collected from Example 1 to Example 9 and Comparative Example 1 and the second reaction gas collected at 300 mA / cm 2 The first reaction gas obtained was collected at a current density of , and the gas selectivity was calculated and the results were recorded in Table 1.

[0105] Table 1

[0106]

[0107]

[0108] The test results show that:

[0109] (1) As can be seen from Application Examples 1 to 9 and Comparative Application Example 1, the present invention adopts ultrasonic synthesis to coordinate non-precious metal elements with organic ligands. The preparation method is simple, the synthesis time can be significantly shortened, and the MOF can be ensured to crystallize rapidly under mild conditions. The prepared catalyst has multiple catalytic sites and high catalytic activity. At the same time, the present invention selects pyromellitic acid as the organic ligand, which has a multi-dentate coordination ability and can form a stable coordination structure with the non-precious metal source, thereby improving the thermal stability and chemical stability of the catalyst. The catalyst of the present invention has high catalytic activity and ethylene selectivity, and the stability of the catalyst is excellent at high current density.

[0110] (2) It can be seen from Application Examples 1 and 4-5 that the present invention can further improve the selectivity of ethylene in the catalytic product by further regulating the molar ratio of the non-noble metal source and the organic ligand pyromellitic acid.

[0111] (3) It can be seen from Application Examples 1 and 6-7 that the present invention can further improve the selectivity of ethylene in the catalytic product by further regulating the ultrasonic frequency of ultrasonic synthesis.

[0112] (4) It can be seen from Application Examples 1 and 8-9 that the present invention can further improve the selectivity of ethylene in the catalytic product by further regulating the type of non-precious metal source.

[0113] (5) It can be seen from Application Example 1 and Comparative Application Example 1 that the ultrasonically synthesized non-precious metal-based MOF catalyst prepared by selecting pyromellitic acid as the organic ligand in the present invention has further improved thermal stability and chemical stability, and the selectivity of ethylene in the catalytic product is also further improved.

[0114] In summary, the present invention adopts ultrasonic synthesis method to coordinate non-precious metal elements with organic ligands, and the preparation method is simple, can significantly shorten the synthesis time, ensure that MOF is rapidly crystallized under mild conditions, and the catalyst prepared has many catalytic sites and high catalytic activity. At the same time, the present invention selects pyromellitic acid as organic ligand, which has multi-dentate coordination ability and can form a stable coordination structure with a non-precious metal source, thereby improving the thermal stability and chemical stability of the catalyst. The catalytic activity and ethylene selectivity of the catalyst of the present invention are high, and under high current density, the stability of the catalyst is excellent.

[0115] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for preparing a non-precious metal-based MOF catalyst by ultrasonic synthesis, characterized in that: The preparation method comprises the following steps: A non-noble metal source, an organic ligand, and a solvent are mixed to obtain a mixed solution, and a non-noble metal-based MOF catalyst is synthesized by ultrasonication; The non-noble metal source includes a copper source and / or a cerium source; The organic ligand includes pyromellitic acid.

2. The preparation method according to claim 1, characterized in that The molar ratio of the non-noble metal source to the organic ligand is (1-10):(1-10), preferably (1-6):(1-6).

3. The preparation method according to claim 1 or 2, characterized in that The solvent includes N,N-dimethylformamide, ethanol and deionized water; Preferably, in the mixed solution, the volume of the solvent accounts for 80%-99% of the total volume of the mixed solution.

4. The preparation method according to any one of claims 1 to 3, characterized in that The mixed solution further includes a regulator; Preferably, the modifier comprises triethylamine; Preferably, in the mixed solution, the volume of the regulator accounts for 1%-20% of the total volume of the mixed solution.

5. The preparation method according to any one of claims 1 to 4, characterized in that The ultrasonic frequency of the ultrasonic synthesis is 30Hz-100Hz; Preferably, the ultrasonic synthesis time is 2h-8h.

6. The preparation method according to any one of claims 1 to 5, characterized in that After the ultrasonic synthesis, solid-liquid separation, washing, freezing and drying are carried out in sequence.

7. The preparation method according to claim 6, characterized in that The solid-liquid separation includes centrifugation; Preferably, the washing detergent comprises N,N-dimethylformamide and / or ethanol; Preferably, the freezing method includes liquid nitrogen freezing and / or refrigerator freezing; Preferably, the drying method comprises vacuum drying and / or freeze drying.

8. An ultrasonic synthesis of non-precious metal-based MOF catalyst, characterized in that The ultrasonically synthesized non-noble metal-based MOF catalyst is prepared by the preparation method according to any one of claims 1 to 7.

9. An application of the ultrasonic synthesis of non-noble metal-based MOF catalyst as claimed in claim 8, characterized in that: The ultrasonically synthesized non-noble metal-based MOF catalyst is applied to electrocatalytic carbon dioxide reduction.

10. The use according to claim 9, characterized in that The product of the electrocatalytic carbon dioxide reduction includes ethylene.

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