CN113355688B - Electrocatalytic reduction of CO2Cu-MOF material and preparation method thereof - Google Patents

Electrocatalytic reduction of CO2Cu-MOF material and preparation method thereof Download PDF

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CN113355688B
CN113355688B CN202110597920.6A CN202110597920A CN113355688B CN 113355688 B CN113355688 B CN 113355688B CN 202110597920 A CN202110597920 A CN 202110597920A CN 113355688 B CN113355688 B CN 113355688B
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CN113355688A (en
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张颖
归家宁
杨蓝翔
娄阳
潘成思
朱永法
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Jiangnan University
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Abstract

The invention discloses an electrocatalytic reduction method for CO2Belonging to the technical field of electrocatalytic reduction. Dissolving 3,4,9, 10-perylenetetracarboxylic dianhydride in N, N-dimethylformamide as a solvent, reacting with 1- (3-aminopropyl) imidazole to generate perylene tetracarboxylic acid bis (propylimidazole), namely PDI, washing and drying; dissolving the obtained PDI in a chloroform solution, and filtering to obtain a chloroform saturated solution of the PDI; finally, placing the chloroform saturated solution of PDI and the methanol solution of copper chloride in a closed container, heating to 40-80 ℃, reacting for 2-6h at constant temperature, carrying out solid-liquid separation to obtain precipitate, washing and drying to obtain the electro-catalytic reduction CO2The Cu-MOF material of (1). The Cu-MOF material prepared by the invention is used for treating CO2The electrocatalytic reduction has good catalytic activity and stability. And the preparation process is simple, has low requirements on equipment, and has good industrial application prospects.

Description

Electrocatalytic reduction of CO2Cu-MOF material and preparation method thereof
Technical Field
The invention relates to an electrocatalytic reduction method for CO2Belonging to the field of electrocatalytic reduction.
Background
CO with the growing and industrialized expansion of the world population2The discharge amount is increased year by year, and the greenhouse effect caused by the discharge amount causes the problems of sea level rise, glacier melting, reduction of animal and plant species and the like for human beings. Therefore, there are increasing attempts to recover carbon dioxide because it is not a waste material, but an abundant and inexpensive carbon source, which can be used to produce value-added chemicals.
How to convert carbon dioxide into chemicals with added values is one of the hot directions of current research. The current ways of chemically converting carbon dioxide include thermocatalysis, photocatalysis, electrocatalysis and the like. Electrocatalysis is a new technology which is currently recognized in the world and can solve the problems of environment and energy sources and has the most application prospect, because the electrocatalysis has the following advantages: (1) the reaction can be carried out at normal temperature and normal pressure; (2) by changing reaction voltage, temperature and the like, the direction and degree of reaction can be controlled, and controllability is achieved; (3) the electric energy required by the reaction can be generated by new energy sources such as solar energy, wind energy and the like; (4) the electrolyte solution in the reaction supports recycling, so that the energy consumption of the whole reaction is reduced to the minimum.
Reduction of CO by electrocatalysis2The development of catalytic materials will determine the extent of their future development. According to the current research, CO can be reduced2The transition metals are divided into the following categories, (1) Pb, Hg, Sn, Cd and the like, and the catalytic products of the metals are mostly formic acid and CO2The binding capacity of the intermediates is weak; (2) au, Ag, Zn, etc. to CO2The binding capacity of the intermediate is moderate, but the adsorption capacity of the intermediate to CO is weak, the C-C coupling in the next step is difficult, and the product is mainly CO; (3) cu, both of which can bind CO2Intermediates, which can also further reduce CO, thus enabling Cu-based catalysts to catalyze CO2And generating the alkane product with higher added value. However, the direct use of transition metals as catalysts has disadvantages, and the Cu-based catalysts can convert CO2The catalyst is converted into alkane products, but the catalytic products have low selectivity and yield and poor stability. Electrochemical catalytic reduction of CO with metal complexes2They have the advantages of low overpotential, high catalytic rate and selectivity, and extended durability due to their unique ability to retain electrons to aid metal complexes in multiple electron conversion and to change the electronic properties or lewis acidity, etc., of the central metal ion.
Disclosure of Invention
The invention aims to provide an electrocatalytic reduction method for CO2The MOF material and the preparation method thereof form a high molecular metal-organic complex through coordination of copper chloride dihydrate and an organic matter PDI, and the complex has good electrochemical catalytic reduction CO2Has high catalytic activity and high stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
electrocatalytic reduction of CO2The preparation method of the Cu-MOF material comprises the following steps: dissolving 3,4,9, 10-perylenetetracarboxylic dianhydride in N, N-dimethylformamide as a solvent, reacting with 1- (3-aminopropyl) imidazole to generate perylene tetracarboxylic acid bis (propylimidazole), namely PDI, washing and drying; dissolving the obtained PDI in a chloroform solution, and filtering to obtain a chloroform saturated solution of the PDI; finally, placing the chloroform saturated solution of PDI and the methanol solution of copper chloride in a closed container, heating to 40-80 ℃, reacting for 2-6h at constant temperature, carrying out solid-liquid separation to obtain precipitate, washing and drying to obtain the electro-catalytic reduction CO2I.e. a PDI-Cu material.
In one embodiment of the invention, the mass ratio of PDI to copper chloride is 2:1 to 2: 4.
In one embodiment of the invention, the concentration of the methanolic copper chloride dihydrate solution is in the range of 0.1 to 0.4 g/mL.
In one embodiment of the present invention, the method for producing PDI specifically includes: dissolving 3,4,9, 10-perylenetetracarboxylic dianhydride in N, N-dimethylformamide to prepare a solution of 3,4,9, 10-perylenetetracarboxylic dianhydride with the concentration of 0.01-0.2 g/mL, then dropwise adding 1- (3-aminopropyl) imidazole with the mass-volume ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride of 0.067-1.667 g/mL, heating to 120-150 ℃, condensing and refluxing, stirring for 10-16h at constant temperature in an inert gas environment, then performing suction filtration and washing by using tetrahydrofuran, and drying to obtain the red powdery PDI.
In one embodiment of the invention, the inert gas environment is preferably argon.
In one embodiment of the invention, the purpose of the suction filtration washing is to remove 1- (3-aminopropyl) imidazole remaining on the surface.
In one embodiment of the invention, the drying is vacuum drying, at a temperature of 40-80 ℃ for a period of 4-10 hours, in order to remove residual tetrahydrofuran.
In one embodiment of the present invention, the method for preparing a chloroform-saturated solution of PDI comprises: adding excessive PDI into chloroform, carrying out closed ultrasonic treatment for 0.5-1h to obtain a chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting a filtrate with a fluorescent color, namely the chloroform saturated solution of the PDI.
In one embodiment of the invention, when preparing the PDI-Cu material, a copper chloride dihydrate methanol solution is dropwise added into a PDI chloroform saturated solution, the temperature is raised to 40-80 ℃ in a closed container, the reaction is carried out for 2-6h at constant temperature, a sand core filtering device is used for filtering to obtain a crude product of the PDI-Cu, the crude product is washed by methanol to remove the residual copper chloride dihydrate on the surface, the crude product is put into a vacuum oven, the temperature is raised to 40-80 ℃, and the drying is carried out for 3-6 h at constant temperature to remove the methanol, so that the Cu-MOF material electrocatalyst is obtained.
In one embodiment of the invention, the sand core filtering device is a microporous filtering membrane made of polyvinylidene fluoride.
The invention also provides the electrocatalytic reduction CO prepared by the preparation method2The Cu-MOF material of (1).
The invention also provides an electro-catalytic reduction method for CO2By electrocatalytic reduction of CO as described above2As an electrocatalytic material.
Has the advantages that:
the PDI-Cu obtained by the invention utilizes the unique capability of metal complex multi-electron conversion and change of electronic properties or Lewis acidity of central metal ions, and has the advantages of reduction of overpotential, improvement of catalytic rate and selectivity, prolongation of durability and the like. And the preparation of the catalyst has simple process and low requirement on equipment, and has better industrial application prospect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of PDI-Cu prepared in example 1, (a) and (b) is a SEM photograph of PDI-Cu under the same conditions after multiple cycles of reaction.
FIG. 2 shows that PDI-Cu prepared in example 1 is used as a catalyst, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a platinum mesh is used as a counter electrode, Nafion N117 is used as a proton exchange membrane in a flow-cell type electrolytic cell, in a 1M potassium hydroxide solution,CO2the flow rate of (2) is 20sccm, and the faradic efficiency of CO is shown at each voltage.
FIG. 3 is a UV spectrum of PDI and PDI-Cu prepared in example 2.
FIG. 4 is a graph of the CO Faraday efficiency of the PDI-Cu catalyst prepared in comparative example 1 under experimental conditions.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Adding 5g of 3,4,9, 10-perylenetetracarboxylic dianhydride into 100mL of N, N-dimethylformamide solution, stirring, dropwise adding 15mL of 1- (3-aminopropyl) imidazole, heating to 140 ℃, condensing, refluxing, stirring for 12h at constant temperature in an inert gas environment, performing suction filtration and washing by using tetrahydrofuran to remove 1- (3-aminopropyl) imidazole remaining on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at constant temperature for 8 h to remove the remaining THF, thereby obtaining a red powdery PDI product.
(2) Adding 300mL of chloroform solution into 4g of PDI prepared in the step (1), carrying out closed ultrasonic treatment for 0.5h to obtain chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is chloroform saturated solution of the PDI;
an appropriate amount of copper chloride dihydrate was dissolved in methanol to prepare a 0.3g/mL copper chloride dihydrate methanol solution.
(3) And (3) slowly dripping 15mL of copper chloride dihydrate methanol solution obtained in the step (2) into 300mL of PDI chloroform saturated solution obtained in the step (2), heating to 60 ℃ in a closed container, reacting at a constant temperature for 4 hours, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using methanol to remove residual copper chloride dihydrate on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at a constant temperature for 4 hours to remove the methanol, thus obtaining the Cu-MOF material electrocatalyst.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of PDI-Cu prepared in this example, showing that PDI-Cu is in an aggregate form.
FIG. 2 shows that PDI-Cu prepared in this example is a catalyst,saturated Calomel Electrode (SCE) as reference electrode, platinum mesh as counter electrode, in flow-cell type electrolytic cell, Nafion N117 as proton exchange membrane, in 1M potassium hydroxide solution, CO2The flow rate of (2) is 20sccm, the Faraday efficiency and current density of CO are shown by a trend graph along with the change of potential. Therefore, the Faraday efficiency of CO is about 50%, the selectivity is good, and the catalyst shows good catalytic performance.
FIG. 1(b) is an SEM image of PDI-Cu after multiple cycles of reaction under the same conditions, and it can be seen that the morphology is almost unchanged from that before the reaction, which illustrates that the material of the present invention has excellent stability.
Example 2
(1) Adding 3g of 3,4,9, 10-perylenetetracarboxylic dianhydride into a 100mLN, N-dimethylformamide solution, stirring, then dropwise adding 10mL of 1- (3-aminopropyl) imidazole, heating to 140 ℃, condensing, refluxing, stirring at constant temperature in an inert gas environment for 12h, performing suction filtration and washing with tetrahydrofuran, removing residual 1- (3-aminopropyl) imidazole on the surface, placing in a vacuum oven, heating to 60 ℃, and drying at constant temperature for 8 h to remove residual THF, thus obtaining a red powdery PDI product.
(2) Taking 2g of the PDI prepared in the step (1), adding 150mL of chloroform solution, carrying out closed ultrasonic treatment for 0.5h to obtain chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is chloroform saturated solution of the PDI;
an appropriate amount of copper chloride dihydrate was dissolved in methanol to prepare a 0.2g/mL copper chloride dihydrate methanol solution.
(3) And (3) slowly dripping 7.5mL of copper chloride dihydrate methanol solution obtained in the step (2) into 150mL of PDI chloroform saturated solution obtained in the step (2), heating to 60 ℃ in a closed container, reacting at constant temperature for 4h, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using methanol to remove residual copper chloride dihydrate, putting into a vacuum oven, heating to 60 ℃, and drying at constant temperature for 4h to remove methanol, thus obtaining the Cu-MOF material electrocatalyst.
FIG. 3 is a graph of the ultraviolet absorption spectrum (UV) of PDI-Cu prepared in this example, where PDI strongly interacts at 491 and 526nm, mainly due to the pi-pi transition of the perylene core [ Keerthi, A.; valiyaveettil, S.Regioisters of Perylenediide Synthesis, Photophysical, and Electrochemical Properties.J.Phys.chem.B 2012, 116,4603-4614 ] when PDI was bound to Cu (II) ions, the peak at 491nm red-shifted to 520nm, while the peak at 526nm red-shifted to 582nm, indicated that PDI had a strong intercoupling effect with Cu (II). .
Example 3
(1) Adding 4g of 3,4,9, 10-perylenetetracarboxylic dianhydride into 50mL of N, N-dimethylformamide solution, stirring, then dropwise adding 10mL of 1- (3-aminopropyl) imidazole, heating to 120 ℃, condensing, refluxing, stirring for 16h at constant temperature in an inert gas environment, performing suction filtration and washing by using tetrahydrofuran, removing 1- (3-aminopropyl) imidazole remaining on the surface, putting into a vacuum oven, heating to 80 ℃, and drying at constant temperature for 4h to remove the remaining THF, thus obtaining a red powdery PDI product.
(2) Adding 300mL of chloroform solution into 4g of PDI prepared in the step (1), carrying out closed ultrasonic treatment for 1h to obtain chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is chloroform saturated solution of the PDI;
an appropriate amount of copper chloride dihydrate was dissolved in methanol to prepare a 0.4g/mL copper chloride dihydrate methanol solution.
(3) And (3) slowly dripping 20mL of copper chloride dihydrate methanol solution obtained in the step (2) into 300mL of PDI chloroform saturated solution obtained in the step (2), heating to 40 ℃ in a closed container, reacting at a constant temperature for 6h, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using methanol to remove residual copper chloride dihydrate on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at a constant temperature for 4h to remove the methanol, thus obtaining the Cu-MOF material electrocatalyst.
Comparative example 1
(1) Adding 5g of 3,4,9, 10-perylenetetracarboxylic dianhydride into 100mL of N, N-dimethylformamide solution, stirring, then dropwise adding 15mL of 1- (3-aminopropyl) imidazole, heating to 140 ℃, condensing and refluxing, stirring for 12h at constant temperature in an inert gas environment, cooling the reaction mixture to room temperature, dissolving the crude solid in 250 mL of trichloromethane, and carrying out ultrasonic treatment for 30 min. 300ml of deionized water was added to the chloroform solution, and the unreacted anhydride precipitate was separated by filtration. The remaining compound in the chloroform solution was further washed several times with deionized water to remove dissolved imidazole. Finally, PDI was obtained after evaporation of chloroform.
(2) Adding 300mL of chloroform solution into 4g of PDI prepared in the step (1), carrying out closed ultrasonic treatment for 0.5h to obtain chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is chloroform saturated solution of the PDI;
an appropriate amount of copper chloride dihydrate was dissolved in methanol to prepare a 0.3g/mL copper chloride dihydrate methanol solution.
(3) And (3) slowly dripping 15mL of copper chloride dihydrate methanol solution obtained in the step (2) into 300mL of PDI chloroform saturated solution obtained in the step (2), heating to 60 ℃ in a closed container, reacting at a constant temperature for 4 hours, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using methanol to remove residual copper chloride dihydrate on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at a constant temperature for 4 hours to remove the methanol, thus obtaining the Cu-MOF material electrocatalyst.
Catalytic reduction of CO in a flow-cell apparatus with the PDI-Cu obtained in this comparative example as a catalyst2FIG. 4 is a graph showing the Faraday efficiency of product CO, which is clearly lower than that of example 1 by comparison, and shows that the performance of the catalyst is reduced.
Comparative example 2
(1) Adding 5g of 3,4,9, 10-perylenetetracarboxylic dianhydride into 100mL of N, N-dimethylformamide solution, stirring, dropwise adding 15mL of 1- (3-aminopropyl) imidazole, heating to 140 ℃, condensing, refluxing, stirring for 12h at constant temperature in an inert gas environment, performing suction filtration and washing by using tetrahydrofuran to remove 1- (3-aminopropyl) imidazole remaining on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at constant temperature for 8 h to remove the remaining THF, thereby obtaining a red powdery PDI product.
(2) Taking 0.5g of PDI prepared in the step (1), adding 300mL of chloroform solution, carrying out closed ultrasonic treatment for 0.5h to obtain chloroform extremely diluted solution of PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is the chloroform extremely diluted solution of PDI;
an appropriate amount of copper chloride dihydrate was dissolved in a methanol solution to prepare a 0.3g/mL copper chloride dihydrate methanol solution.
(3) And (3) slowly dripping 15mL of copper chloride dihydrate methanol solution obtained in the step (2) into 300mL of PDI chloroform extremely dilute solution obtained in the step (2), heating to 60 ℃ in a closed container, reacting at constant temperature for 4 hours, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using methanol to remove residual copper chloride dihydrate, putting into a vacuum oven, heating to 60 ℃, and drying at constant temperature for 4 hours to remove the methanol, thus obtaining the Cu-MOF material electrocatalyst.
The yield of PDI-Cu obtained by the preparation of the comparative example was weighed to be 6.1mg, and the mass of PDI-Cu obtained by the preparation of example 1 was 24.4mg, and the yield was found to be greatly reduced by comparison.
Comparative example 3
(1) Adding 5g of 3,4,9, 10-perylenetetracarboxylic dianhydride into 100mL of N, N-dimethylformamide solution, stirring, dropwise adding 15mL of 1- (3-aminopropyl) imidazole, heating to 140 ℃, condensing, refluxing, stirring for 12h at constant temperature in an inert gas environment, performing suction filtration and washing by using tetrahydrofuran to remove 1- (3-aminopropyl) imidazole remaining on the surface, putting into a vacuum oven, heating to 60 ℃, and drying at constant temperature for 8 h to remove the remaining THF, thereby obtaining a red powdery PDI product.
(2) Taking 4g of PDI treated in the step (1), adding 300mL of chloroform solution, carrying out closed ultrasonic treatment for 0.5h to obtain chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting filtrate with fluorescent color, wherein the filtrate is chloroform saturated solution of the PDI;
an appropriate amount of copper chloride dihydrate was dissolved in ethanol to prepare a 0.3g/mL ethanol solution of copper chloride dihydrate.
(3) And (3) slowly dripping 15mL of the ethanol solution of copper chloride dihydrate obtained in the step (2) into 300mL of the chloroform saturated solution of PDI obtained in the step (2), heating to 60 ℃ in a closed container, reacting at a constant temperature for 4 hours, filtering by using a sand core filtering device to obtain a crude product of PDI-Cu, washing by using ethanol to remove the residual copper chloride dihydrate on the surface, and drying at a constant temperature for 4 hours in a common oven to remove ethanol, thus obtaining the Cu-MOF material electrocatalyst.
The yield of PDI-Cu obtained in the preparation of this comparative example was weighed to 4.8mg, and the yield was significantly reduced compared to 24.4mg obtained in example 1.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. Electrocatalytic reduction of CO2The preparation method of the Cu-MOF material is characterized in that N, N-dimethylformamide is used as a solvent to dissolve 3,4,9, 10-perylenetetracarboxylic dianhydride, the 3,4,9, 10-perylenetetracarboxylic dianhydride reacts with 1- (3-aminopropyl) imidazole to generate perylene tetracarboxylic acid bis (propylimidazole), namely PDI, and the perylene tetracarboxylic acid bis (propylimidazole), namely PDI, is washed and dried; dissolving the obtained PDI in a chloroform solution, and filtering to obtain a chloroform saturated solution of the PDI; finally, placing the chloroform saturated solution of PDI and the methanol solution of copper chloride in a closed container, heating to 40-80 ℃, reacting for 2-6h at constant temperature, carrying out solid-liquid separation to obtain precipitate, washing and drying to obtain the electro-catalytic reduction CO2I.e. a PDI-Cu material.
2. The production method according to claim 1, wherein the mass ratio of PDI to copper chloride is 2:1 to 2: 4.
3. The method according to claim 1, wherein the concentration of the methanolic solution of copper chloride is 0.1 to 0.4 g/mL.
4. The preparation method according to any one of claims 1 to 3, characterized in that 3,4,9, 10-perylenetetracarboxylic dianhydride is dissolved in N, N-dimethylformamide to prepare a solution of 3,4,9, 10-perylenetetracarboxylic dianhydride with the concentration of 0.01 to 0.2g/mL, then 1- (3-aminopropyl) imidazole with the mass-to-volume ratio of 3,4,9, 10-perylenetetracarboxylic dianhydride of 0.067 to 1.667g/mL is added dropwise, the temperature is raised to 120 ℃ and 150 ℃, the solution is condensed and refluxed, the solution is stirred for 10 to 16 hours at constant temperature in an inert gas environment, and then tetrahydrofuran is used for suction filtration and washing, and the red powdery PDI is prepared after drying.
5. The method according to claim 4, wherein the drying is vacuum drying at 40-80 ℃ for 4-10 hours.
6. The method according to claim 1, wherein the method for producing a chloroform-saturated solution of PDI comprises: adding excessive PDI into chloroform, carrying out closed ultrasonic treatment for 0.5-1h to obtain a chloroform supersaturated solution of the PDI, filtering by using a sand core filtering device, removing a filter cake, and collecting a filtrate with a fluorescent color, namely the chloroform saturated solution of the PDI.
7. The preparation method of claim 1, wherein when the PDI-Cu material is prepared, a copper chloride dihydrate methanol solution is dropwise added into a PDI chloroform saturated solution, the temperature is raised to 40-80 ℃ in a closed container, the reaction is carried out for 2-6h at constant temperature, a sand core filtering device is used for filtering to obtain a crude product of the PDI-Cu, the crude product is washed by methanol to remove the residual copper chloride dihydrate on the surface, the crude product is placed into a vacuum oven, the temperature is raised to 40-80 ℃, and the drying is carried out for 3-6 h at constant temperature to remove the methanol, so that the Cu-MOF material electrocatalyst is obtained.
8. Electrocatalytic reduction CO prepared by the preparation method of any one of claims 1 to 72The Cu-MOF material of (1).
9. Electrocatalytic reduction of CO2The method of claim 8, wherein the electrocatalytic reduction of CO is performed by the method of claim 82As an electrocatalytic material.
10. The method according to any one of claims 1 to 7 or the electrocatalytic reduction of CO according to claim 82In the presence of Cu-MOF materialApplication in the field of catalytic reduction.
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