CN111715297A - Preparation of manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst and electroreduction of CO2Method of producing a composite material - Google Patents

Preparation of manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst and electroreduction of CO2Method of producing a composite material Download PDF

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CN111715297A
CN111715297A CN202010709534.7A CN202010709534A CN111715297A CN 111715297 A CN111715297 A CN 111715297A CN 202010709534 A CN202010709534 A CN 202010709534A CN 111715297 A CN111715297 A CN 111715297A
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based catalyst
carbon
manganese phthalocyanine
shaped carbon
mixture
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CN111715297B (en
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程军
岑可法
周俊虎
刘建忠
杨卫娟
王智化
张彦威
周志军
何勇
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Zhejiang University ZJU
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    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese

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Abstract

The invention relates to the technical field of building materials, and aims to provide a preparation method of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst. The method comprises the following steps: calcining a mixture of ammonium bromide and melamine to obtain carbon nitride, and pyrolyzing the carbon nitride in a nitrogen atmosphere; cleaning and drying the product to obtain the ox horn-shaped carbon-based catalyst; dispersing the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst in N-N-dimethylformamide solution, adding manganese phthalocyanine molecules after ultrasonic treatment, and cleaning and drying after ultrasonic treatment and stirring to obtain the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst. The product of the invention has rich porous structure, higher specific surface area, high content of pyridine nitrogen and pyrrole nitrogen active sites, good conductivity and high efficiency cathode catalyst. Carbon-based catalyst with ox horn-shaped structureThe agent has a tip effect under the action of an electric field to enrich charges and promote CO2High-efficiency reduction reaction. Manganese single atom in phthalocyanmanganese molecule is used as active site, and CO is reduced2Reduction to intermediate COOH, promoting CO2The conversion reaction to CO gas products has high Faraday efficiency.

Description

Preparation of manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst and electroreduction of CO2Method of producing a composite material
Technical Field
The invention relates to a greenhouse gas CO2The conversion and utilization technology of (2), in particular to the preparation of manganese phthalocyanine modified bullhorn carbon-based catalyst and the electro-reduction of CO2A method.
Background
Coal-fired flue gas CO reduction and conversion by utilizing wind power and photoelectric energy storage2The production of renewable fuel has important significance for energy conservation and environmental protection and new energy development. Due to CO2Stable molecular chemical properties, CO2The reduction process is accompanied by hydrogen evolution reaction, so that it is difficult to catalytically reduce CO with high efficiency and high selectivity2. In order to solve these technical bottlenecks, the development of efficient electrocatalysts for CO conversion is urgently needed2Reducing the fuel into renewable fuel. In recent years researchers have been improving electrochemical reduction of CO2A great deal of effort has been put into the catalyst aspect of (1). The transition metal monatomic catalyst is suitable for reducing CO due to high atom utilization rate, excellent electrochemical performance and strong chemical stability2The catalyst is high-efficiency. However, the transition metal monoatomic group also has problems such as low metal loading rate and complex and various coordination structures (e.g., metal-carbon, metal-nitrogen), and the like, resulting in CO2The faradaic efficiency of the reduction is low. Experiments prove that: the adoption of the manganese phthalocyanine micromolecules can not only improve the metal loading rate, but also change the reaction energy barrier of intermediate products such as COOH, CO and the like, thereby improving the target productSelectivity of CO gas fuel. Because the manganese phthalocyanine micromolecules have rich metal-nitrogen coordination active sites, the method is favorable for CO2And the adsorption of intermediates thereof. Carbon-based catalyst with ox horn structure in CO2Has the effect of enriching the tip charge in the reduction process and can obviously promote CO2High efficiency transformation of (1). Therefore, the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst can effectively improve CO2And the adsorption capacity of the intermediate product thereof, thereby improving CO2Conversion capability for reduction to CO gas fuel with utilization of CO2Wide application prospect in producing chemicals.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides preparation of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst and electric reduction of CO2A method.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst comprises the following steps:
(1) taking 23.3g of ammonium bromide and 1g of melamine, and adding 30mL of deionized water; stirring for 24 hours after ultrasonic treatment for 1 hour; then placing the mixture in a vacuum oven to dry for 8 hours at the temperature of 100 ℃ to obtain a mixture;
(2) placing the mixture obtained in the step (1) in a crucible, and moving the crucible to a muffle furnace; heating the mixture from room temperature to 500 ℃, and calcining the mixture for 2 hours at constant temperature to obtain carbon nitride; putting the carbon nitride into a tubular furnace, introducing nitrogen, heating to 600-800 ℃, and pyrolyzing for 2h at constant temperature; centrifugally cleaning the pyrolysis product with deionized water for three times, and drying in a vacuum oven to obtain a horn-shaped carbon-based catalyst;
(3) taking 0.6g of the ox horn-shaped carbon-based catalyst obtained in the step (2), and dispersing in 200mL of N-N-dimethylformamide solution; carrying out ultrasonic treatment for 30min, adding 50-70 mg of manganese phthalocyanine molecules, and carrying out ultrasonic treatment for 1 h; stirring for 24h at room temperature, and centrifugally cleaning with ethanol for three times; and then drying in a vacuum oven to obtain the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst.
In the invention, when the temperature of the muffle furnace in the step (2) is raised, the heating rate is controlled to be 1.8 ℃/min; after the carbon nitride is put into the tube furnace, the heating rate is controlled to be 5 ℃/min.
In the invention, the drying temperature in the vacuum oven in the step (2) is 60 ℃, and the drying temperature in the vacuum oven in the step (3) is 80 ℃.
The invention further provides manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst prepared by the method for electrocatalytic reduction of CO2The method comprises the following steps:
(4.1) taking 10mg of manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst and 200 mul of deionized water 100 mul L, Nafion solution, and carrying out ultrasonic treatment and mixing uniformly; the resulting mixture was then brushed at 1cm2Drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to prepare a cathode electrode;
(4.2) arranging an H-shaped reactor with double electrolytic tanks, installing the cathode electrode prepared in the step (4.1) on one side, and installing a carbon rod anode electrode on the other side; the double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle; connecting the anode electrode and the cathode electrode with wires respectively to form an external circuit;
(4.3) adding a sulfuric acid solution with the concentration of 0.5M into the anode cavity of the double-electrolytic-tank reactor, and adding KHCO with the concentration of 0.5M into the cathode cavity3Solution of CO2Leading the mixture into a cathode cavity through a micron aerator for electro-reduction reaction;
(in CO)2In the reaction process of reducing the carbon into CO, cathode charges are accumulated at the tip of the ox horn-shaped carbon-based catalyst; the intermediate product COOH is controlled at the manganese adsorption sites on the surface of the manganese phthalocyanine molecules, so that COOH is further reduced into intermediate product CO, and finally, the intermediate product CO is desorbed and converted into a CO product. )
(4.4) electrocatalytic reduction of CO2Taking a gas product every 15min in the reaction process; and after reacting for 4h, collecting a liquid product in the cathode cavity, and detecting components of the gas-phase product and the liquid-phase product by using a gas chromatograph.
In the present invention, the mass concentration of the Nafion solution described in the step (4.1) is 10%.
Compared with the prior art, the invention has the beneficial effects that:
1. the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst has rich porous structure, higher specific surface area, high content of pyridine nitrogen and pyrrole nitrogen active sites and good conductivity, so that the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst becomes a high-efficiency cathode catalyst.
2. The manganese phthalocyanine micromolecule can be used as an active site to promote CO2Reduced, Mn-N abundant in itself4Coordination of the active site for CO2And intermediate adsorption thereof; the carbon-based catalyst with the horn-shaped structure has tip effect enriched charges under the action of an electric field, so that CO is promoted2High-efficiency reduction reaction. Manganese single atom in phthalocyanmanganese molecule is used as active site, and CO is reduced2The reduction to intermediate product COOH is carried out, and the enrichment of the charge at the tip of the carbon-based catalyst in the shape of an ox horn is beneficial to the further reduction of COOH to intermediate product CO, thereby promoting the reduction of CO2Conversion reaction to CO gas product.
3. In the prior art, the transition metal monatomic catalyst obtained by pyrolysis is used for reducing carbon dioxide, and the Faraday efficiency of the obtained CO gas product is only 72%; the manganese phthalocyanine modified ox horn-shaped carbon-based catalyst is used for electrically reducing CO2And (3) reacting, wherein components of gas-phase and liquid-phase products are detected by using a gas chromatograph, so that the Faraday efficiency of the obtained CO gas product is up to 87-98%.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The ammonium bromide, the melamine, the N-N-dimethylformamide, the manganese phthalocyanine, the ethanol, the sulfuric acid solution (95 percent) and the potassium bicarbonate used in the invention are all purchased from chemical reagents of Chinese national medicine group, Inc.; nafion solution and Nafion membrane were purchased from dupont; the carbon paper is purchased from Betty new energy materials.
As shown in figure 1 of the drawings, in which,preparation of manganese phthalocyanine modified ox horn carbon-based catalyst and application of catalyst in electroreduction of CO2The method specifically comprises the following steps:
(1) and adding 30mL of deionized water into 23.3g of ammonium bromide and 1g of melamine, carrying out ultrasonic treatment for 1h, stirring for 24h, and then placing in a vacuum oven for drying at 100 ℃ for 8h to obtain a mixture.
(2) And (2) placing the mixture obtained in the step (1) into a crucible, placing the crucible into a muffle furnace at room temperature, controlling the heating rate to be 1.8 ℃/min, heating to 500 ℃, and calcining at constant temperature for 2h to obtain the carbon nitride. And then placing the carbon nitride into a tubular furnace, introducing nitrogen, controlling the heating rate of the tubular furnace to be 5 ℃/min, heating to 600-800 ℃, then carrying out constant-temperature pyrolysis for 2h, centrifugally cleaning a pyrolysis product with deionized water for three times, and then placing the pyrolysis product in a vacuum oven at 60 ℃ for drying to obtain the ox horn-shaped carbon-based catalyst.
(3) And (3) dispersing 0.6g of the bullhorn-shaped carbon-based catalyst obtained in the step (2) in 200mL of N-N-dimethylformamide solution, carrying out ultrasonic treatment for 30min, adding 50-70 mg of manganese phthalocyanine molecules, carrying out ultrasonic treatment for 1h, stirring at room temperature for 24h, carrying out centrifugal cleaning with ethanol for three times, and drying in a vacuum oven at 80 ℃ to obtain the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst.
(4) Taking 10mg of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst in the step (3) and 200 mul (mass concentration of 10%) of deionized water 100 mul L, Nafion solution, uniformly mixing by adopting ultrasonic treatment, and then coating on a 1cm thick layer2And (3) drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to obtain the cathode electrode.
And (3) arranging an H-shaped reactor with double electrolytic tanks, installing the cathode electrode prepared in the step (4) on one side, and installing a carbon rod anode electrode on the other side. The double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle. The anode electrode and the cathode electrode are connected by wires, respectively, to form an external circuit.
(5) Adding sulfuric acid solution with concentration of 0.5M into the anode cavity of the double electrolytic cell reactor, and adding KHCO with concentration of 0.5M into the cathode cavity3Solution of CO2And the mixture is introduced into a cathode cavity through a micron aerator to carry out electro-reduction reaction. In CO2In the reaction process of reducing the carbon into CO, cathode charges are accumulated at the tip of the ox horn-shaped carbon-based catalyst; the intermediate product COOH is controlled at the manganese adsorption sites on the surface of the manganese phthalocyanine molecules, so that COOH is further reduced into intermediate product CO, and finally, the intermediate product CO is desorbed and converted into a CO product.
(6) Electrocatalytic reduction of CO2Taking a gas product every 15min after the reaction, collecting a liquid product in the cathode cavity after reacting for 4h, and detecting the components of the gas-phase product and the liquid-phase product by using a gas chromatograph.
Example 1
And adding 30mL of deionized water into 23.3g of ammonium bromide and 1g of melamine, carrying out ultrasonic treatment for 1h, stirring for 24h, and then placing in a vacuum oven for drying at 100 ℃ for 8h to obtain a mixture. Placing the mixture in a crucible, placing the crucible in a muffle furnace at room temperature, controlling the heating rate to be 1.8 ℃/min, heating to 500 ℃, and calcining at constant temperature for 2h to obtain the carbon nitride. And then putting the carbon nitride into a tubular furnace, introducing nitrogen, controlling the heating rate of the tubular furnace to be 5 ℃/min, heating to 600 ℃, then carrying out constant-temperature pyrolysis for 2h, centrifugally cleaning a pyrolysis product with deionized water for three times, and then placing the pyrolysis product in a vacuum oven at 60 ℃ for drying to obtain the ox horn-shaped carbon-based catalyst. Taking 0.6g of the bullhorn-shaped carbon-based catalyst, dispersing the bullhorn-shaped carbon-based catalyst in 200mL of N-N-dimethylformamide solution, carrying out ultrasonic treatment for 30min, adding 50mg of manganese phthalocyanine molecules, carrying out ultrasonic treatment for 1h, stirring for 24h at room temperature, carrying out centrifugal cleaning for three times by using ethanol, and then drying in a vacuum oven at 80 ℃ to obtain the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst.
Taking 10mg of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst and 200 mu L (mass concentration of 10%) of deionized water 100 mu L, Nafion solution, uniformly mixing by adopting ultrasonic treatment, and brushing on the mixture at 1cm2And (3) drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to obtain the cathode electrode. The double-electrolytic-tank H-shaped reactor is adopted, the cathode electrode is arranged on one side, and the carbon rod anode electrode is arranged on the other side. The double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle. The anode electrode and the cathode electrode are connected to form an external circuit.
Adding sulfuric acid solution with concentration of 0.5M into the anode cavity of the double electrolytic tank reactor, and adding sulfuric acid solution into the cathodeKHCO with a concentration of 0.5M is added into the polar cavity3Solution of CO2And the mixture is introduced into a cathode cavity through a micron aerator to carry out electro-reduction reaction. In CO2In the reaction process of reducing the carbon into CO, cathode charges are accumulated at the tip of the ox horn-shaped carbon-based catalyst; the intermediate product COOH is controlled at the manganese adsorption sites on the surface of the manganese phthalocyanine molecules, so that COOH is further reduced into intermediate product CO, and finally, the intermediate product CO is desorbed and converted into a CO product. Electrocatalytic reduction of CO2Taking a gas product every 15min after the reaction, collecting a liquid product in the cathode cavity after reacting for 4h, and detecting the components of the gas-phase product and the liquid-phase product by using a gas chromatograph to obtain the CO gas product with the Faraday efficiency as high as 87%.
Example 2
And adding 30mL of deionized water into 23.3g of ammonium bromide and 1g of melamine, carrying out ultrasonic treatment for 1h, stirring for 24h, and then placing in a vacuum oven for drying at 100 ℃ for 8h to obtain a mixture. Placing the mixture in a crucible, placing the crucible in a muffle furnace at room temperature, controlling the heating rate to be 1.8 ℃/min, heating to 500 ℃, and calcining at constant temperature for 2h to obtain the carbon nitride. And then putting the carbon nitride into a tubular furnace, introducing nitrogen, controlling the heating rate of the tubular furnace to be 5 ℃/min, heating to 700 ℃, then carrying out constant-temperature pyrolysis for 2h, centrifugally cleaning the pyrolysis product with deionized water for three times, and then placing the pyrolysis product in a vacuum oven at 60 ℃ for drying to obtain the ox horn-shaped carbon-based catalyst. Taking 0.6g of the bullhorn-shaped carbon-based catalyst, dispersing the bullhorn-shaped carbon-based catalyst in 200mL of N-N-dimethylformamide solution, carrying out ultrasonic treatment for 30min, adding 60mg of manganese phthalocyanine molecules, carrying out ultrasonic treatment for 1h, stirring for 24h at room temperature, carrying out centrifugal cleaning for three times by using ethanol, and then drying in a vacuum oven at 80 ℃ to obtain the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst.
Taking 10mg of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst and 200 mu L (mass concentration of 10%) of deionized water 100 mu L, Nafion solution, uniformly mixing by adopting ultrasonic treatment, and brushing on the mixture at 1cm2And (3) drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to obtain the cathode electrode. The double-electrolytic-tank H-shaped reactor is adopted, the cathode electrode is arranged on one side, and the carbon rod anode electrode is arranged on the other side. The double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle. The anode is made ofThe electrode and the cathode electrode are connected to form an external circuit.
Adding sulfuric acid solution with concentration of 0.5M into the anode cavity of the double electrolytic cell reactor, and adding KHCO with concentration of 0.5M into the cathode cavity3Solution of CO2And the mixture is introduced into a cathode cavity through a micron aerator to carry out electro-reduction reaction. In CO2In the reaction process of reducing the carbon into CO, cathode charges are accumulated at the tip of the ox horn-shaped carbon-based catalyst; the intermediate product COOH is controlled at the manganese adsorption sites on the surface of the manganese phthalocyanine molecules, so that COOH is further reduced into intermediate product CO, and finally, the intermediate product CO is desorbed and converted into a CO product. Electrocatalytic reduction of CO2Taking a gas product every 15min after the reaction, collecting a liquid product in the cathode cavity after reacting for 4h, and detecting the components of the gas-phase product and the liquid-phase product by using a gas chromatograph to obtain the CO gas product with the Faraday efficiency as high as 92%.
Example 3
And adding 30mL of deionized water into 23.3g of ammonium bromide and 1g of melamine, carrying out ultrasonic treatment for 1h, stirring for 24h, and then placing in a vacuum oven for drying at 100 ℃ for 8h to obtain a mixture. Placing the mixture in a crucible, placing the crucible in a muffle furnace at room temperature, controlling the heating rate to be 1.8 ℃/min, heating to 500 ℃, and calcining at constant temperature for 2h to obtain the carbon nitride. And then putting the carbon nitride into a tubular furnace, introducing nitrogen, controlling the heating rate of the tubular furnace to be 5 ℃/min, heating to 800 ℃, then carrying out constant-temperature pyrolysis for 2h, centrifugally cleaning a pyrolysis product with deionized water for three times, and then placing the pyrolysis product in a vacuum oven at 60 ℃ for drying to obtain the ox horn-shaped carbon-based catalyst. Taking 0.6g of the bullhorn-shaped carbon-based catalyst, dispersing the bullhorn-shaped carbon-based catalyst in 200mL of N-N-dimethylformamide solution, carrying out ultrasonic treatment for 30min, adding 70mg of manganese phthalocyanine molecules, carrying out ultrasonic treatment for 1h, stirring for 24h at room temperature, carrying out centrifugal cleaning for three times by using ethanol, and then drying in a vacuum oven at 80 ℃ to obtain the manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst.
Taking 10mg of manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst and 200 mu L (mass concentration of 10%) of deionized water 100 mu L, Nafion solution, uniformly mixing by adopting ultrasonic treatment, and brushing on the mixture at 1cm2And (3) drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to obtain the cathode electrode. An H-shaped reactor with double electrolytic tanks is arranged on one sideThe cathode electrode and the other side are provided with a carbon rod anode electrode. The double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle. The anode electrode and the cathode electrode are connected to form an external circuit.
Adding sulfuric acid solution with concentration of 0.5M into the anode cavity of the double electrolytic cell reactor, and adding KHCO with concentration of 0.5M into the cathode cavity3Solution of CO2And the mixture is introduced into a cathode cavity through a micron aerator to carry out electro-reduction reaction. In CO2In the reaction process of reducing the carbon into CO, cathode charges are accumulated at the tip of the ox horn-shaped carbon-based catalyst; the intermediate product COOH is controlled at the manganese adsorption sites on the surface of the manganese phthalocyanine molecules, so that COOH is further reduced into intermediate product CO, and finally, the intermediate product CO is desorbed and converted into a CO product. Electrocatalytic reduction of CO2Taking a gas product every 15min after the reaction, collecting a liquid product in the cathode cavity after reacting for 4h, and detecting the components of the gas-phase product and the liquid-phase product by using a gas chromatograph to obtain the CO gas product with the Faraday efficiency as high as 98%.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (5)

1. The preparation method of the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst is characterized by comprising the following steps:
(1) taking 23.3g of ammonium bromide and 1g of melamine, and adding 30mL of deionized water; stirring for 24 hours after ultrasonic treatment for 1 hour; then placing the mixture in a vacuum oven to dry for 8 hours at the temperature of 100 ℃ to obtain a mixture;
(2) placing the mixture obtained in the step (1) in a crucible, and moving the crucible to a muffle furnace; heating the mixture from room temperature to 500 ℃, and calcining the mixture for 2 hours at constant temperature to obtain carbon nitride; putting the carbon nitride into a tubular furnace, introducing nitrogen, heating to 600-800 ℃, and pyrolyzing for 2h at constant temperature; centrifugally cleaning the pyrolysis product with deionized water for three times, and drying in a vacuum oven to obtain a horn-shaped carbon-based catalyst;
(3) taking 0.6g of the ox horn-shaped carbon-based catalyst obtained in the step (2), and dispersing in 200mL of N-N-dimethylformamide solution; carrying out ultrasonic treatment for 30min, adding 50-70 mg of manganese phthalocyanine molecules, and carrying out ultrasonic treatment for 1 h; stirring for 24h at room temperature, and centrifugally cleaning with ethanol for three times; and then drying in a vacuum oven to obtain the manganese phthalocyanine modified oxhorn-shaped carbon-based catalyst.
2. The method according to claim 1, wherein in the step (2), when the temperature of the muffle furnace is increased, the heating rate is controlled to be 1.8 ℃/min; after the carbon nitride is put into the tube furnace, the heating rate is controlled to be 5 ℃/min.
3. The method according to claim 1, wherein the drying temperature in the vacuum oven in step (2) is 60 ℃ and the drying temperature in the vacuum oven in step (3) is 80 ℃.
4. Electrocatalytic reduction of CO by manganese phthalocyanine modified bullhorn-based catalyst prepared by the method of claim 12The method is characterized by comprising the following steps:
(4.1) taking 10mg of manganese phthalocyanine modified bullhorn-shaped carbon-based catalyst and 200 mul of deionized water 100 mul L, Nafion solution, and carrying out ultrasonic treatment and mixing uniformly; the resulting mixture was then brushed at 1cm2Drying the carbon paper in a vacuum oven at 80 ℃ for 8 hours to prepare a cathode electrode;
(4.2) arranging an H-shaped reactor with double electrolytic tanks, installing the cathode electrode prepared in the step (4.1) on one side, and installing a carbon rod anode electrode on the other side; the double electrolytic tank reactor is sealed by polytetrafluoroethylene, and is connected and separated by a cation exchange membrane in the middle; connecting the anode electrode and the cathode electrode with wires respectively to form an external circuit;
(4.3) adding a sulfuric acid solution with the concentration of 0.5M into the anode cavity of the double-electrolytic-tank reactor, and adding KHCO with the concentration of 0.5M into the cathode cavity3Solution of CO2Leading the mixture into a cathode cavity through a micron aerator for electro-reduction reaction;
(4.4) electrocatalysisReduction of CO2Taking a gas product every 15min in the reaction process; and after reacting for 4h, collecting a liquid product in the cathode cavity, and detecting components of the gas-phase product and the liquid-phase product by using a gas chromatograph.
5. The method according to claim 1, wherein the mass concentration of the Nafion solution in step (4.1) is 10%.
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