CN110629245A - Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material - Google Patents

Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material Download PDF

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CN110629245A
CN110629245A CN201910950776.2A CN201910950776A CN110629245A CN 110629245 A CN110629245 A CN 110629245A CN 201910950776 A CN201910950776 A CN 201910950776A CN 110629245 A CN110629245 A CN 110629245A
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cadmium sulfide
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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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Abstract

The invention relates to CO2The conversion and utilization technology aims at providing a nitrogen-doped carbon-coated copper cadmium sulfide catalyst for the photoelectric reduction of CO2A method. The method comprises the following steps: one side of a reactor of the double electric tanks is provided with a cathode electrode made of a nitrogen-doped carbon-coated copper-cadmium sulfide catalyst, and the other side is provided with NiO/Fe2O3@g‑C3N4An anode electrode made of a catalyst; adding deionized water solution into the anode cavity, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2Leading the mixture into a cathode cavity through a micron aerator for carrying out photoelectric reduction reaction; in the cathode chamber, CO2After photoelectric reduction reaction, the first is generatedAn alcohol. In the invention, the photoanode catalyst NiO/Fe2O3@g‑C3N4The carbon-coated copper cadmium sulfide nano-particles doped with nitrogen and cooperated with the electro-cathode catalyst can efficiently catalyze and reduce CO2Promoting the formation of liquid methanol fuel product. Compared with a pure nitrogen-doped carbon catalyst or a copper-cadmium sulfide nanoparticle catalyst, the catalyst can reduce CO2The selectivity of the methanol product in the reaction is improved by over 60 percent.

Description

Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material
Technical Field
The invention relates to a greenhouse gas CO2The conversion and utilization technology of (1), in particular to a nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photo-reduction of CO2A method.
Background
The widespread use of fossil fuels poses a number of environmental problems, particularly the increase in the greenhouse gas CO2Emission, how to discharge CO2The conversion of hydrocarbons into economically valuable products by recycling has received much attention. In addition to the traditional thermochemical cycle methods, the use of a Photoelectrochemical (PEC) system is believed to address CO2A promising approach to the problem of efficient transformation. But due to CO2Thermodynamic stability of the molecule, CO2Difficult to convert into multiple electron transfer products in CO2Higher overpotential is needed in the reduction process, so that efficient photocatalysts are developed to convert CO2The reduction of the alcohol into liquid alcohol chemicals with high selectivity and low overpotential becomes a research hotspot.
In recent years many researchers have been working on improving electrochemical reduction of CO2The transition metal sulfide of interest has the advantages of complex valence state, excellent electrochemical performance, high chemical stability and the like, soCan be used for reducing CO2The catalyst is high-efficiency. However, transition metal sulfides have problems of low catalytic efficiency, low conductivity, and the like, and thus are difficult to industrialize. Recently, it has been reported in literature that sulfur vacancies can not only improve the electronic structure of the material surface, but also reduce the reaction energy barrier, and thus it is expected to solve the above problems. Preparation of cadmium sulfide and carbon nanotube composite material for CO by Binhao Qin and the like2In the reduction reaction, the carbon nano tube is used as a conductive catalyst carrier, so that the catalytic performance is improved, the Faraday efficiency of the obtained CO reduction reaction is up to 95%, but the reduction product lacks of expected alcohol chemicals.
The imidazole organic framework as a new material has the advantages of zeolite three-dimensional topological structure, high metal ion content, rich carbon-nitrogen ligands and the like, so the performance of the imidazole organic framework is superior to that of a carbon nano tube in many aspects. Whether the nitrogen-doped carbon material-wrapped copper-cadmium sulfide catalyst of the core-shell structure nano-particles is possible to be constructed by adopting a pyrolysis method or not so as to effectively improve CO2Product selectivity for conversion to liquid alcohol fuels, a very interesting technical direction to have conversion to CO2The method has a strong application prospect in producing high-value chemicals, but no literature report exists in the research on the aspect.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photo-reduction of CO2A method.
In order to solve the technical problem, the solution of the invention is as follows:
provides a nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photo-reduction of CO2The method comprises the following steps:
(1) taking Cd (NO) according to the proportion of 3.5 mmol: 7.0 mmol: 70mL3)2·4H2O、Cu(NO3)2·4H2Mixing and dissolving O, thiourea, polyvinylpyrrolidone and anhydrous glycol, and then carrying out ultrasonic treatment to form a uniform solution; pouring the solution into a stainless steel autoclave, and heating for 4 hours at 120 ℃ to obtain copper-cadmium sulfide nano particles;
(2) dissolving 2.5mg of the copper-cadmium sulfide nano-particles in the step (1) in 2mL of anhydrous methanol; then dropwise adding the mixture into 30mL of dimethyl imidazole solution; the mass concentration of the dimethyl imidazole solution is 10mM, and absolute methanol is used as a solvent; the mixed solution was sonicated for 15min, then 10mL of Zn (NO) with a mass concentration of 10mM3)2·6H2Pouring the absolute methanol solution of O into the mixed solution, and reacting for 2 hours at room temperature; after the reaction is finished, precipitating and centrifuging, and washing with anhydrous methanol; drying at 80 ℃ for 12h to obtain solid mixture imidazole organic framework coated copper-cadmium sulfide nanoparticles;
(3) putting the solid mixture in the step (2) into a tube furnace, and introducing N2Heating to 300-700 ℃; calcining for 2 hours at constant temperature to prepare the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst; taking 10mg of the catalyst, 100 mu L of deionized water and 200 mu L of Nafion solution, carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture to be 1cm2On the carbon cloth; then drying the mixture in a vacuum oven at 80 ℃ for 8 hours to prepare a cathode electrode;
(4) 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2O, pouring into 50mL of deionized water, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; grinding the solid in a mortar, pouring the ground solid into a crucible, and calcining the crucible in a muffle furnace at the constant temperature of 550 ℃ for 5 hours to obtain NiO/Fe2O3A catalyst;
(5) 20.3g of g-C3N4Adding into 25mL of absolute ethyl alcohol, stirring and then carrying out ultrasonic treatment for 0.5 h; 6g of NiO/Fe were subsequently added2O3Catalyst is poured into the g-C3N4Stirring the solution for 24 hours to form a uniform suspension solution; transferring the suspension solution into a stainless steel autoclave, heating at 150 deg.C for 4 hr, naturally cooling, filtering, and drying at 60 deg.C to obtain NiO/Fe2O3@g-C3N4A catalyst; taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution, carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture to be 1cm2On the carbon cloth; then theDrying in a vacuum oven at 60 deg.C for 12 hr to obtain anode electrode;
(6) adopting a reactor with double cells, installing the cathode electrode prepared in the step (3) on one side, and installing the anode electrode prepared in the step (5) on the other side; the middle of the double-electric-tank reactor is connected by a sand core for isolation, and the whole reactor is sealed by optical glass; simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit;
(7) adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2Leading the mixture into a cathode cavity through a micron aerator for carrying out photoelectric reduction reaction; in the cathode chamber, CO2And generating methanol after photoelectric reduction reaction.
In CO2Reduction of CO by sulfur vacancies during the reduction reaction2The energy barrier for conversion to methanol, the nitrogen-doped carbon lowers the energy barrier for the conversion of intermediate COOH to CO, which is then transferred to the surface of copper cadmium sulfide rich in sulfur vacancies for reduction to methanol product. Photoelectric reduction of CO2And after reacting for 4 hours, collecting liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity in the liquid product as high as 80-95%.
In the step (1), the average diameter of the prepared copper-cadmium sulfide nanoparticles is 70 nm.
In the step (2), the rotating speed is controlled to be 10000rpm during sedimentation and centrifugation, and the centrifugation treatment time is 10 min.
In the step (3), the temperature rise speed of the tubular furnace is 5 ℃/min, and the average diameter of the prepared nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm.
In the step (3) and the step (5) of the present invention, the mass concentration of the Nafion solution is 10%.
Compared with the prior art, the invention has the beneficial effects that:
1. the cathode catalyst N-doped carbon-coated copper cadmium sulfide nano-particle has rich porous structure, higher specific surface area and large volumeThe amount of sulfur vacancy, high content of pyridine nitrogen and good conductivity make it a highly effective CO-promoting agent2Cathode catalyst for reduction reaction. Copper cadmium sulfide containing a large number of sulfur vacancies and nitrogen-doped carbon with high pyridine nitrogen content form a heterojunction, so that an intermediate product can be selectively adsorbed and reduced on active sites with lower energy barriers, and CO is reduced compared with a pure nitrogen-doped carbon catalyst or a copper cadmium sulfide nanoparticle catalyst2The selectivity of the methanol product in the reaction is improved by over 60 percent.
2. The photoanode catalyst NiO/Fe in the invention2O3@g-C3N4The separation efficiency of the photoproduction electron-hole is improved and the recombination of the photoproduction electron-hole is inhibited, so that more photoproduction electrons in the system are transferred to the cathode to supply CO2Reduction to produce large amounts of H+Then CO is promoted2Selectivity to hydrocarbons in the reduction process, CO2The total carbon atom conversion rate in the reduction process reaches 6310nmol/h cm2This is 3.2 times the dark reaction. Therefore, the photoanode catalyst NiO/Fe2O3@g-C3N4The carbon-coated copper cadmium sulfide nano-particles doped with nitrogen and cooperated with the electro-cathode catalyst can efficiently catalyze and reduce CO2Promoting the formation of liquid methanol fuel product.
Drawings
FIG. 1 is a flow chart of the process of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
the reagents used were: cd (NO) used in the present invention3)2·4H2O、Cu(NO3)2·4H2O, thiourea, polyvinylpyrrolidone (PVP), dimethylimidazole, Zn (NO)3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)2·9H2O, ethanol, H2SO4And NaHCO3All purchased from chemical reagents of the Chinese national medicine group, Inc.; nafion solution and Nafion membrane were purchased from dupont; carbon clothFrom Betty New energy materials, Inc., Jiangsu, China.
As shown in figure 1, the nitrogen-doped carbon-coated copper cadmium sulfide catalyst photo-electrically reduces CO2The method specifically comprises the following steps:
(1) adding Cd (NO)3)2·4H2O(3.5mmol)、Cu(NO3)2·4H2O (3.5mmol), thiourea (7.0mmol) and polyvinylpyrrolidone (7.0mmol) were dissolved in 70mL of anhydrous ethylene glycol and sonicated to form a homogeneous solution. The solution was then poured into a stainless steel autoclave and heated at 120 ℃ for 4 hours to give copper cadmium sulfide nanoparticles (average diameter of copper cadmium sulfide nanoparticles is 70 nm).
(2) And (2) dissolving 2.5mg of the copper-cadmium sulfide nanoparticles in the step (1) in 2mL of anhydrous methanol solution, and dropwise adding 30mL of dimethyl imidazole solution (the mass concentration of the dimethyl imidazole dissolved in the anhydrous methanol is 10 mM). Treating the mixed solution with ultrasound for 15min to obtain solution containing Zn (NO)3)2·6H210mL of an anhydrous methanol solution of O (10 mM in terms of mass concentration) was poured into the mixed solution, and the mixture was reacted at room temperature for 2 hours. And (4) precipitating, centrifuging (10000rpm,10min), washing with anhydrous methanol, and drying at 80 ℃ for 12h to obtain the solid mixture imidazole organic framework coated copper-cadmium sulfide nanoparticles.
(3) Putting the solid mixture in the step (2) into a tube furnace, and introducing N2And heating to 300-700 ℃ (the heating rate is 5 ℃/min), calcining for 2 hours at constant temperature, and obtaining the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst (the average diameter of the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm). Taking 10mg of the catalyst and 200 mu L of deionized water 100 mu L, Nafion solution (the mass concentration is 10 percent), evenly mixing by adopting ultrasonic treatment, and brushing on 1cm2And then drying the carbon cloth in a vacuum oven at 80 ℃ for 8 hours to prepare the cathode electrode.
(4) 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2Pouring O into deionized water in a 50mL beaker, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; to fix the head to the baseGrinding the mixture in a mortar, pouring the ground mixture into a crucible, and calcining the mixture for 5 hours in a muffle furnace at the constant temperature of 550 ℃ to obtain NiO/Fe2O3A catalyst.
(5) 20.3g of g-C are taken3N4Anhydrous ethanol (25mL) was added with stirring and then sonicated for 0.5 h. 6g of NiO/Fe were subsequently added2O3Poured into the solution and stirred for 24h to form a uniform suspension solution. Finally transferring the suspension solution into a stainless steel autoclave, heating for 4 hours at 150 ℃, then naturally cooling, filtering and drying at 60 ℃ to obtain NiO/Fe2O3@g-C3N4A catalyst. Taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution, carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture to be 1cm2On the carbon cloth; then placing the anode in a vacuum oven at 60 ℃ for drying for 12 hours to prepare an anode electrode;
(6) adopting a reactor with double cells, installing the cathode electrode in the step (3) on one side, installing the anode electrode in the step (5) on the other side, sealing the reactor with optical glass, and connecting and separating the reactor with sand cores in the middle; and simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit.
(7) Adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2And the solution is introduced into a cathode cavity through a micron aerator to carry out photoelectric reduction reaction. In CO2Reduction of CO by sulfur vacancies during the reduction reaction2The energy barrier for conversion to methanol, the nitrogen-doped carbon lowers the energy barrier for the conversion of intermediate COOH to CO, which is then transferred to the surface of copper cadmium sulfide rich in sulfur vacancies for reduction to methanol product.
(8) Photoelectric reduction of CO2And after reacting for 4 hours, collecting liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity in the liquid product as high as 80-95%.
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.
Example 1
Adding Cd (NO)3)2·4H2O(3.5mmol)、Cu(NO3)2·4H2O (3.5mmol), thiourea (7.0mmol) and polyvinylpyrrolidone (7.0mmol) were dissolved in 70mL of anhydrous ethylene glycol and sonicated to form a homogeneous solution. The solution was then poured into a stainless steel autoclave and heated at 120 ℃ for 4 hours to give copper cadmium sulfide nanoparticles (average diameter of copper cadmium sulfide nanoparticles is 70 nm). 2.5mg of the copper-cadmium sulfide nanoparticles are dissolved in 2mL of anhydrous methanol solution, and 30mL of dimethyl imidazole solution (the mass concentration of dimethyl imidazole dissolved in anhydrous methanol is 10mM) is added dropwise. Treating the mixed solution with ultrasound for 15min to obtain solution containing Zn (NO)3)2·6H210mL of an anhydrous methanol solution of O (10 mM in terms of mass concentration) was poured into the mixed solution, and the mixture was reacted at room temperature for 2 hours. And (4) precipitating, centrifuging (10000rpm,10min), washing with anhydrous methanol, and drying at 80 ℃ for 12h to obtain the solid mixture imidazole organic framework coated copper-cadmium sulfide nanoparticles. The solid mixture was placed in a tube furnace and N was passed through2And heating to 300 ℃ (the heating rate is 5 ℃/min), calcining at constant temperature for 2 hours to prepare the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst (the average diameter of the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm). At the moment, the conductivity of the nitrogen-doped carbon shell is improved after calcination treatment, carbon atoms and single atoms have higher catalytic performance after high-temperature activation, copper-cadmium sulfide hardly changes, and sulfur vacancies are slightly increased. Taking 10mg of the catalyst and 200 mu L of deionized water 100 mu L, Nafion solution (the mass concentration is 10 percent), evenly mixing by adopting ultrasonic treatment, and brushing on 1cm2And then drying the carbon cloth in a vacuum oven at 80 ℃ for 8 hours to prepare the cathode electrode. 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2Pouring O into deionized water in a 50mL beaker, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; grinding the solid in a mortar, pouring the ground solid into a crucible, and calcining the solid for 5 hours in a muffle furnace at the constant temperature of 550 ℃ to obtain the catalystTo NiO/Fe2O3A catalyst. 20.3g of g-C are taken3N4Anhydrous ethanol (25mL) was added with stirring and then sonicated for 0.5 h. 6g of NiO/Fe were subsequently added2O3Poured into the solution and stirred for 24h to form a uniform suspension solution. Finally transferring the suspension solution into a stainless steel autoclave, heating for 4 hours at 150 ℃, then naturally cooling, filtering and drying at 60 ℃ to obtain NiO/Fe2O3@g-C3N4A catalyst. Taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution (the mass concentration is 10 percent), carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture on a 1cm substrate2On the carbon cloth; then, the mixture was dried in a vacuum oven at 60 ℃ for 12 hours to obtain an anode electrode. Adopting a reactor with double electric tanks, wherein a cathode electrode is arranged on one side, an anode electrode is arranged on the other side, and the reactor with the double electric tanks is sealed by optical glass, connected and separated by a sand core in the middle; and simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit. Adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2And the solution is introduced into a cathode cavity through a micron aerator to carry out photoelectric reduction reaction. In CO2Reduction of CO by sulfur vacancies during the reduction reaction2The energy barrier for conversion to methanol, the nitrogen-doped carbon lowers the energy barrier for the conversion of intermediate COOH to CO, which is then transferred to the surface of copper cadmium sulfide rich in sulfur vacancies for reduction to methanol product. Photoelectric reduction of CO2After reacting for 4h, collecting the liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity in the liquid product as high as 80%.
Example 2
Adding Cd (NO)3)2·4H2O(3.5mmol)、Cu(NO3)2·4H2O (3.5mmol), thiourea (7.0mmol) and polyvinylpyrrolidone (7.0mmol) were dissolved in 70mL of anhydrous ethylene glycol and sonicated to form a homogeneous solution. Then pouring the solution into a stainless steel autoclave, and heating for 4 hours at 120 ℃ to obtain copper-cadmium sulfide nano particles (copper-cadmium sulfide)The average diameter of the nanoparticles was 70 nm). 2.5mg of the copper-cadmium sulfide nanoparticles are dissolved in 2mL of anhydrous methanol solution, and 30mL of dimethyl imidazole solution (the mass concentration of dimethyl imidazole dissolved in anhydrous methanol is 10mM) is added dropwise. Treating the mixed solution with ultrasound for 15min to obtain solution containing Zn (NO)3)2·6H210mL of an anhydrous methanol solution of O (10 mM in terms of mass concentration) was poured into the mixed solution, and the mixture was reacted at room temperature for 2 hours. And (4) precipitating, centrifuging (10000rpm,10min), washing with anhydrous methanol, and drying at 80 ℃ for 12h to obtain the solid mixture imidazole organic framework coated copper-cadmium sulfide nanoparticles. The solid mixture was placed in a tube furnace and N was passed through2And heating to 500 ℃ (the heating rate is 5 ℃/min), calcining at constant temperature for 2 hours to prepare the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst (the average diameter of the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm). The percentage of pyridine nitrogen in the nitrogen-doped carbon shell is increased, i.e. CO is adsorbed2The number of active sites of the reduction intermediate product is increased, and the content of sulfur vacancies in the copper-cadmium sulfide is obviously increased, thereby reducing CO2A reaction barrier to reduction to methanol. Taking 10mg of the catalyst and 200 mu L of deionized water 100 mu L, Nafion solution (the mass concentration is 10 percent), evenly mixing by adopting ultrasonic treatment, and brushing on 1cm2And then drying the carbon cloth in a vacuum oven at 80 ℃ for 8 hours to prepare the cathode electrode. 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2Pouring O into deionized water in a 50mL beaker, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; grinding the solid in a mortar, pouring the ground solid into a crucible, and calcining the crucible in a muffle furnace at the constant temperature of 550 ℃ for 5 hours to obtain NiO/Fe2O3A catalyst. 20.3g of g-C are taken3N4Anhydrous ethanol (25mL) was added with stirring and then sonicated for 0.5 h. 6g of NiO/Fe were subsequently added2O3Poured into the solution and stirred for 24h to form a uniform suspension solution. Finally transferring the suspension solution into a stainless steel autoclave, heating for 4 hours at 150 ℃, then naturally cooling, filtering and drying at 60 ℃ to obtain NiO/Fe2O3@g-C3N4A catalyst. Taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution (the mass concentration is 10 percent), carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture on a 1cm substrate2On the carbon cloth; then, the mixture was dried in a vacuum oven at 60 ℃ for 12 hours to obtain an anode electrode. Adopting a reactor with double electric tanks, wherein a cathode electrode is arranged on one side, an anode electrode is arranged on the other side, and the reactor with the double electric tanks is sealed by optical glass, connected and separated by a sand core in the middle; and simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit. Adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2And the solution is introduced into a cathode cavity through a micron aerator to carry out photoelectric reduction reaction. In CO2Reduction of CO by sulfur vacancies during the reduction reaction2The energy barrier for conversion to methanol, the nitrogen-doped carbon lowers the energy barrier for the conversion of intermediate COOH to CO, which is then transferred to the surface of copper cadmium sulfide rich in sulfur vacancies for reduction to methanol product. Photoelectric reduction of CO2After reacting for 4h, collecting the liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity in the liquid product as high as 95%.
Example 3
Adding Cd (NO)3)2·4H2O(3.5mmol)、Cu(NO3)2·4H2O (3.5mmol), thiourea (7.0mmol) and polyvinylpyrrolidone (7.0mmol) were dissolved in 70mL of anhydrous ethylene glycol and sonicated to form a homogeneous solution. The solution was then poured into a stainless steel autoclave and heated at 120 ℃ for 4 hours to give copper cadmium sulfide nanoparticles (average diameter of copper cadmium sulfide nanoparticles is 70 nm). 2.5mg of the copper-cadmium sulfide nanoparticles are dissolved in 2mL of anhydrous methanol solution, and 30mL of dimethyl imidazole solution (the mass concentration of dimethyl imidazole dissolved in anhydrous methanol is 10mM) is added dropwise. Treating the mixed solution with ultrasound for 15min to obtain solution containing Zn (NO)3)2·6H210mL of an anhydrous methanol solution of O (10 mM in terms of mass concentration) was poured into the mixed solution, and the mixture was reacted at room temperature for 2 hours. Precipitating and separatingAnd (4) washing the core (10000rpm,10min) by using absolute methanol, and drying at 80 ℃ for 12h to obtain the solid mixture imidazole organic framework coated copper-cadmium sulfide nano-particles. The solid mixture was placed in a tube furnace and N was passed through2And heating to 700 ℃ (the heating rate is 5 ℃/min), calcining at constant temperature for 2 hours to prepare the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst (the average diameter of the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm). At the moment, the conductivity of the nitrogen-doped carbon shell is good, and the nitrogen content of pyridine is almost unchanged, which is beneficial to CO2And the adsorption and reduction reaction of intermediate products, but the copper-cadmium sulfide is completely volatilized due to overhigh calcination temperature, so that CO is caused2The reduction efficiency is reduced. Taking 10mg of the catalyst and 200 mu L of deionized water 100 mu L, Nafion solution (the mass concentration is 10 percent), evenly mixing by adopting ultrasonic treatment, and brushing on 1cm2And then drying the carbon cloth in a vacuum oven at 80 ℃ for 8 hours to prepare the cathode electrode. 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2Pouring O into deionized water in a 50mL beaker, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; grinding the solid in a mortar, pouring the ground solid into a crucible, and calcining the crucible in a muffle furnace at the constant temperature of 550 ℃ for 5 hours to obtain NiO/Fe2O3A catalyst. 20.3g of g-C are taken3N4Anhydrous ethanol (25mL) was added with stirring and then sonicated for 0.5 h. 6g of NiO/Fe were subsequently added2O3Poured into the solution and stirred for 24h to form a uniform suspension solution. Finally transferring the suspension solution into a stainless steel autoclave, heating for 4 hours at 150 ℃, then naturally cooling, filtering and drying at 60 ℃ to obtain NiO/Fe2O3@g-C3N4A catalyst. Taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution (the mass concentration is 10 percent), carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture on a 1cm substrate2On the carbon cloth; then, the mixture was dried in a vacuum oven at 60 ℃ for 12 hours to obtain an anode electrode. The reactor adopts a double-electric-tank reactor, one side is provided with a cathode electrode, the other side is provided with an anode electrode, and the double-electric-tank reactor adopts lightSealing the glass and connecting and separating the glass and the glass by a sand core in the middle; and simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit. Adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2And the solution is introduced into a cathode cavity through a micron aerator to carry out photoelectric reduction reaction. In CO2Reduction of CO by sulfur vacancies during the reduction reaction2The energy barrier for conversion to methanol, the nitrogen-doped carbon lowers the energy barrier for the conversion of intermediate COOH to CO, which is then transferred to the surface of copper cadmium sulfide rich in sulfur vacancies for reduction to methanol product. Photoelectric reduction of CO2After reacting for 4h, collecting the liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph, wherein the selectivity of methanol in the obtained liquid product is up to 87%.
Comparative example 1
Zinc zeolite imidazolate framework ZIF8 was placed in a tube furnace and N was passed through2Heating to 500 deg.c at 5 deg.c/min, constant temperature calcining and carbonizing for 2 hr to obtain pure nitrogen doped carbon catalyst. A cathode electrode was constructed in example 2 using this catalyst, and otherwise exactly the same manner as in example 2 was employed. Photoelectric reduction of CO2After reacting for 4h, collecting the liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity in the liquid product of 32%. Example 2 photo-reduction of CO under the same conditions as the pure nitrogen-doped carbon catalyst2The selectivity of methanol generated by the reaction is 63 percent higher.
Comparative example 2
Putting the copper-cadmium sulfide nano particles into a tube furnace, and introducing N2Heating to 500 ℃ at the speed of 5 ℃/min, calcining at constant temperature and carbonizing for 2 hours to prepare the copper-cadmium sulfide nanoparticle catalyst rich in sulfur vacancies. A cathode electrode was constructed in example 2 using this catalyst, and otherwise exactly the same manner as in example 2 was employed. Photoelectric reduction of CO2After reacting for 4h, collecting the liquid in the cathode cavity, and detecting the components of the liquid phase product by using a gas chromatograph to obtain the methanol selectivity of 21% in the liquid product. Relative copperCadmium sulfide nanoparticle catalyst, example 2, photo-electro reduction of CO under the same conditions2The selectivity of methanol generated by the reaction is higher than 74%.
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. Nitrogen-doped carbon-coated copper-cadmium sulfide catalyst for photo-reduction of CO2The method is characterized by comprising the following steps:
(1) taking Cd (NO) according to the proportion of 3.5 mmol: 7.0 mmol: 70mL3)2·4H2O、Cu(NO3)2·4H2Mixing and dissolving O, thiourea, polyvinylpyrrolidone and anhydrous glycol, and then carrying out ultrasonic treatment to form a uniform solution; pouring the solution into a stainless steel autoclave, and heating for 4 hours at 120 ℃ to obtain copper-cadmium sulfide nano particles;
(2) dissolving 2.5mg of the copper-cadmium sulfide nano-particles in the step (1) in 2mL of anhydrous methanol; then dropwise adding the mixture into 30mL of dimethyl imidazole solution; the mass concentration of the dimethyl imidazole solution is 10mM, and absolute methanol is used as a solvent; the mixed solution was sonicated for 15min, then 10mL of Zn (NO) with a mass concentration of 10mM3)2·6H2Pouring the absolute methanol solution of O into the mixed solution, and reacting for 2 hours at room temperature; after the reaction is finished, precipitating and centrifuging, and washing with anhydrous methanol; drying at 80 ℃ for 12h to obtain solid mixture imidazole organic framework coated copper-cadmium sulfide nanoparticles;
(3) putting the solid mixture in the step (2) into a tube furnace, and introducing N2Heating to 300-700 ℃; calcining for 2 hours at constant temperature to prepare the nitrogen-doped carbon-coated copper-cadmium sulfide catalyst; taking 10mg of the catalyst, 100 mu L of deionized water and 200 mu L of Nafion solution, carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture to be 1cm2On the carbon cloth; then placing the mixture in vacuum at 80 DEG CDrying in an oven for 8 hours to prepare a cathode electrode;
(4) 12.3g of Fe (NO) are taken3)3·9H2O and 12.3g of Ni (NO)3)2·6H2O, pouring into 50mL of deionized water, and stirring for 30 minutes to obtain a mixed solution; heating the mixed solution in a water bath at 110 ℃ for 30 minutes until water is completely evaporated to obtain a solid; grinding the solid in a mortar, pouring the ground solid into a crucible, and calcining the crucible in a muffle furnace at the constant temperature of 550 ℃ for 5 hours to obtain NiO/Fe2O3A catalyst;
(5) 20.3g of g-C3N4Adding into 25mL of absolute ethyl alcohol, stirring and then carrying out ultrasonic treatment for 0.5 h; 6g of NiO/Fe were subsequently added2O3Catalyst is poured into the g-C3N4Stirring the solution for 24 hours to form a uniform suspension solution; transferring the suspension solution into a stainless steel autoclave, heating at 150 deg.C for 4 hr, naturally cooling, filtering, and drying at 60 deg.C to obtain NiO/Fe2O3@g-C3N4A catalyst; taking 50mg of the catalyst, 300 mu L of deionized water and 300 mu L of Nafion solution, carrying out ultrasonic treatment, mixing uniformly, and brushing on the mixture to be 1cm2On the carbon cloth; then placing the anode in a vacuum oven at 60 ℃ for drying for 12 hours to prepare an anode electrode;
(6) adopting a reactor with double cells, installing the cathode electrode prepared in the step (3) on one side, and installing the anode electrode prepared in the step (5) on the other side; the middle of the double-electric-tank reactor is connected by a sand core for isolation, and the whole reactor is sealed by optical glass; simulating solar ultraviolet light by using an ultraviolet lamp to irradiate the anode electrode, and connecting the anode electrode and the cathode electrode to form an external circuit;
(7) adding deionized water solution into the anode cavity of the double-electric-tank reactor, adding anhydrous dimethylformamide organic solution into the cathode cavity, and adding CO2Leading the mixture into a cathode cavity through a micron aerator for carrying out photoelectric reduction reaction; in the cathode chamber, CO2And generating methanol after photoelectric reduction reaction.
2. The method of claim 1, wherein in step (1), the average diameter of the prepared copper-cadmium sulfide nanoparticles is 70 nm.
3. The method according to claim 1, wherein in the step (2), the control rotation speed for the sedimentation centrifugation is 10000rpm, and the centrifugation treatment time is 10 min.
4. The method of claim 1, wherein in the step (3), the temperature rise rate of the tube furnace is 5 ℃/min, and the average diameter of the prepared nitrogen-doped carbon-coated copper-cadmium sulfide catalyst is 370 nm.
5. The method according to claim 1, wherein in the step (3) and the step (5), the mass concentration of the Nafion solution is 10%.
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