CN114369843B - CO (carbon monoxide) 2 Catalytic reduction device and application thereof - Google Patents

CO (carbon monoxide) 2 Catalytic reduction device and application thereof Download PDF

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CN114369843B
CN114369843B CN202210089354.2A CN202210089354A CN114369843B CN 114369843 B CN114369843 B CN 114369843B CN 202210089354 A CN202210089354 A CN 202210089354A CN 114369843 B CN114369843 B CN 114369843B
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exchange membrane
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CN114369843A (en
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刘宪
文斌
赵婷婷
董金龙
陈恒
白宇洁
曹晋瑜
李子怡
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Taiyuan Normal University
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    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
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    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/21—Photoelectrolysis
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention belongs to CO 2 The field of catalytic reduction, in particular to CO 2 A catalytic reduction device and application thereof, aiming at solving the problem that the prior enzyme catalyzes CO 2 In the reduction technology, the problem that coenzyme is difficult to recycle is solved, and the traditional catalytic system is difficult to simultaneously have the problems of mild and controllable process, high catalytic efficiency and good selectivity 2 And (4) a reduction device. The device comprises a photoelectrocatalysis composite membrane, an anode chamber and a cathode chamber which are divided by the photoelectrocatalysis composite membrane, and an anode and a cathode. The photoelectrocatalysis composite membrane is taken as a diaphragm of an anode chamber and a cathode chamber, electrolyte aqueous solution is added into the anode chamber, and CO containing enzyme and coenzyme is added into the cathode chamber 2 PBS solution, CO is carried out under xenon lamp illumination and external voltage 2 And (4) carrying out reduction reaction.

Description

CO (carbon monoxide) 2 Catalytic reduction device and application thereof
Technical Field
The invention belongs to CO 2 Catalytic reductionField, in particular to CO 2 A catalytic reduction device and application thereof.
Background
Carbon dioxide is one of the major gases responsible for the global "greenhouse effect". The reduction of carbon dioxide into low-carbon new energy can not only reduce CO 2 The method has the advantages of discharging, generating basic chemicals and fuels, having very important practical significance for solving increasingly serious environmental and energy problems, and having positive propulsion effect on realizing strategic goals of carbon peak reaching and carbon neutralization in China. Currently, researchers have developed a variety of COs 2 Conversion pathways such as thermochemical, photochemical, electrochemical, and biological enzymatic methods, and the like. However, due to CO 2 Stable molecule, high activation difficulty, and reduction of CO by the above method 2 In the meantime, it is difficult to construct a catalytic system having a mild and controllable process, high catalytic efficiency, and good selectivity.
As a green catalysis technology, the enzyme catalysis method has the characteristics of mild conditions, high efficiency and high selectivity, and is widely applied to the fields of biological pharmacy, biological sensing and the like. Reduction of CO by enzyme catalysis 2 In the process, not only can the reactant molecules be activated, but also the activation energy required by the reaction can be reduced. However, in the enzyme catalysis process, coenzyme is required to be added continuously, but the expensive coenzyme greatly limits the large-scale production and application of the coenzyme. Therefore, how to achieve recycling of coenzymes is a currently challenging obstacle. Coenzyme circulation is conventionally performed by chemical, electrochemical, photochemical methods, and the like. The main disadvantages of chemical methods are the lack of specificity, the easy inactivation of the coenzyme, the difficult separation of the product due to the contamination of the chemical reagent, and even the influence on the stability of the enzyme; the electrochemical method has the disadvantages that higher overpotential needs to be overcome, and unnecessary side reactions are caused; photochemical methods generally require the addition of an electron mediator and are slow in reaction rate.
Disclosure of Invention
The invention aims to solve the problem that the prior enzyme catalyzes CO 2 In the reduction technology, coenzyme is difficult to recycle, and the traditional catalytic system is difficult to simultaneously have the problems of mild and controllable process, high catalytic efficiency and good selectivityAnd provides a device containing the photoelectrocatalysis composite membrane, which can realize the photoelectrocatalysis and enzyme catalysis coupled CO of coenzyme cyclic utilization 2 A reduction device and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
CO (carbon monoxide) 2 The catalytic reduction device comprises a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a direct current power supply and a light source; the photoelectrocatalysis composite membrane is arranged in a reactor, the reactor is divided into an anode chamber and a cathode chamber, an anode and a cathode are respectively arranged in the anode chamber and the cathode chamber, a positive pole and a negative pole of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a metal nickel net with a surface loaded with a photoelectrocatalysis, wherein the bipolar membrane is formed by compounding an anion exchange membrane and a cation exchange membrane, the metal nickel net is used as a cathode, and the metal nickel net with the surface loaded with the photoelectrocatalysis is attached to the cation exchange membrane;
the anode chamber is electrolyte aqueous solution, and the cathode chamber is CO containing enzyme and coenzyme 2 PBS aqueous solution, and the light source is a xenon lamp.
Further, the preparation method of the photoelectric catalytic composite membrane comprises the following steps:
(1) One or a mixture of a plurality of polyvinyl alcohol, polyvinylpyrrolidone, polysulfone and polyvinyl benzyl chloride in any proportion is used as the support of an anion exchange membrane, one or a plurality of compounds which are mixed according to any proportion and contain primary amino, secondary amino, tertiary amino or quaternary amino are used as the fixed group of the anion exchange membrane, glutaraldehyde solution is added as a cross-linking agent to prepare anion exchange membrane liquid, and the anion exchange membrane is prepared by a tape casting method;
(2) One or a mixture of a plurality of polyvinyl alcohol, polyvinylpyrrolidone, polyphenyl ether, polysulfone and styrene in any proportion is used as the support of the cation exchange membrane, one or a plurality of compounds containing sulfonic acid group, carboxylic acid group or phosphoric acid group which are mixed according to any proportion are used as the fixed group of the cation exchange membrane, and F is addedeCl 3 Or CaCl 2 Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and performing curtain coating on the surface of the anion exchange membrane prepared in the step (1) to obtain a cation exchange membrane;
(3) Before the cation exchange membrane is not completely dried, a metal nickel net is attached to the surface of the cation exchange membrane, and then the photocatalyst aqueous solution or the anhydrous ethanol solution dispersed by ultrasonic is cast on the surface of the metal nickel net in a flow mode to obtain the photoelectrocatalysis composite membrane.
Further, the photoelectric catalyst is C 3 N 4 、TiO 2 、MoS 2 、CdS、Cu 2 O、Fe 2 O 3 And BiOCl.
Further, the electrolyte aqueous solution is Na 2 SO 4 NaOH or KOH with a concentration of 0.01 to 3.0mol L -1 Said CO is 2 The PBS solution is CO 2 The CO2 PBS solution was formed by bubbling into a PBS solution of pH =7.2, the enzyme was formate dehydrogenase or a mixed enzyme composed of formate dehydrogenase, formaldehyde dehydrogenase and methanol dehydrogenase, and the coenzymes were reduced coenzymes including nicotinamide adenine dinucleotide and nicotinamide adenine dinucleotide phosphate, abbreviated as NADH and NADPH.
Further, the anode is a platinum sheet, and the voltage of the direct current power supply is 0.4-1.5V.
CO (carbon monoxide) 2 Use of a catalytic reduction unit in CO 2 And (4) catalyzing reduction reaction.
Compared with the prior art, the invention has the following advantages:
(1) The coenzyme NADH or NADPH in the PBS solution of the cathode chamber is used for synergistically catalyzing and reducing CO 2 Then, it becomes oxidized form NAD with one unit positive charge + Or NADP + H generated by water dissociation of the intermediate interface layer of the bipolar membrane and migrating to the surface of the cation exchange membrane under the attraction of anion groups fixed in the cation exchange membrane + Combining with the electrons generated by the photocatalyst to regenerate reduced NADH or NADPH which is neutral or weakly electronegative to CO 2 The migration of PBS solution continues to participate in CO 2 The catalytic reduction reaction realizes the recycling of the coenzyme.
(2) The invention adopts the photoelectrocatalysis method to carry out coenzyme circulation, realizes the coenzyme circulation under low voltage, solves the problems that the single electrochemical method needs to overcome higher overpotential and causes unnecessary side reaction, and simultaneously solves the problem that the single photochemical method has slow reaction rate.
(3) The invention utilizes the oxidation state NAD after the reaction of the fixed anion group pair in the bipolar membrane cation exchange membrane + Or NADP + By attraction of NAD + Or NADP + Attracted to the surface of the photoelectric catalyst, directly contacted with the photoelectric catalyst, and combined with electrons generated by the photoelectric catalyst without adding an electron vector; simultaneously utilizes H generated by water dissociation of intermediate interface layer of bipolar membrane + Provides protons for coenzyme cyclic regeneration, and can control H by regulating and controlling the water dissociation rate of the bipolar membrane intermediate interface layer + Generation rate of H is avoided + Too fast a rate of formation, resulting in loss of stability of the enzyme and coenzyme, or the appearance of H + The rate of formation is too slow, limiting the protons required for coenzyme cycling.
(4) The invention pastes the metallic nickel net and the photoelectric catalyst on the surface of the cation exchange membrane, and because the special environments on the surface of the cation exchange membrane comprise an electric field formed between an anode and a cathode, an internal electric field formed between the cation exchange membrane and the anion exchange membrane, and a solid-liquid interface formed between the metallic nickel net covered with the photoelectric catalyst material on the surface and the liquid in the cathode chamber, the special environments have promotion effects on the directional conduction of electrons, hydrogen ions and coenzyme. Effectively improves the coenzyme circulation rate, thereby improving CO 2 Catalytic reduction efficiency.
(5) The invention utilizes the characteristic that the membrane liquid is sticky, and pastes the photoelectric catalyst and the metal nickel net on the surface of the cationic membrane, thereby not only effectively avoiding the agglomeration phenomenon caused by directly adding the catalyst powder into an oil-water two-phase system in the traditional method, but also being convenient for recycling the photoelectric catalyst.
Drawings
FIG. 1 is a CO of the present invention 2 A schematic diagram of a catalytic reduction unit;
FIG. 2 is a cross-sectional SEM image of a bipolar membrane after brittle fracture in liquid nitrogen;
FIG. 3 shows FeCl used for preparing cation exchange membrane in example 1 of the present invention 3 A solution cross-linking schematic;
FIG. 4 is a MoS prepared according to example 1 of the present invention 2 Topography of the photocatalyst.
Detailed Description
Example 1
As shown in FIG. 1, a CO 2 The catalytic reduction device comprises a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a direct current power supply and a light source; the photoelectrocatalysis composite membrane is arranged in a reactor, the reactor is divided into an anode chamber and a cathode chamber, the anode and the cathode are respectively arranged in the anode chamber and the cathode chamber, the anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a metallic nickel net loaded with a photoelectrocatalysis on the surface, the bipolar membrane is formed by compounding an anion exchange membrane and a cation exchange membrane, the metallic nickel net is used as a cathode, a platinum sheet is used as an anode, and the metallic nickel net loaded with the photoelectrocatalysis on the surface is attached to the cation exchange membrane;
the anode chamber is electrolyte aqueous solution, and the cathode chamber is CO containing enzyme and coenzyme 2 PBS aqueous solution, and the light source is a xenon lamp.
The preparation method of the photoelectric catalytic composite membrane comprises the following steps:
(1) Mixing polyvinyl alcohol and chitosan with equal mass, pouring the mixture into a beaker, adding an acetic acid aqueous solution with the mass fraction of 0.01%, continuously stirring the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃, adding glutaraldehyde after the mixture is completely dissolved, continuously stirring the mixture for 1 hour, standing and defoaming the mixture, casting the mixture on a smooth and dry and clean glass plate with a frame, and putting the glass plate with the frame into a blast drying oven to dry the glass plate to obtain an anion exchange membrane;
(2) Mixing equal mass of polyvinyl alcohol and sodium carboxymethylcellulose, pouring into a beaker, adding deionized water under stirring, heating to 60 deg.C for dissolving, and dissolving completelyAdding FeCl 3 Continuously stirring the solution for 1h, standing for defoaming, and then curtain coating on the surface of the prepared anion exchange membrane to obtain a cation exchange membrane;
(3) Before the cation exchange membrane is not completely dried, a metallic nickel net is attached to the surface of the cation exchange membrane, and then the MoS dispersed by ultrasonic waves is applied 2 And (3) casting the aqueous solution of the photoelectric catalyst on the surface of the metal nickel screen to obtain the photoelectric catalytic composite membrane.
The photoelectrocatalysis composite membrane is taken as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the anode chamber is 0.01mol L -1 Na of (2) 2 SO 4 Adding PBS solution containing formate dehydrogenase and reduced coenzyme NADPH into the cathode chamber, and introducing CO by bubbling 2 Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 1.0V, CO is produced 2 Preparing formic acid by catalytic reduction. After 30 hours of reaction, a sample was taken from the cathode chamber and the formic acid concentration was measured by gas chromatography to be 0.157mol L -1 。
Fig. 2 is a cross-sectional SEM image of the bipolar membrane after it has been embrittled in liquid nitrogen, from which the anion-exchange membrane and the cation-exchange membrane constituting the bipolar membrane, and the intermediate interface layer between the two membrane layers, can be clearly seen. The thickness of the middle interface layer of the bipolar membrane is only nano-scale thickness, so that even if a small voltage is applied to two sides of the bipolar membrane, the middle interface layer of the bipolar membrane can form a strong electric field, and under the action of the strong electric field, water molecules in the middle interface layer of the bipolar membrane can be dissociated.
FIG. 3 is a schematic representation of the use of FeCl 3 Schematic representation of solution cross-linking of cation exchange membranes, as can be seen from the figure, by FeCl 3 After the solution is crosslinked, the cation exchange membrane forms a net structure, which is beneficial to improving the mechanical property of the membrane, thereby prolonging the service life of the membrane.
FIG. 4 is a MoS prepared 2 Morphology of the photocatalyst, from which the MoS can be seen 2 The photocatalyst has a single-layer or few-layer lamellar structure, and is beneficial to improving the separation efficiency of photon-generated carriers, thereby improving the photoelectric catalysis efficiency.
Example 2
The difference from the embodiment 1 is that the preparation method of the photoelectric catalytic composite membrane comprises the following specific steps:
(1) Mixing polyvinylpyrrolidone and quaternary ammonium polysulfone in a mass ratio of 2;
(2) Mixing polyvinylpyrrolidone and sodium cellulose phosphate with equal mass, pouring into a beaker, adding deionized water under stirring, heating to 60 ℃ for dissolving, adding CaCl after completely dissolving 2 And continuously stirring the solution for 1h, standing for defoaming, and then casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) Attaching a metallic nickel net on the surface of the cation exchange membrane before the cation exchange membrane is not completely dried, and then attaching the TiO dispersed by ultrasonic 2 And casting the aqueous solution of the photoelectric catalyst on the surface of the metal nickel screen to obtain the photoelectric catalytic composite membrane.
The photoelectrocatalysis composite membrane is taken as a diaphragm of an anode chamber and a cathode chamber, and the anode chamber is added with 3.0mol L of water -1 K of 2 SO 4 Adding electrolyte aqueous solution into cathode chamber, adding PBS solution containing formate dehydrogenase and reduced coenzyme NADH, and introducing CO by bubbling 2 Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 1.5V, CO is produced 2 Preparing formic acid by catalytic reduction. After 38 hours of reaction, a sample was taken from the cathode chamber and the formic acid concentration was measured by gas chromatography to be 0.162mol L -1 。
Example 3
The difference from the embodiment 1 is that the preparation method of the photoelectric catalytic composite membrane comprises the following specific steps:
(1) Mixing polyethylene benzyl chloride and polyimide in a mass ratio of 3;
(2) Mixing polyphenyl ether and sodium cellulose sulfonate with equal mass, pouring into a beaker, adding deionized water while stirring, heating to 70 ℃ for dissolution, adding CaCl after complete dissolution 2 And continuously stirring the solution for 1h, standing for defoaming, and then casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) Attaching a metallic nickel net on the surface of the cation exchange membrane before the cation exchange membrane is not completely dried, and then attaching the ultrasonically dispersed C 3 N 4 And (3) casting the aqueous solution of the photoelectric catalyst on the surface of the metal nickel screen to obtain the photoelectric catalytic composite membrane.
The photoelectrocatalysis composite membrane is taken as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the added water in the anode chamber is 0.01mol L -1 K of 2 SO 4 Adding PBS solution containing formate dehydrogenase, formaldehyde dehydrogenase, methanol dehydrogenase and reduced coenzyme NADPH into cathode chamber, and introducing CO by bubbling 2 Gas, under the irradiation of xenon lamp light source and DC power supply voltage of 0.8V, CO treatment 2 And (3) preparing methanol by catalytic reduction. Samples were taken periodically from the cathode chamber and analyzed by gas chromatography for their catalytic efficiency. After 12 hours of reaction, a sample was taken from the cathode chamber and the concentration of methanol was 56.28. Mu. Mol L as measured by gas chromatography -1 。
Example 4
The difference from the embodiment 1 is that the preparation method of the photoelectric catalytic composite membrane comprises the following specific steps:
(1) Mixing polysulfone and glyceryl trimethyl ammonium chloride in a mass ratio of 0.5;
(2) Mixing polysulfone and cellulose acetate with equal mass, pouring into a beaker, adding 0.05 mass percent of phosphoric acid water under stirringHeating the solution to 70 ℃ to dissolve the solution, adding FeCl after the solution is completely dissolved 3 And continuously stirring the solution for 1h, standing for defoaming, and then casting on the surface of the prepared anion exchange membrane to obtain the cation exchange membrane.
(3) And (3) attaching a metal nickel net to the surface of the cation exchange membrane before the cation exchange membrane is not completely dried, and then casting the ultrasonically dispersed BiOCl photocatalyst aqueous solution on the surface of the metal nickel net to obtain the photoelectrocatalysis composite membrane.
The photoelectrocatalysis composite membrane is taken as a diaphragm of an anode chamber and a cathode chamber, and the concentration of the added water in the anode chamber is 0.01mol L -1 Adding PBS solution containing formate dehydrogenase, formaldehyde dehydrogenase, methanol dehydrogenase and reduced coenzyme NADH into the cathode chamber, and introducing CO by bubbling 2 Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 0.4V, CO is produced 2 The methanol is prepared by catalytic reduction. Samples were taken periodically from the cathode chamber and analyzed by gas chromatography for catalytic efficiency. After 10 hours of reaction, a sample was taken from the cathode chamber and the concentration of methanol was measured by gas chromatography to be 10.28. Mu. Mol L -1 。

Claims (4)

1. CO (carbon monoxide) 2 The catalytic reduction device is characterized by comprising a reactor, a photoelectrocatalysis composite membrane, a cathode, an anode, a direct current power supply and a light source; the photoelectrocatalysis composite membrane is arranged in a reactor, the reactor is divided into an anode chamber and a cathode chamber, the anode and the cathode are respectively arranged in the anode chamber and the cathode chamber, the anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode, and the light source is arranged above the cathode chamber;
the photoelectrocatalysis composite membrane consists of a bipolar membrane and a metal nickel net with a surface loaded with a photoelectrocatalysis, wherein the bipolar membrane is formed by compounding an anion exchange membrane and a cation exchange membrane, the metal nickel net is used as a cathode, and the metal nickel net with the surface loaded with the photoelectrocatalysis is attached to the cation exchange membrane;
the anode chamber is electrolyte aqueous solution, and the cathode chamber is CO containing enzyme and coenzyme 2 PBS aqueous solution, the said light source is xenon lamp;
the photoelectric catalyst is C 3 N 4 、TiO 2 、MoS 2 、CdS、Cu 2 O、Fe 2 O 3 And BiOCl; the electrolyte aqueous solution is Na 2 SO 4 NaOH or KOH with the concentration of 0.01 to 3.0 mol/L, and the CO 2 The PBS solution is CO 2 Bubbling into a PBS solution with pH =7.2 to form CO 2 The enzyme is formate dehydrogenase or a mixed enzyme consisting of formate dehydrogenase, formaldehyde dehydrogenase and methanol dehydrogenase, the coenzyme is reduced coenzyme, and the reduced coenzyme is nicotinamide adenine dinucleotide or nicotinamide adenine dinucleotide phosphate.
2. CO according to claim 1 2 The catalytic reduction device is characterized in that the preparation method of the photoelectrocatalysis composite membrane is as follows:
(1) One or a mixture of a plurality of polyvinyl alcohol, polyvinylpyrrolidone, polysulfone and polyvinyl benzyl chloride in any proportion is used as the support of an anion exchange membrane, one or a plurality of compounds which are mixed according to any proportion and contain primary amino, secondary amino, tertiary amino or quaternary amino are used as the fixed group of the anion exchange membrane, glutaraldehyde solution is added as a cross-linking agent to prepare anion exchange membrane liquid, and the anion exchange membrane is prepared by a tape casting method;
(2) One or a mixture of a plurality of polyvinyl alcohol, polyvinylpyrrolidone, polyphenyl ether, polysulfone and styrene in any proportion is used as the support of the cation exchange membrane, one or a plurality of compounds containing sulfonic acid group, carboxylic acid group or phosphoric acid group which are mixed according to any proportion are used as the fixed group of the cation exchange membrane, feCl is added 3 Or CaCl 2 Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and performing curtain coating on the surface of the anion exchange membrane prepared in the step (1) to obtain a cation exchange membrane;
(3) Before the cation exchange membrane is not completely dried, a metal nickel net is attached to the surface of the cation exchange membrane, and then the photocatalyst aqueous solution or the anhydrous ethanol solution dispersed by ultrasonic is cast on the surface of the metal nickel net in a flow mode to obtain the photoelectrocatalysis composite membrane.
3. CO according to claim 1 2 The catalytic reduction device is characterized in that the anode is a platinum sheet, and the voltage of the direct current power supply is 0.4-1.5V.
4. CO according to claim 1 2 Use of a catalytic reduction unit in CO 2 And (4) carrying out catalytic reduction reaction.
CN202210089354.2A 2022-01-25 2022-01-25 CO (carbon monoxide) 2 Catalytic reduction device and application thereof Active CN114369843B (en)

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