CN114369843A - CO (carbon monoxide)2Catalytic reduction device and application thereof - Google Patents

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

Info

Publication number
CN114369843A
CN114369843A CN202210089354.2A CN202210089354A CN114369843A CN 114369843 A CN114369843 A CN 114369843A CN 202210089354 A CN202210089354 A CN 202210089354A CN 114369843 A CN114369843 A CN 114369843A
Authority
CN
China
Prior art keywords
exchange membrane
photoelectrocatalysis
cathode
anode
membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210089354.2A
Other languages
Chinese (zh)
Other versions
CN114369843B (en
Inventor
刘宪
文斌
赵婷婷
董金龙
陈恒
白宇洁
曹晋瑜
李子怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyuan Normal University
Original Assignee
Taiyuan Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyuan Normal University filed Critical Taiyuan Normal University
Priority to CN202210089354.2A priority Critical patent/CN114369843B/en
Publication of CN114369843A publication Critical patent/CN114369843A/en
Application granted granted Critical
Publication of CN114369843B publication Critical patent/CN114369843B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to CO2The field of catalytic reduction, in particular to CO2Catalytic reduction device and application thereof, aiming at solving the problem that the prior enzyme catalyzes CO2In the reduction technology, the problem that coenzyme is difficult to recycle is solved, the traditional catalytic system is difficult to simultaneously have the problems of mild and controllable process, high catalytic efficiency and good selectivity, and the invention is a device containing a photoelectrocatalysis composite membrane, which can realize photoelectrocatalysis and enzyme catalysis coupled CO recycling coenzyme2And (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 membraneAn 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 chamber2PBS solution, CO is carried out under xenon lamp illumination and external voltage2And (4) carrying out reduction reaction.

Description

CO (carbon monoxide)2Catalytic reduction device and application thereof
Technical Field
The invention belongs to CO2The field of catalytic reduction, in particular to CO2Catalytic 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 CO2The 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 COs2Conversion pathways such as thermochemical, photochemical, electrochemical, and biological enzymatic methods, and the like. However, due to CO2Stable molecule, high activation difficulty, and reduction of CO by the above method2In the meantime, it is difficult to construct a catalytic system having a mild and controllable process, high catalytic efficiency, and good selectivity.
The enzyme catalysis method is a green catalysis technology, has the characteristics of mild conditions, high efficiency and high selectivity, and is widely applied to the fields of biopharmaceuticals, biosensing and the like. Reduction of CO by enzyme catalysis2In 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 scale production and application of the coenzyme. Therefore, how to achieve recycling of coenzymes is a currently challenging obstacle. Coenzyme circulation is carried out by a traditional method, and a chemical method is generally adopted,Electrochemical methods, 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 also have a slow reaction rate.
Disclosure of Invention
The invention aims to solve the problem that the prior enzyme catalyzes CO2In the reduction technology, the coenzyme is difficult to recycle, the traditional catalytic system is difficult to simultaneously have the problems of mild and controllable process, high catalytic efficiency and good selectivity, a device containing a photoelectrocatalysis composite membrane is provided, and photoelectrocatalysis and enzyme catalysis coupled CO capable of recycling the coenzyme2A reduction device and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
CO (carbon monoxide)2The 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 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 coenzyme2PBS 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, FeCl is added3Or CaCl2Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and carrying out 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 C3N4、TiO2、MoS2、CdS、Cu2O、Fe2O3And BiOCl.
Further, the electrolyte aqueous solution is Na2SO4NaOH or KOH in a concentration of 0.01 to 3.0mol L-1Said CO2The PBS solution is CO2The CO2 PBS solution was formed by bubbling into a PBS solution at pH 7.2, which was formate dehydrogenase or a mixed enzyme consisting 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)2Use of a catalytic reduction unit in CO2And (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 CO2Then, it becomes an oxidized form NAD having a single 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 electrons generated by the photocatalyst to regenerate reduced NADH or NADPH which is neutral or weakly electronegative to CO2Continued participation of PBS solution migration in CO2The 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+The light is attracted to the surface of the photoelectric catalyst and directly contacts with the photoelectric catalyst, and can be 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 (2) avoiding the occurrence of H+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 of the special environment of the surface of the cation exchange membrane, the invention comprises 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 shape between the metallic nickel net covered with the photoelectric catalyst material on the surface and the liquid in the cathode chamberThe special environments of the solid-liquid interface have promotion effect on the directional conduction of electrons, hydrogen ions and coenzyme. Effectively improves the coenzyme circulation rate, thereby improving CO2Catalytic 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 invention2A 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 invention3A solution cross-linking scheme;
FIG. 4 is a MoS prepared according to example 1 of the present invention2Topography of the photocatalyst.
Detailed Description
Example 1
As shown in FIG. 1, a CO2The 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 coenzyme2PBS 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 polyvinyl alcohol and sodium carboxymethylcellulose with equal mass, pouring into a beaker, adding deionized water under stirring, heating to 60 ℃ for dissolving, adding FeCl after completely dissolving3Continuously 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 applied2And (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-1Na of (2)2SO4Adding PBS solution containing formate dehydrogenase and reduced coenzyme NADPH into the cathode chamber, and introducing CO by bubbling2Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 1.0V, CO is produced2Preparing 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 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 FeCl3Schematic representation of solution cross-linking cation exchange membranes, as can be seen from the figure, by FeCl3After 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 prepared2Morphology of the photocatalyst, from which the MoS can be seen2The 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 2:1, pouring the mixture into a beaker, adding an acetic acid aqueous solution with the mass fraction of 0.02%, continuously stirring the mixture in a constant-temperature water bath kettle at 50 ℃, 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 clean glass plate with a frame, and putting the glass plate with the frame into a blast drying box for drying to obtain an anion exchange membrane;
(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 dissolving2And 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) Before the cation exchange membrane is not completely dried, a metallic nickel net is stuck on the surface of the cation exchange membrane, and then TiO dispersed by ultrasonic is added2And (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 3.0mol L-1K of2SO4Adding electrolyte aqueous solution into cathode chamber, adding PBS solution containing formate dehydrogenase and reduced coenzyme NADH, and introducing CO by bubbling2Gas under the irradiation of xenon lamp light source and with DC power supply voltage of 1.5VCO2Preparing 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 3:1, pouring the mixture into a beaker, adding 0.03 mass percent of acetic acid aqueous solution, continuously stirring the mixture in a constant-temperature water bath kettle at 60 ℃, adding glutaraldehyde after the mixture is completely dissolved, continuously stirring the mixture for 1.5 hours, standing and defoaming the mixture, casting the mixture on a smooth and clean glass plate with a frame, and putting the glass plate with the frame into a blast drying box for drying to obtain an anion exchange membrane;
(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 dissolution2And 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) Before the cation exchange membrane is not completely dried, a metallic nickel net is stuck on the surface of the cation exchange membrane, and then the C dispersed by ultrasonic wave is added3N4And (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-1K of2SO4Adding PBS solution containing formate dehydrogenase, formaldehyde dehydrogenase, methanol dehydrogenase and reduced coenzyme NADPH into cathode chamber, and introducing CO by bubbling2Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 0.8V, CO is produced2And (3) preparing methanol by catalytic reduction. Samples were taken periodically from the cathode chamber and analyzed by gas chromatography for catalytic efficiency. After 12 hours of reaction, a sample was taken from the cathode chamber and the methanol concentration 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 0.5:1, pouring into a beaker, adding an acetic acid aqueous solution with the mass fraction of 0.005%, continuously stirring in a constant-temperature water bath kettle at 70 ℃, adding glutaraldehyde after complete dissolution, continuously stirring for 2.5h, standing for defoaming, casting on a flat and clean glass plate with a frame, and putting into a blast drying box for drying to obtain an anion exchange membrane;
(2) mixing polysulfone and cellulose acetate with equal mass, pouring into a beaker, adding 0.05% phosphoric acid aqueous solution under stirring, heating to 70 deg.C for dissolving, adding FeCl after completely dissolving3And 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) 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 ultrasonically dispersed BiOCl photocatalyst aqueous solution is cast on the surface of the metal nickel net in a flow mode 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-1Adding PBS solution containing formate dehydrogenase, formaldehyde dehydrogenase, methanol dehydrogenase and reduced coenzyme NADH into the cathode chamber, and introducing CO by bubbling2Gas, under the irradiation of xenon lamp light source and with DC power supply voltage of 0.4V, CO is produced2And (3) preparing methanol 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 (6)

1. CO (carbon monoxide)2The 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 the reactor, the reactor is divided into an anode chamber and a cathode chamber, and the anode and the cathode are respectively arranged in the anode chamber and the cathode chamberThe anode and the cathode of the direct current power supply are respectively connected with the anode and the cathode in the cathode chamber, 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 coenzyme2PBS aqueous solution, and the light source is a xenon lamp.
2. CO according to claim 12The 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 added3Or CaCl2Preparing a cation exchange membrane solution by taking the solution as a cross-linking agent, and carrying out 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 12The catalytic reduction device is characterized in that the photoelectric catalyst is C3N4、TiO2、MoS2、CdS、Cu2O、Fe2O3And BiOCl.
4. CO according to claim 12The catalytic reduction device is characterized in that the electrolyte aqueous solution is Na2SO4NaOH or KOH in a concentration of 0.01 to 3.0mol L-1Said CO2The PBS solution is CO2Adding the mixture into a PBS solution with the pH value of 7.2 by a bubbling mode to form a CO2 PBS solution, wherein the enzyme is formate dehydrogenase or a mixed enzyme consisting of formate dehydrogenase, formaldehyde dehydrogenase and methanol dehydrogenase, and the coenzyme is reduced coenzyme comprising nicotinamide adenine dinucleotide and nicotinamide adenine dinucleotide phosphate.
5. CO according to claim 12The 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.
6. A CO as claimed in claim 12Use of a catalytic reduction unit in CO2And (4) catalyzing reduction reaction.
CN202210089354.2A 2022-01-25 2022-01-25 CO (carbon monoxide) 2 Catalytic reduction device and application thereof Active CN114369843B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210089354.2A CN114369843B (en) 2022-01-25 2022-01-25 CO (carbon monoxide) 2 Catalytic reduction device and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210089354.2A CN114369843B (en) 2022-01-25 2022-01-25 CO (carbon monoxide) 2 Catalytic reduction device and application thereof

Publications (2)

Publication Number Publication Date
CN114369843A true CN114369843A (en) 2022-04-19
CN114369843B CN114369843B (en) 2023-02-03

Family

ID=81146743

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210089354.2A Active CN114369843B (en) 2022-01-25 2022-01-25 CO (carbon monoxide) 2 Catalytic reduction device and application thereof

Country Status (1)

Country Link
CN (1) CN114369843B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110315560A1 (en) * 2008-12-18 2011-12-29 The University Of Queensland Process for the production of chemicals
CN104818540A (en) * 2015-04-03 2015-08-05 中国科学院过程工程研究所 Bioactive hollow nano-fibers and hollow microcapsules for efficiently catalyzing conversion of CO2 into methanol
CN107099815A (en) * 2017-04-24 2017-08-29 太原师范学院 A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction
CN107429264A (en) * 2014-11-17 2017-12-01 詹索里克有限责任公司 Method and apparatus for chemical recycling of carbon dioxide
US20210123146A1 (en) * 2018-04-25 2021-04-29 The University Of British Columbia Systems and methods for electrochemical generation of syngas and other useful chemicals
CN113546661A (en) * 2021-07-09 2021-10-26 青岛科技大学 Carbon-based single-atom photocatalyst and preparation method and application thereof
CN113663723A (en) * 2021-07-19 2021-11-19 苏州科技大学 Carbon nitride composite material, preparation method thereof and application thereof in artificial photosynthesis
CN113981478A (en) * 2021-10-09 2022-01-28 河北工业大学 Method for carrying out bioelectrocatalysis carbon dioxide reduction on mesoporous material immobilized enzyme and application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110315560A1 (en) * 2008-12-18 2011-12-29 The University Of Queensland Process for the production of chemicals
CN107429264A (en) * 2014-11-17 2017-12-01 詹索里克有限责任公司 Method and apparatus for chemical recycling of carbon dioxide
CN104818540A (en) * 2015-04-03 2015-08-05 中国科学院过程工程研究所 Bioactive hollow nano-fibers and hollow microcapsules for efficiently catalyzing conversion of CO2 into methanol
CN107099815A (en) * 2017-04-24 2017-08-29 太原师范学院 A kind of application of Bipolar Membrane surface powder state photochemical catalyst in CO2 reduction
US20210123146A1 (en) * 2018-04-25 2021-04-29 The University Of British Columbia Systems and methods for electrochemical generation of syngas and other useful chemicals
CN113546661A (en) * 2021-07-09 2021-10-26 青岛科技大学 Carbon-based single-atom photocatalyst and preparation method and application thereof
CN113663723A (en) * 2021-07-19 2021-11-19 苏州科技大学 Carbon nitride composite material, preparation method thereof and application thereof in artificial photosynthesis
CN113981478A (en) * 2021-10-09 2022-01-28 河北工业大学 Method for carrying out bioelectrocatalysis carbon dioxide reduction on mesoporous material immobilized enzyme and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAHINDER RAMDIN等: "High-Pressure Electrochemical Reduction of CO2 to Formic Add/Formate: Effect of pH on the Downstream Separation Process and Economics", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 *

Also Published As

Publication number Publication date
CN114369843B (en) 2023-02-03

Similar Documents

Publication Publication Date Title
CN105289695B (en) A kind of graphene-supported Co-N-C oxygen reduction catalysts and preparation method thereof
CN114405437B (en) Photoelectrocatalysis device and application thereof
CN112609199A (en) Electrocatalysis H2O2Solution preparation method and device
CN102916209B (en) Maskless direct alcohol fuel cell and preparation method thereof
CN110965076A (en) Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure
CN109304464B (en) Hollow cage-shaped carbon/Ru composite microsphere for hydrogen production by electrolyzing water and preparation method thereof
CN105107539A (en) Graphene-iron-nitrogen codoped porous carbon composite catalyst for fuel cell and preparation method for graphene-iron-nitrogen codoped porous carbon composite catalyst
CN108441885A (en) A kind of composite material and its application in urea aoxidizes assistance Acid-Base electrolytic cell device for preparing hydrogen
CN109786762A (en) Structure of gradient hydrophilic-hydrophobic/air electrode and preparation method thereof
CN113549942A (en) Method and device for improving hydrogen production efficiency by electrolyzing water
CN110479277B (en) Method for promoting catalytic nitrogen fixation reaction of nano cobalt oxyhydroxide
CN114517308A (en) Bi-MOF material electrode with catalytic selectivity and preparation method thereof
CN114369843B (en) CO (carbon monoxide) 2 Catalytic reduction device and application thereof
CN109652820B (en) CO (carbon monoxide)2Preparation of electrode for electrochemical reduction, electrode and application thereof
WO2022068491A1 (en) Lead nanosheet-graphene two-dimensional composite, preparation method and application thereof
CN109833835B (en) Preparation method of concave hollow platinum-palladium nanocrystal, concave hollow platinum-palladium nanocrystal and application thereof
US20140342248A1 (en) Fuel cell
CN114774987B (en) Iron-based bipolar membrane and preparation method and application thereof
CN111905739B (en) Preparation method of catalyst applied to oxygen generator
CN110201726B (en) Ferrochromium-decorated UiO-66-based carbon dioxide photocatalytic reduction catalyst and preparation method and application thereof
CN114411176B (en) Photoelectrocatalysis preparation H 2 O 2 Device and application thereof
CN104953132A (en) Liquid flow-type alcohol-hydrogen peroxide fuel cell and manufacturing method thereof
Kurayama et al. A feasibility study of a new photosynthesis bioreactor design using TiO2 particles combined with enzymes
Xu et al. Enrichment strategies for efficient CO2 electroreduction in acidic electrolytes
Yin et al. Co3O4/C derived from ZIF-67 cathode enhances the microbial electrosynthesis of acetate from CO2

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant