CN114908363A - Membrane electrode assembly reactor and application thereof - Google Patents
Membrane electrode assembly reactor and application thereof Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
- C25B11/032—Gas diffusion electrodes
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
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- C25B3/00—Electrolytic production of organic compounds
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- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the field of electrochemical catalysis, and particularly relates to a membrane electrode assembly reactor and application thereof. To solve the problem of electrochemical CO 2 A series of challenges in the field of reducing formic acid and researching that CO can be converted 2 A system for converting into a pure formic acid solution, which simultaneously meets the following basic requirements: the product is pure, has higher concentration and can meet the requirement of stable production. The invention aims to electrocatalysis of CO by adopting a metal bismuth-based material as a catalyst based on a membrane electrode assembly reactor 2 Reduction productionThe formic acid solution, especially the structure of the device is designed and optimized, the system does not need to introduce metal salt electrolyte, and pure formic acid solution with higher concentration can be directly obtained by continuously introducing water vapor into the anode.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and particularly relates to a membrane electrode assembly reactor and application thereof.
Background
Today, energy shortage and environmental pollution are two major global challenges facing society. The increasing activities not only accelerate the dependence and consumption of fossil fuels, but also lead to the greenhouse gas CO 2 An increase in the amount of emissions. How to effectively reduce CO in the atmosphere 2 Leveling and achieving further utilization has become an important research topic.
Existing realization of CO 2 The conversion method comprises a mineralization method, a chemical reforming method, an enzyme catalysis method, a light/electrochemical method and the like. Wherein CO is driven by renewable energy 2 Electrocatalytic reduction of CO 2 The method has special advantages such as mild operation conditions, adjustable product selectivity and the like by converting the raw materials into chemical raw materials with high added values.
In electrocatalysis of CO 2 Reduction reaction (CO) 2 RR) System, the metal catalysts are generally divided into four groups, CO-selective metal, HCOOH-selective metal, and H, depending on the type of the reduction product 2 Selective metals and Cu which can produce deep reduction products. Electrochemical CO 2 The types and the distribution of the reduced products are complex, and the improvement of the selectivity of a single product has important significance.
In electrocatalysis of CO 2 In the RR system, a great deal of research has been carried out on HCOOH which is a two-electron transfer liquid product, and the research has important significance. HCOOH is one of basic organic chemical raw materials, and is widely used in various fields, for example, as an antibacterial agent in animal feed additives, an important additive for leather textile processing, a drug, an important intermediate for organic synthesis, and the like. Whether the product exists in HCOOH or formate form depends on the pH value of the system, so that a certain space exists for regulation. In the common H-type electrolytic cell and liquid phase flowing electrolytic cell reactor, KHCO is often added into the electrolyte 3 KOH, etc. to increase the conductivity of the electrolyte and the faradic efficiency of the product.
In the common neutral/alkaline electrocatalytic system, due to KHCO in the electrolyte 3 Presence of KOH, etcThe reduction product usually exists in the form of formate, and is mixed with electrolyte impurities, the concentration is low, the value of the reduction product is slightly discounted compared with that of a pure formic acid solution, and the production cost is increased due to the complicated operations of subsequent product separation, purification and the like.
To solve the problem of electrochemical CO 2 A series of challenges in the field of reducing formic acid and researching that CO can be converted 2 A system for converting into a pure formic acid solution, which simultaneously meets the following basic requirements: the product is pure, has higher concentration and can meet the requirement of stable production.
Disclosure of Invention
The invention aims to electrocatalysis of CO by taking a metal bismuth (Bi) based material as a catalyst based on a membrane electrode assembly reactor 2 The formic acid solution is produced by reduction, particularly, the structures of devices are designed and optimized, the system does not need to introduce metal salt electrolyte, and pure formic acid solution with higher concentration can be directly obtained by continuously introducing water vapor into the anode.
The invention provides a membrane electrode assembly reactor which comprises a cathode catalytic electrode and an anode catalytic electrode, wherein an anion exchange membrane is arranged between the cathode catalytic electrode and the anode catalytic electrode, and the cathode catalytic electrode comprises a gas diffusion electrode and a catalyst layer.
The gas diffusion electrode is characterized in that a catalyst layer is arranged on the surface of one side, close to the anion exchange membrane, of the gas diffusion electrode, and the catalyst layer is formed by coating a mixed solution A of a Bi-based catalyst and an anion binder on the surface of the gas diffusion electrode.
The anode catalytic electrode is etched by a titanium mesh and then put in HCl and IrCl 3 ·xH 2 And calcining the soaked mixed solution B of O to obtain the catalyst.
Preferably, the membrane electrode assembly reactor comprises a cathode plate and an anode plate; the cathode plate is arranged on the outer surface of the gas diffusion electrode, and the anode plate is arranged on the outer surface of the anode catalytic electrode.
Further, the membrane electrode assembly reactor is mainly constructed and tested to meet the following requirements: the interior of the membrane electrode assembly reactor is guaranteed to be completely sealed; the cathode device is completely sealed before being partially introduced into the gas chromatograph to prevent O 2 Equal impurities enter the membrane electrode assembly reactor to influence CO 2 The efficiency of the RR.
The negative plate is provided with a negative plate pore passage, an air inlet hole and an air outlet hole, the negative plate pore passage is arranged on the surface of one side, close to the anion exchange membrane, of the negative plate, and the air outlet hole and the air inlet hole are communicated with the negative plate pore passage.
The anode plate is provided with an anode plate pore passage, a water inlet hole and a water drain hole, the anode plate pore passage is arranged on the surface of one side, close to the anion exchange membrane, of the anode plate, and the water inlet hole and the water drain hole are communicated with the anode plate pore passage.
The contact area of the cathode plate pore channel and the anode plate pore channel with the electrode is 4-6cm 2 The two sides of the pore passage are provided with silica gel sealing gaskets with the thickness of 1-2 mm; the anode plate is a titanium metal plate, and the cathode plate is a stainless steel plate.
The pore channel of the negative plate is connected with the air inlet hole and the air outlet hole.
The pore channel of the anode plate is connected with the water inlet hole and the water discharge hole.
Preferably, the solvent of the mixed solution a is methanol or ethanol.
Preferably, the gas diffusion electrode comprises carbon paper or carbon cloth, such as Freudenberg H14C9 carbon paper; the Bi-based catalyst is Bi 2 O 3 Or BiPO 4 And (3) nanoparticles.
Preferably, the solvent of the mixed solution B is isopropanol or ethanol.
Further, said Bi 2 O 3 Purchased from Alfa Angsa (China) chemical Co., Ltd., and the purity is more than or equal to 99.9%.
Further, the BiPO 4 The nano-particles are prepared by taking bismuth nitrate pentahydrate and phosphoric acid as raw materials and carrying out one-step solvothermal reaction in ethylene glycol.
Preferably, the anionic binder comprises one or more of poly (N-methyl-piperidine-copper-terphenyl) quaternary ammonium salt (QAPT), superstationinoxa-9, XB7, XC-1, XC-2, Pention-D18, D35, D72, Orion TM1 and polyarylpiperidine resin (Piperion).
Preferably, the anion exchange membrane mainly comprises: dioxide Materials conservation X37-50-grade T, Dioxide Materials conservation X37-50-grade 60, Versogen A80-HCO3, Versogen A60-HCO3, fumsep FAA-3-50, and fumsep FAB-PK-130; the pretreatment mode of the fumasep FAA-3-50 is to place the membrane sample in 0.5-1.0M NaOH or KOH aqueous solution to keep at least 24h at room temperature, and wash the membrane sample with deionized water for multiple times for later use after being taken out.
Preferably, the catalyst amount of the catalyst layer is 0.2 to 0.6mg/cm 2 (ii) a The catalyst loading amount in the anode catalytic electrode is 1-3mg/cm 2 。
Preferably, the mass ratio of the Bi-based catalyst to the solvent of the mixed solution a is 1: 60-100 parts of; the volume ratio of the anionic adhesive to the solvent of the mixed solution A is 1: 80-120.
Preferably, the etching method is to put the titanium mesh into HCl solution with the temperature of 80-100 ℃ for 20-60 min.
Preferably, the concentration of HCl in the mixed solution B is 8-12 wt%; IrCl 3 ·xH 2 The concentration of O is 2-4 mg/mL.
The invention also provides an application of the membrane electrode assembly reactor in preparation of formic acid.
Preferably, the application comprises the following steps:
the construction and test of the membrane electrode assembly reactor mainly comprises the following steps: and introducing water vapor into the air inlet hole on the anode, and directly collecting the liquid product by the anode drain hole for subsequent detection. At the cathode, high-purity CO is mixed 2 After being humidified by water, the gas product enters the electrolytic cell from the gas inlet, flows into the cold trap through the gas outlet and is connected with relevant data of gas chromatography detection. The electrochemical test is carried out in a constant current mode, and the voltage values are not subjected to iR compensation.
At the anode, a proper amount of deionized water is added into a 100mL flask and heated to boil, water vapor is continuously conveyed into an air inlet, and a drain hole directly collects a liquid product, namely pure formic acid solution, within a certain reaction time; at the cathode, a certain flow rate of CO 2 The gas is delivered into the cathode gas inlet and the gas outlet through the humidifying water containerThe body flow rate is measured by a soap film flowmeter for calculating the gas by-product (H) 2 CO, etc.). Wherein the gas product was analyzed by on-line gas chromatography (Shanghai ramin GC 2060); the liquid product is analyzed by means of ion chromatography (Samerfei ICS-600) or nuclear magnetism, etc.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. on the basis of structural design and optimization of a membrane electrode assembly reactor, pure formic acid solution with higher concentration can be directly obtained by continuously introducing water vapor into an anode.
2. Compared with common neutral/alkaline electrochemical CO 2 The system for producing the formate from RR does not need to introduce metal salt electrolyte, simplifies the operation steps to a certain extent, reduces the cost of raw materials, and ensures that the product formic acid is pure and has higher concentration and can meet the requirement of stable production.
Drawings
FIG. 1 is a schematic diagram of a membrane electrode assembly reactor configuration;
FIG. 2 is commercial Bi of example 2 2 O 3 SEM image of the catalyst;
FIG. 3 is BiPO synthesized in example 3 4 SEM image of nanoparticle catalyst.
Description of reference numerals: 1-cathode plate, 2-gas diffusion electrode, 3-catalyst layer, 4-anion exchange membrane, 5-anode catalytic electrode, 6-anode plate, 7-air inlet hole, 8-air outlet hole, 9-water inlet hole and 10-water outlet hole.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Attempts to use different Bi-based electrocatalysts (commercial Bi) 2 O 3 Synthesized BiPO 4 Nanoparticles) testing of CO in a membrane electrode assembly reactor 2 RR yields the performance of a pure formic acid solution.
Example 1
A membrane electrode assembly reactor comprises a cathode catalytic electrode and an anode catalytic electrode, wherein an anion exchange membrane is arranged between the cathode catalytic electrode and the anode catalytic electrode, and the cathode catalytic electrode comprises a gas diffusion electrode and a catalyst layer.
The catalyst layer is prepared by coating a mixed solution A on the surface of the gas diffusion electrode, wherein the mixed solution A is a mixed solution of a Bi-based catalyst and an anionic binder.
The membrane electrode assembly reactor also comprises a cathode plate and an anode plate, wherein the cathode plate is arranged on the outer surface of the gas diffusion electrode, and the anode plate is arranged on the outer surface of the anode catalytic electrode; the anode plate is a titanium metal plate, and the cathode plate is a stainless steel plate.
The negative plate is provided with a negative plate pore passage, an air inlet and an air outlet, the negative plate pore passage is arranged on the surface of one side of the negative plate close to the gas diffusion electrode, and the air outlet and the air inlet are communicated with the negative plate pore passage; the anode plate is provided with an anode plate pore canal, a water inlet hole and a water outlet hole, the anode plate pore canal is arranged on the surface of one side of the anode plate close to the anode catalytic electrode, and the water inlet hole and the water outlet hole are communicated with the anode plate pore canal.
The contact area of the cathode plate pore channel and the anode plate pore channel with the electrode is 5cm 2 And silica gel sealing gaskets with the thickness of 1mm are arranged on two sides of the pore channel.
Example 2
Commercial Bi 2 O 3 CO 2 RR Performance test
(1) Preparation of an anode catalytic electrode: fully cleaning a 100-mesh titanium net by using ethanol and deionized water, and then putting the titanium net into an HCl solution at the temperature of 90 ℃ for etching for 40min to remove oil stains on the surface; the titanium mesh was then placed in 10mL of a solution containing 10 wt% HCl and 30mg of IrCl 3 ·xH 2 Soaking in isopropanol solution of O; and finally, taking out the titanium mesh, and calcining the titanium mesh in a muffle furnace at high temperature to prepare the anode catalyst electrode. Wherein the anode catalytic electrode is cut into 3 × 3cm 2 On which catalyst IrO 2 Has a loading of about 2mg/cm 2 。
(2) Preparation of gas diffusion electrode: freudenberg H14C9 carbon paper is directly used as a gas diffusion electrode; 20mg of commercial Bi 2 O 3 (alfa aesar ≥ 99.9%), 20 μ L of anionic binder (QAPT) dispersed in 2mL of methanol, continuously sonicating for more than 5h, and spraying the uniformly dispersed catalyst slurry on the surface of the gas diffusion electrode by using an N2 protection spray gun. And after the gas diffusion electrode is prepared, drying the gas diffusion electrode in a vacuum drying oven for 12 hours for later use. Wherein the gas diffusion electrode is cut into 3 × 3cm 2 The loading of the catalyst thereon was about 0.4mg/cm 2 。
(3) The cathode and the anode are separated by an anion exchange membrane (fumasep FAA-3-50), and the anion exchange membrane is pretreated and then placed in distilled water to be fully wetted, so that the surface is smooth and free of wrinkles.
(4) Assembling the membrane electrode assembly reactor: firstly, a gas diffusion electrode is placed on a cathode stainless steel metal plate so that a catalyst layer faces upwards; then, the wetted anion exchange membrane is placed on a gas diffusion electrode and is laid flat to avoid bubbles; then, 3-4 pieces of anode catalyst are placed on the anion exchange membrane; and finally, the anode plate is added, the nuts are screwed up by applying force, the force balance of the four nuts is ensured, and the assembly of the membrane electrode reactor is completed.
(5) And (3) building and testing an electrochemical testing device: and water vapor is introduced into the upper inlet end of the anode, and the liquid product is directly collected at the outlet end of the anode for subsequent detection. High purity CO is mixed at the cathode 2 After humidification, the water enters the electrolytic cell from the upper inlet end, and the lower outlet flows into the cold trap and then is connected with gas chromatography to detect relevant data of gas products. The electrochemical test is carried out in a constant current mode, the current values are respectively set to be-100, -200, -300, -500 and-700 mA for testing, and the test data refer to the table 1.
TABLE 1 electrochemical test data under different current conditions
Example 3
Synthetic BiPO 4 Nanoparticle CO 2 RR Performance test
(1) Preparing an anode catalytic electrode: fully cleaning a 100-mesh titanium mesh with ethanol and deionized water, and then putting the cleaned titanium mesh into an HCl solution at 90 ℃ for etching for 40min to remove oil stains on the surface; the titanium mesh was then placed in 10mL of a solution containing 10 wt% HCl and 30mg of IrCl 3 ·xH 2 Soaking in isopropanol solution of O; and finally, taking out the titanium mesh, and calcining the titanium mesh in a muffle furnace at high temperature to prepare the anode catalyst electrode. Wherein the anode catalytic electrode is cut into 3 × 3cm 2 On which catalyst IrO 2 Has a loading of about 2mg/cm 2 。
(2) Preparation of gas diffusion electrode: freudenberg H14C9 carbon paper is directly used as a gas diffusion electrode; 20mg of BiPO were added 4 The nano-particles (prepared by adopting pentahydrate bismuth nitrate and phosphoric acid as raw materials through one-step solvothermal reaction in ethylene glycol) and 20 mu L of anion adhesive (QAPT) are dispersed in 2mL of methanol and then continuously subjected to ultrasonic treatment for more than 5h, and the uniformly dispersed catalyst slurry is subjected to N-based ultrasonic treatment 2 The protective spray gun is sprayed on the surface of the gas diffusion electrode. And after the gas diffusion electrode is prepared, drying the gas diffusion electrode in a vacuum drying oven for 12 hours for later use. Wherein the gas diffusion electrode is cut into 3 × 3cm 2 The loading of the catalyst thereon was about 0.4mg/cm 2 。
(3) The cathode catalytic electrode and the anode catalytic electrode are separated by an anion exchange membrane (fumap FAA-3-50), and the anion exchange membrane is pretreated and then placed in distilled water to be fully wetted, so that the surface is smooth and free of wrinkles.
(4) Assembling the membrane electrode assembly reactor: firstly, a gas diffusion electrode is placed on a cathode stainless steel metal plate so that a catalyst layer faces upwards; then, the wetted anion exchange membrane is placed on a gas diffusion electrode and is laid flat to avoid bubbles; then, 3-4 pieces of anode catalyst are placed on the anion exchange membrane; and finally, the anode plate is added, the nuts are screwed up by applying force, the force balance of the four nuts is ensured, and the assembly of the membrane electrode reactor is completed.
(5) And (3) building and testing an electrochemical testing device: the upper inlet end of the anode is introduced with water vapor, and the outlet end of the anode directly collects liquid products for subsequent detectionAnd (6) measuring. High purity CO is mixed at the cathode 2 After humidification, the water enters the electrolytic cell from the upper inlet end, and the lower outlet flows into the cold trap and then is connected with gas chromatography to detect relevant data of gas products. The electrochemical test is carried out in a constant current mode, and the current values are respectively set to be-100, -200, -300, -500 and-700 mA for testing.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A membrane electrode assembly reactor comprises a cathode catalytic electrode and an anode catalytic electrode (5), an anion exchange membrane (4) is arranged between the cathode catalytic electrode and the anode catalytic electrode (5), and is characterized in that,
the cathode catalytic electrode comprises a gas diffusion electrode (2) and a catalyst layer (3);
the surface of one side, close to the anion exchange membrane (4), of the gas diffusion electrode (2) is provided with a catalyst layer (3), the catalyst layer (3) is prepared by coating a mixed solution A on the surface of the gas diffusion electrode (2), and the mixed solution A is a mixed solution of a Bi-based catalyst and an anion adhesive;
the anode catalytic electrode (5) is prepared by processing an etched titanium mesh by a mixed solution B and calcining the etched titanium mesh, wherein the mixed solution B is HCl and IrCl 3 ·xH 2 A mixed solution of O;
the etched titanium mesh is obtained by putting the titanium mesh into HCl solution with the temperature of 80-100 ℃ for 20-60 min.
2. A membrane electrode assembly reactor according to claim 1, further comprising a cathode plate (1) and an anode plate (6); the cathode plate (1) is arranged on the outer surface of the gas diffusion electrode (2), and the anode plate (6) is arranged on the outer surface of the anode catalytic electrode (5).
3. A membrane electrode assembly reactor according to claim 1, wherein the cathode plate (1) is provided with a cathode plate duct provided on the surface of the cathode plate (1) on the side close to the gas diffusion electrode (2), an air inlet hole (7) and an air outlet hole (8), the air outlet hole (7) and the air inlet hole (8) being in communication with the cathode plate duct;
the anode plate (6) is provided with an anode plate pore canal, a water inlet hole (9) and a water drain hole (10), the anode plate pore canal is arranged on the surface of one side of the anode plate (6) close to the anode catalytic electrode (5), and the water inlet hole (9) and the water drain hole (10) are communicated with the anode plate pore canal.
4. A membrane electrode assembly reactor according to claim 1, wherein the solvent of the mixed solution a is methanol or ethanol.
5. The membrane electrode assembly reactor according to claim 1, wherein the solvent of the mixed solution B is isopropyl alcohol or ethanol.
6. The membrane electrode assembly reactor of claim 1, wherein the Bi-based catalyst is Bi 2 O 3 Or BiPO 4 。
7. A membrane electrode assembly reactor according to claim 1, characterized in that the catalyst amount of the catalyst layer (3) is 0.2-0.6mg/cm 2 (ii) a The catalyst loading in the anode catalytic electrode (5) is 1-3mg/cm 2 。
8. A membrane electrode assembly reactor according to claim 1, wherein the concentration of HCl in the mixed solution B is 8-12 wt%; IrCl in the mixed solution B 3 ·xH 2 The concentration of O is 2-4 mg/mL.
9. Use of a membrane electrode assembly reactor according to any one of claims 1 to 8 for the preparation of formic acid.
10. Use according to claim 9, characterized in that it comprises the following steps:
s1, introducing water into the anode catalytic electrode (5);
at the same time, CO is introduced 2 Mixing with water and then introducing the mixture into the gas diffusion electrode (2);
and S2, carrying out constant current electrifying reaction on the anode catalytic electrode (5) and the gas diffusion electrode (2) to obtain formic acid.
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