CN114134521B - For electrocatalytic CO2Reduced flow field membrane reactor - Google Patents
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- CN114134521B CN114134521B CN202110964402.3A CN202110964402A CN114134521B CN 114134521 B CN114134521 B CN 114134521B CN 202110964402 A CN202110964402 A CN 202110964402A CN 114134521 B CN114134521 B CN 114134521B
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Classifications
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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
- C25B3/03—Acyclic or carbocyclic hydrocarbons
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- 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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- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
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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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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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
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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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
- 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
- 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
- C25B9/60—Constructional parts of cells
Abstract
The invention discloses a through flow field membrane reactor for electrocatalytic CO 2 reduction, which consists of a cathode end plate, a cathode gas chamber, a cathode through flow field plate, a cathode gas diffusion electrode, a porous polymer diaphragm, an oxygen-evolving anode, an anode through flow field plate, an anolyte chamber and an anode end plate, wherein all the plates are sealed by extrusion of bolts and gaskets, the anode plate and the cathode plate are connected with an external circuit, the cathode gas chamber is connected with an inlet and outlet pipeline of CO 2 gas and products, and the anolyte chamber is connected with an inlet and outlet pipeline of electrolyte and products. The structure of the reactor penetrating the flow field polar plate realizes the rapid separation of anode oxygen, solves the problem of permeation of the anode electrolyte to the cathode gas diffusion electrode catalytic layer caused by oxygen pressure holding, is beneficial to discharging the cathode electrolyte, and effectively relieves the cathode flooding problem; the reactor structure can replace an expensive ionic polymer membrane by an inexpensive porous polymer membrane, and simultaneously achieves good CO 2 electrolysis stability and higher C 2H4 Faraday efficiency.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and relates to a through flow field membrane reactor for electrocatalytic CO 2 reduction.
Background
The large use of fossil energy (coal, oil and natural gas) causes a dramatic increase in the amount of CO 2 -like chamber gas emissions, causing an increasingly serious environmental problem such as global warming. The electrocatalytic CO 2 reduction reaction (CO 2 RR) generates electricity by utilizing renewable solar energy and wind energy, drives CO 2 to be converted into fuel and chemicals, and simultaneously realizes the recycling utilization of CO 2 and the effective storage of clean electric energy. In electrocatalytic CO 2 RR, the reactor structure is related to the supply and transmission process of reactants (CO 2,H2 O) and ions and other substances in the reduction process of CO 2, and is important to the formation of a gas-liquid-solid three-phase reaction interface, the system stability and the Energy Conversion Efficiency (ECE).
The performance research of the current CO 2 RR catalyst mainly uses a traditional two-chamber electrolytic cell system, namely, CO 2 dissolved in an aqueous electrolyte is used for reaction, but the solubility of CO 2 in the aqueous electrolyte is low, the diffusion path of CO 2 in a liquid phase is long, the catalytic process is limited by a CO 2 mass transfer step, the activity is difficult to improve, and even if disturbance mass transfer is increased through magnetic stirring, the current density is difficult to reach 100mA cm -2. In order to solve the problem of limited mass transfer of CO 2, a three-chamber flow electrolytic cell comprising a cathode-anode electrolyte chamber and a CO 2 air chamber is developed, CO 2 gas is directly transmitted into a catalytic layer to participate in a reaction through a gas diffusion electrode strategy, the problem of limited transmission and supply of a traditional reaction system CO 2 is avoided, and the current density can be remarkably improved (> 200mA cm -2). The three-chamber flow electrolytic cell system meets the requirement of basic research, but the larger cathode-anode distance causes large internal resistance of the system, and the ohmic polarization energy loss is increased sharply during high-current operation, so that the energy conversion efficiency is lower; in addition, the catalytic layer is easy to be flooded and blocked by crystalline salt in the long-time operation process, the transmission path of CO 2 is blocked, serious hydrogen evolution side reaction is caused, and the conversion rate of CO 2 is obviously reduced. Aiming at the problem of large internal resistance of the system, researchers use the fuel electrode structure to tightly press the cathode and anode catalytic layers and the polymer electrolyte membrane, and the integrated membrane electrode structure can greatly reduce the internal resistance of the system, but the system needs to develop an efficient and stable alkaline polymer electrolyte membrane (an alkaline membrane is still a limiting factor for the development of an alkaline fuel cell), and in addition, the difficulty that the catalytic layers are easy to flood is also existed.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a through-flow field membrane reactor for electrocatalytic CO 2 reduction, which solves the above-described series of problems with the prior art reactors.
To achieve the above and other related objects, the present invention provides a through flow field membrane reactor for electrocatalytic CO 2 reduction, comprising:
The cathode end plate, the cathode gas chamber, the cathode penetrating flow field plate, the cathode gas diffusion electrode, the porous polymer membrane, the oxygen-separating anode, the anode penetrating flow field plate, the anode electrolyte chamber and the anode end plate;
all the plates are sealed by bolt and gasket extrusion, the cathode plate is connected with an external circuit, the cathode gas chamber is connected with an inlet and outlet pipeline of CO 2 gas and products, and the anode electrolyte chamber is connected with an inlet and outlet pipeline of electrolyte and products.
Optionally, the cathode end plate, the cathode gas chamber plate, the anolyte chamber plate, and the anode end plate may be made of one or more of Polytetrafluoroethylene (PTFE), plexiglas, and polyetheretherketone.
Alternatively, the cathode plate and the anode plate may be made of one or more of stainless steel, titanium plate and stone-grinding plate.
Optionally, the cathode plate and the anode plate adopt a penetrating flow field structure, the penetrating flow field structure adopts equidistant rectangular holes, the width of the rectangular holes is about 1.5mm, and the area ratio of the holes is about 50%.
Alternatively, the porous polymer membrane is made of a hydrophilic porous Polytetrafluoroethylene (PTFE) membrane resistant to strong acid and alkali, and the pore size of the porous polymer membrane is in the range of 0.1-5 μm.
Optionally, the cathode gas diffusion electrode adopts a structure of integrating a carbon paper layer, a microporous layer and a catalytic layer, and the mass content range of PTFE of the microporous layer of the cathode gas diffusion electrode comprises 10-60%.
The invention provides a through flow field membrane reactor which is constructed by the design method.
The invention provides application of a through flow field membrane reactor, which is constructed by the design method, and is applied to electrocatalytic CO 2 reduction for preparing C 2H4.
Alternatively, the process of electrocatalytic CO 2 reduction to make C 2H4 across a flow field membrane reactor employs a commercial Cu powder catalyst, wherein the faradaic efficiency of C 2H4 for Cu electrocatalytic CO 2 reduction across a flow field membrane reactor is 37% (-3V).
As described above, the through flow field membrane reactor for electrocatalytic CO 2 reduction of the invention comprises a cathode end plate, a cathode gas chamber, a cathode through flow field plate, a cathode gas diffusion electrode, a porous polymer membrane, an oxygen-evolving anode, an anode through flow field plate, an anolyte chamber and an anode end plate, wherein the plates are sealed by bolt and gasket extrusion, the anode plate and the cathode plate are connected with an external circuit, the cathode gas chamber is connected with an inlet and outlet pipeline of CO 2 gas and products, and the anolyte chamber is connected with an inlet and outlet pipeline of electrolyte and products. The through flow field plate structure of the reactor cooperates with the porous polymer diaphragm structure to realize rapid separation of anode oxygen and discharge of catholyte, so that the problem of cathode flooding is effectively relieved; the reactor structure can realize that the cheap porous polymer membrane replaces the expensive ionic polymer membrane, and simultaneously realize good CO 2 electrolysis stability and higher energy conversion efficiency.
Drawings
Fig. 1 shows a block diagram of a flow field membrane reactor according to the present invention.
Fig. 2 shows a flow field plate structure of a flow field membrane reactor of example 1.
Fig. 3 shows the schematic representation of the co-operation of the flow field plate and porous polymer separator membrane to achieve O 2 release and fluid drainage in example 1.
Fig. 4 shows the performance graphs of the polymer electrolyte membrane reactors (a, b) and the 3V cell pressure electrolysis CO 2 reduction through the flow field membrane reactors (c, d) in example 2.
FIG. 5 shows the reduction performance of CO 2 by 3V cell pressure electrolysis through a flow field membrane reactor using an AT-1 anion exchange membrane and a 0.45 μm pore size hydrophilic PFFE polymer membrane, respectively, in example 2.
FIG. 6 shows the performance of 150mA cm -2 constant current electrolysis CO 2 reduction across a flow field membrane reactor using hydrophilic PFFE polymer membranes of different pore sizes in example 2.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Further, in describing the embodiments of the present invention in detail, the cross-sectional view of the device structure is not partially enlarged to a general scale for convenience of description, and the schematic is only an example, which should not limit the scope of protection of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in actual fabrication.
As shown in fig. 1, the present embodiment provides a through flow field membrane reactor for electrocatalytic CO 2 reduction, and the present embodiment adopts a through flow field plate structure to realize rapid separation of anode oxygen and rapid discharge of catholyte, so as to effectively alleviate cathode flooding problem; the embodiment replaces an expensive ionic polymer membrane by an inexpensive porous polymer membrane, and simultaneously realizes good CO 2 electrolysis stability and higher Faraday efficiency. The reactor comprises a cathode end plate 1, a cathode gas chamber 2, a cathode penetrating flow field polar plate 3, a cathode gas diffusion electrode 4, a porous polymer diaphragm 5, an anode end plate 6, an anolyte chamber 7, an anode penetrating flow field polar plate 8 and an oxygen-evolving anode 9, wherein the plates are sealed by gaskets 10 and bolts 11. The cathode gas chamber 2 is connected to a gas inlet line 12 and a gas outlet line 13, and the anolyte chamber 7 is connected to a liquid inlet line 14 and a liquid outlet line 15. The porous polymer membrane 5 is located between the cathode gas diffusion electrode 4 and the porous oxygen evolving anode 9, and serves three functions: (1) insulating effect, isolating the cathode and anode; (2) transport and transfer of electrolyte and ions; (3) blocking diffusion of the cathode gas to the anode. The cathode plate 3 and the anode plate 8 are connected with an external circuit to play a role of collecting current. The penetrating flow field structure of the cathode penetrating flow field polar plate 3 allows CO 2 gas to diffuse to the cathode catalytic layer through the gas diffusion layer and the micropore layer of the cathode gas diffusion electrode 4, and simultaneously is beneficial to discharging electrolyte accumulated in the cathode catalytic layer from a cathode cavity, the penetrating flow field structure of the anode polar plate 8 allows circulation of anolyte and timely discharging of an anode product O 2, and smooth discharging of O 2 can prevent formation of anode gas holding pressure and alleviate flooding problem caused by rapid infiltration of the anolyte into the cathode catalytic layer.
As an example, the materials of the cathode end plate 1, the cathode gas chamber 5, the anolyte chamber 6 and the anode end plate 2 may be one or more of Polytetrafluoroethylene (PTFE), organic glass and polyetheretherketone, and may be selected according to the application environment and specific requirements.
As an example, the materials of the cathode plate 1 and the anode plate 2 may be one or more of stainless steel, titanium plate and stone-milled plate, and may be specifically selected according to the needs.
As an example, the cathode plate 1 and the anode plate 2 adopt a penetrating flow field structure, the penetrating flow field structure adopts equidistant rectangular holes, the width of the rectangular holes is about 1.5mm, and the proportion of the open area is about 50%.
As an example, the porous polymer membrane 7 is made of porous Polytetrafluoroethylene (PTFE) and a membrane which can resist strong acid and alkali, and the pore size of the porous polymer membrane is in the range of 0.1 μm to 5 μm.
As an example, the cathode gas diffusion electrode 8 adopts a structure of integrating a carbon paper layer, a microporous layer and a catalytic layer, and the mass content range of the microporous layer PTFE of the cathode gas diffusion electrode comprises 10-60%.
The embodiment provides a through flow field membrane reactor, which is constructed by adopting the design. The through flow field membrane reactor constructed by the embodiment can alleviate the problem of cathode flooding through the synergistic effect of the through flow field polar plate and the porous polymer membrane, has low system internal resistance, and simultaneously replaces the ionic polymer membrane with the low porous polymer membrane, thereby greatly reducing the cost of the reactor.
The embodiment also provides an application of the through flow field membrane reactor in electrocatalytic CO 2 reduction, wherein the through flow field membrane reactor is constructed by adopting the design method, and the through flow field membrane reactor in electrocatalytic CO 2 reduction adopts a commercial Cu catalyst to prepare C 2H4. In this example, the C 2H4 faraday efficiency of commercial Cu electrocatalytic CO 2 reduction in a flow field membrane reactor was 37% (-3V).
The following is further illustrated by specific examples:
Example 1
The cathode gas diffusion electrode 4 is prepared by taking commercial Cu powder as a cathode catalyst, and comprises the following specific steps: weighing 20mg of commercial Cu powder and 100mg of Nafion solution (5 wt.%), adding 1mL of ethanol, uniformly dispersing by ultrasonic, spraying on a carbon paper gas diffusion layer (Dongli Japan) with a microporous layer, controlling the temperature of a heating platform to 60 ℃, controlling the spraying effective area of a stainless steel template to 4cm 2, and determining the metal loading of a catalytic layer to be 1+/-0.1 mg/cm 2 by a weighing method. Wherein, the hydrophobicity of the gas diffusion electrode is further enhanced by brushing PTFE film with a thickness of 8 μm and a pore diameter of 0.3 μm on one side of the gas diffusion layer carbon paper.
The testing process comprises the following steps: the foam NiFe oxide electrode is taken as an oxygen evolution electrode 9, a 0.45 mu m aperture hydrophilic PFFE polymer membrane is taken as a porous polymer membrane 5, the structure of a penetrating flow field polar plate of fig. 2 is adopted, the electrolytic test of the reactor is assembled according to fig. 1, a cathode gas chamber 2 is filled with high-purity CO 2 gas through a gas inlet pipeline 12, a mass flowmeter is used for controlling the gas flow rate to be 80sccm on the gas inlet pipeline 12, a soap film flowmeter is used for measuring the gas outlet flow rate on a gas outlet pipeline 13, and the concentration of a gas product is measured by gas chromatography and is used for calculating the gas phase Faraday efficiency. Anolyte was pumped by peristaltic pump circulation on anolyte (1M KOH solution) inlet line 15, controlling the flow rate to 5mL/min.
FIGS. 4a-b and FIGS. 4c-d correspond to the performance of a conventional polymer electrolyte membrane reactor employing an AT-1 anion exchange membrane and a through flow field membrane reactor employing a 0.45 μm pore size hydrophilic PFFE polymer membrane, respectively, in the reduction of electrolytic CO 2. Compared with the traditional polymer electrolyte membrane reactor, the through flow field membrane reactor can obtain larger current density, electrolytic stability and C 2H4 selectivity under the same cell pressure (3V), and can keep FE H2 and FE C2H4 stable and FE C2H4 reaches 37 percent after reacting for 1 hour under the cell pressure of 3V.
FIGS. 5a-c are properties of electrolytic CO 2 reduction using an AT-1 anion exchange membrane and a 0.45 μm pore size hydrophilic PFFE polymer membrane, respectively, in a through-flow field membrane reactor. The FE H2 was larger with anion exchange membranes and less than 20% FE C2H4, while the co-porous PFFE polymer membrane achieved greater activity and C 2H4 selectivity across the flow field plate structure (fig. 5 a).
Example 2
The gas diffusion electrode preparation method and test procedure of example 1 were employed.
FIG. 6 shows the performance of commercial Cu powder in electrocatalytic CO 2 reduction when hydrophilic PFFE polymer membranes with different pore sizes are adopted in a through-flow field membrane reactor, and the Faraday efficiency of H 2 is suppressed to about 20% and FE C2H4 reaches about 35% when constant current electrolysis is carried out under the condition of 150mA cm -2 under the condition of moderate membrane pore diameter (0.45-1.2 um), and the ion transfer process is influenced by using too small pore diameter membranes, and the cathode electrolyte is too fast permeated due to too large pore diameter membranes, so that the Faraday efficiency of H 2 is increased.
Claims (6)
1. A through flow field membrane reactor for electrocatalytic CO 2 reduction, comprising:
A cathode end plate, a cathode gas chamber plate, a cathode penetrating flow field plate, a cathode gas diffusion electrode, a porous polymer diaphragm, an oxygen-evolving anode, an anode penetrating flow field plate, an anode electrolyte chamber plate and an anode end plate;
The plates are sealed by bolt and gasket extrusion, the cathode plate is connected with an external circuit, the cathode gas chamber is connected with an inlet and outlet pipeline of CO 2 gas and products, and the anode electrolyte chamber is connected with an inlet and outlet pipeline of electrolyte and products;
The through flow field plate structure and the porous polymer diaphragm structure are cooperatively used for rapidly separating anode oxygen and discharging catholyte; in the penetrating flow field plate structure, the penetrating flow field structure of the cathode penetrating flow field plate allows CO 2 gas to diffuse to the cathode catalytic layer through the gas diffusion layer and the microporous layer of the cathode gas diffusion electrode, electrolyte accumulated in the cathode catalytic layer is discharged from the cathode cavity, the penetrating flow field structure of the anode plate allows circulation of anolyte and timely discharge of anode product O 2, and the anode plate is used for relieving rapid infiltration of anolyte into the cathode catalytic layer;
The porous polymer membrane is made of a hydrophilic porous polytetrafluoroethylene membrane resistant to strong acid and alkali, and the pore diameter of the porous polymer membrane is 0.45-1.2 um.
2. The through flow field membrane reactor according to claim 1, wherein: the cathode end plate, the cathode gas chamber plate, the anode electrolyte chamber plate and the anode end plate are made of one or more of polytetrafluoroethylene, organic glass and polyether-ether-ketone.
3. The through flow field membrane reactor according to claim 1, wherein: the cathode plate and the anode plate are made of one or more of stainless steel, titanium plate and graphite plate.
4. The through flow field membrane reactor according to claim 1, wherein: the through flow field structure adopts equidistant rectangular holes, the width of the rectangular holes is 1.5mm, and the proportion of the open areas is 50%.
5. The through flow field membrane reactor according to claim 1, wherein: the cathode gas diffusion electrode adopts an integrated structure of a carbon paper layer, a microporous layer and a catalytic layer.
6. The cathode gas diffusion electrode according to claim 5, wherein: the microporous layer PTFE mass content of the cathode gas diffusion electrode ranges from 10% to 60%.
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| CN103160851A (en) * | 2011-12-12 | 2013-06-19 | 清华大学 | Membrane reactor |
| CN109560312A (en) * | 2018-11-27 | 2019-04-02 | 杭州电子科技大学温州研究院有限公司 | A kind of micro fuel cell and its charging method suitable for high concentration methanol |
| CN212770994U (en) * | 2020-07-08 | 2021-03-23 | 福建师范大学 | Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction |
| CN113113647A (en) * | 2021-04-07 | 2021-07-13 | 南京理工大学 | Anode assembly for hydrogen-oxygen fuel cell and hydrogen-oxygen fuel cell |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160851A (en) * | 2011-12-12 | 2013-06-19 | 清华大学 | Membrane reactor |
| CN109560312A (en) * | 2018-11-27 | 2019-04-02 | 杭州电子科技大学温州研究院有限公司 | A kind of micro fuel cell and its charging method suitable for high concentration methanol |
| CN212770994U (en) * | 2020-07-08 | 2021-03-23 | 福建师范大学 | Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction |
| CN113113647A (en) * | 2021-04-07 | 2021-07-13 | 南京理工大学 | Anode assembly for hydrogen-oxygen fuel cell and hydrogen-oxygen fuel cell |
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