CN111733425A - Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction - Google Patents
Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction Download PDFInfo
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- CN111733425A CN111733425A CN202010653285.4A CN202010653285A CN111733425A CN 111733425 A CN111733425 A CN 111733425A CN 202010653285 A CN202010653285 A CN 202010653285A CN 111733425 A CN111733425 A CN 111733425A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 230000009467 reduction Effects 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title description 4
- 239000007788 liquid Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000009792 diffusion process Methods 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000004255 ion exchange chromatography Methods 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 15
- 239000012263 liquid product Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000005465 channeling Effects 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 238000004817 gas chromatography Methods 0.000 abstract description 5
- 230000008676 import Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 63
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
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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
- C25B15/00—Operating or servicing cells
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a multifunctional electrolytic cell device for electrocatalysis of carbon dioxide reduction; comprises an anode chamber circulation groove plate, a proton exchange membrane, a cathode chamber circulation groove plate and an end plate component which are arranged in sequence; the end plate component is an end plate or an end plate structure assembly which is provided with a carbon dioxide channel communicated with the cathode chamber and can be internally provided with a working electrode. The invention can realize the switching of two electrolytic cells by selecting and assembling the cell plates according to requirements, wherein a similar cross frame is arranged in the middle of the S-shaped flow channel cell plate of the end plate structure assembly to form four small windows, so that the introduced gas has long disturbance residence time, and carbon paper is used as a gas diffusion layer to be matched with the gas chamber flow channel cell plate and the cathode chamber flow channel plate, so that the diffusion of the gas to the carbon paper is enhanced, and the permeation of the liquid to the gas chamber is reduced. And the anode/cathode chamber circulation frid is all opened with the gas-liquid import and export, and external peristaltic pump can realize the real-time renewal of electrolyte, simultaneously, can realize real-time on-line detection analysis through gas chromatography and ion chromatography detection means.
Description
Technical Field
The invention relates to the technical field of electrocatalytic carbon dioxide reduction, and relates to multifunctional electrocatalytic carbon dioxide reduction (CO)2RR) and especially to a multifunctional electrolytic cell device which can be freely assembled into a T-EC two-chamber (liquid-liquid) and a T-GDE three-chamber (gas-liquid) through practical requirements.
Background
Electrocatalytic CO2Conversion to fuels or other useful chemicals is considered to be one of the most promising routes that are controllable, environmentally friendly and efficient. However, CO2The inherent chemical inertness and its high bond energy make the activation process particularly difficult, with CO2The electroreduction process is simultaneously accompanied by H2Etc. are produced, resulting in CO2The Faraday efficiency of the electroreduction is low, and the like.
The device of the electrocatalytic reaction is an important influence factor such as pH of the electrolyte solution, dissolution and diffusion of gas, separation detection of products, and reaction efficiency, and thus the electrolytic cell device has an extremely important influence on the reaction. The commonly used H-type electrolytic cell is a typical two-chamber electrolytic cell, but the anode and cathode are far apart, the mass transfer distance is large, the energy loss is high, and the solubility of the electrolyte is changed, so that the reaction efficiency is low, and simultaneously, the raw material gas CO is low2The three-chamber electrolytic cell is modified by a fuel cell, has a small gas flow field and a small effective catalytic area, and can cause liquid seepage phenomenon, so that the reaction efficiency is low.
Disclosure of Invention
In order to solve the problems, the invention provides a multifunctional electrolytic cell device for electrocatalytic carbon dioxide reduction; the cell plates can be selected according to requirements to be assembled to realize the switching of two electrolytic cells, the distance between the anode and the cathode can be greatly shortened, the mass transfer distance and the energy loss are reduced, the electrolyte is updated in real time, the gas flow field and the retention time are increased, the contact area is increased, the liquid seepage phenomenon is reduced, and the catalytic reaction efficiency is greatly enhanced.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention relates to a multifunctional electrolytic cell device for electrocatalysis carbon dioxide reduction, which comprises an anode chamber circulation groove plate, a proton exchange membrane, a cathode chamber circulation groove plate and an end plate component which are arranged in sequence and sealed by a sealing gasket;
a concave part is arranged on the anode chamber circulation groove plate to form an anode chamber; the anode chamber circulation cell plate is respectively provided with a gas inlet and a gas outlet, a liquid inlet and a liquid outlet and two through holes provided with hollow screws, wherein one hollow screw is inserted into the counter electrode; the gas inlet and outlet are arranged to be in a lower inlet and an upper outlet; the liquid in the anode chamber enters from bottom to top;
a hollow cathode chamber is arranged in the cathode chamber flow groove plate, a gas inlet and a gas outlet, a liquid inlet and a liquid outlet and two through holes provided with hollow screws are respectively arranged on the cathode chamber flow groove plate, and a reference electrode is inserted into one hollow screw; the gas and the liquid in the cathode chamber are all discharged from the bottom to the top;
the end plate component is an end plate or an end plate structure assembly which is provided with a carbon dioxide channel communicated with the cathode chamber and can be internally provided with a working electrode.
When the end plate component is an end plate, the working electrode is inserted into the other hollow screw of the cathode chamber flow groove plate, and during operation, carbon dioxide is connected into the gas inlet and outlet according to the principle of downward inlet and upward outlet.
As an embodiment of the invention, the end plate structure assembly consists of a gas chamber flow channel groove plate, a working electrode fixing plate and a working electrode;
two layers of concave diversion trenches are arranged on the air chamber flow channel groove plate: the gas diversion groove is arranged at the lower layer of the rectangular diversion groove; the gas diversion groove is internally provided with a baffle block which can prolong the staying time of the gas in the gas diversion groove; the upper and lower parts of the two sides of the air chamber flow channel groove plate are respectively provided with a hole communicated with the air flow channel in the groove plate (the hole is provided with an air circulation quick connector);
windows communicated with the gas diversion grooves are formed in the positions, contacting with the carbon paper diffusion layer on the working electrode, on the working electrode fixing plate;
the working electrode is fixed by the working electrode fixing plates on two sides and then is attached to the grooves on the periphery of the rectangular diversion trench, and the working electrode fixing plates on the outer side are flush with the edge surfaces of the air chamber runner channel plates.
As an embodiment of the present invention, the gas guiding groove is an S-shaped guiding groove; the part of the S-shaped diversion trench, which is in contact with the carbon paper diffusion layer on the working electrode, is provided with a cross-like structure to form four small window runners; four small windows corresponding to the four small window runners in the S-shaped diversion trench are formed in the positions, in contact with the carbon paper diffusion layer on the working electrode, of the working electrode fixing plate.
As an embodiment of the invention, the working electrode is composed of an electrode plate and a carbon paper diffusion layer, and the electrode plate is a titanium plate with a window for placing the carbon paper diffusion layer in the middle.
As an embodiment of the invention, the upper part of the electrode plate is provided with a protruding slender strip titanium plate; and a groove for placing the slender titanium plate is also arranged above the rectangular diversion trench on the air chamber flow channel slot plate.
As an embodiment of the invention, the upper part and the lower part of one side of the anode chamber circulation groove plate are respectively provided with two holes communicated with the anode chamber, the lower hole is provided with a gas circulation quick joint, the upper hole is provided with a liquid circulation self-locking joint, the lower part of the other side is provided with a hole communicated with the anode chamber, and the liquid circulation self-locking joint is arranged; three holes communicated with the anode chamber are formed above the anode chamber circulation groove plate, and two hollow screws with sealing rings and a gas circulation quick connector are respectively installed on the three holes; one of the hollow screws with the sealing ring is inserted into the counter electrode.
As an embodiment of the invention, two holes communicated with the cathode chamber are respectively arranged at the upper part and the lower part of one side of the cathode chamber circulation groove plate, a gas circulation quick joint is arranged at the lower hole, a liquid circulation self-locking joint is arranged at the upper hole, a hole communicated with the cathode chamber is arranged at the lower part of the other side of the cathode chamber circulation groove plate, and a liquid circulation self-locking joint is arranged; three holes communicated with the cathode chamber are arranged above the cathode chamber flow groove plate, two hollow screws with sealing rings and a gas flow quick connector are respectively arranged, and a reference electrode can be inserted into one hollow screw with a sealing ring.
As an embodiment of the invention, the cathode chamber circulation groove plate and/or the anode chamber circulation groove plate are connected with the peristaltic pump through a liquid circulation self-locking joint.
As an embodiment of the invention, an upper gas flow quick connector on a cathode chamber flow groove plate is connected with a gas chromatography, and the gas product is detected and analyzed on line in real time.
As one embodiment of the invention, the upper liquid circulation self-locking joint on the cathode chamber circulation groove plate is connected with a lead-out device, and the circulating lead-out liquid is periodically extracted to detect the liquid product through ion chromatography.
Compared with the prior art, the invention has the beneficial effects that:
1. can be freely assembled into two electrolytic cells of T-EC two chambers (liquid-liquid) and T-GDE three chambers (gas-liquid) through actual requirements;
2. the T-GDE three-chamber electrolytic cell is additionally provided with the gas chamber, so that not only is the direct sample introduction of reaction gas realized, but also the gas flow field and the retention time are increased, the contact area is increased, the liquid seepage phenomenon is reduced, and the catalytic reaction efficiency is greatly enhanced; particularly, because the middle of the S-shaped flow channel of the air chamber is provided with the four small windows, when the S-shaped flow channel of the air chamber is matched with a carbon paper diffusion layer loaded with a catalyst for use, the contact area can be effectively increased, the retention time is prolonged, the gas can be fully diffused to the surface of the catalyst, meanwhile, the S-shaped flow channel of the air chamber is assembled with a working electrode, the whole flow channel plate of the cathode air chamber can be kept flat, only the four small windows are kept to be in contact with the electrolyte of a flow channel plate of the cathode liquid chamber, and the gas-liquid chambers with all the areas are completely;
3. the cathode liquid chamber flow trough plate and the anode liquid chamber flow trough plate are separated by only a proton exchange membrane (such as a Nafion117 membrane), so that the distances between the cathode and anode can be greatly shortened and are not interfered with each other when the cathode liquid chamber flow trough plate and the anode liquid chamber flow trough plate are used in a matched manner, the mass transfer distance is greatly shortened, and unnecessary energy loss is reduced;
4. the catholyte chamber flow cell plate and the anolyte chamber flow cell plate are both provided with gas-liquid inlet and outlet connectors, gas products can be directly communicated with a gas chromatograph, and real-time online detection and analysis are realized by gas chromatograph and ion chromatograph detection means; the external peristaltic pump realizes the continuous renewal of electrolyte and the timely discharge of liquid products, prevents the change or pollution of the electrolyte solubility, effectively avoids electrode poisoning by improving the conditions, and greatly improves the electrocatalysis of CO2And (4) reducing efficiency.
Drawings
FIG. 1 is a schematic diagram of a T-GDE triple chamber in accordance with an embodiment of the present invention;
FIG. 2 is a schematic diagram of a T-EC two chamber of an embodiment of the invention;
FIG. 3 is a schematic diagram of the construction of a cathode plenum flow field channeled panel in an embodiment of the present invention;
the electrolytic cell comprises an anode chamber flow groove plate 1, a proton exchange membrane 2, a cathode chamber flow groove plate 3, a cathode chamber 4, a gas chamber flow passage groove plate 5, a first working electrode fixing plate 6, a working electrode 7, a second working electrode fixing plate 8, a sealing gasket 9, an electrolyte circulating valve 10, a counter electrode 11, a reference electrode 12, an end plate 13, a rectangular diversion trench 14, an S-shaped diversion trench 15 and a groove 16.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Examples
Referring to FIGS. 1-3, the present example provides an electrocatalytic carbon dioxide reduction (CO)2RR) electrolytic cell, which can be assembled into a T-GDE three-chamber electrolytic cell and a T-EC two-chamber electrolytic cell according to the use requirement.
As shown in fig. 1, the electrolytic cell with three chambers of T-GDE mainly comprises a gas chamber flow channel groove plate 5, working electrode fixing plates (a first working electrode fixing plate 6 and a second working electrode fixing plate 8), an electrode plate 7, a carbon paper diffusion layer, a proton exchange membrane 2, a cathode chamber flow groove plate 3 and an anode chamber flow groove plate 1; wherein the content of the first and second substances,
two layers of concave diversion trenches (figure 3) are arranged on the air chamber flow channel groove plate 5: the gas guide groove is characterized by comprising a rectangular guide groove 14 and a gas guide groove (S-shaped guide groove 15), wherein the S-shaped guide groove 15 is arranged on the lower layer of the rectangular guide groove 14; the part of the S-shaped diversion trench 15, which is in contact with the carbon paper diffusion layer on the working electrode 7, is provided with a cross-like frame to form four small windows, so that the gas stays in the gas chamber for a long time and is fully diffused to the catalytic layer on the carbon paper diffusion layer. Such a cross structure may be: a downward first bulge is arranged at the bottom of the previous flow channel on the part of the S-shaped diversion trench 15, which is in contact with the carbon paper diffusion layer on the working electrode 7, a first concave part is arranged in the middle of the middle flow channel, and a gap for gas to flow is formed between the first bulge and the bottom of the first concave part; an upward second bulge is arranged at the end part of the middle flow passage, and a gap for gas to flow is formed between the second bulge and the bottom of the previous flow passage; and a second concave part is arranged in the middle of the next flow channel, a downward third bulge is arranged at the bottom of the first concave part, and a gap for gas to flow is formed between the third bulge and the bottom of the second concave part. A first working electrode fixing plate 6, a working electrode 7 and a second working electrode fixing plate 8 are sequentially arranged on grooves on the periphery of the rectangular diversion trench 14, the grooves are just tightly attached to be level with the edge of the air chamber flow channel trench plate 5, and liquid seepage from a catholyte chamber to the air chamber is effectively reduced; a groove 16 for placing a long and thin titanium plate protruding from the upper part of the electrode plate (the working electrode 7 is composed of the electrode plate and a carbon paper diffusion layer, and the electrode plate is a titanium plate provided with a window for placing the carbon paper diffusion layer in the middle) is also arranged above the rectangular diversion trench 14 on the air chamber flow channel groove plate 5. Two sides of the air chamber flow channel groove plate 5 are respectively provided with a hole communicated with the S-shaped flow channel, and the holes are provided with air circulation quick connectors.
Four small windows corresponding to the four small windows in the S-shaped diversion trench 15 are formed in the positions, contacting the carbon paper diffusion layer on the working electrode 7, of the first working electrode fixing plate 6 and the second working electrode fixing plate 8.
The electrode plate is a titanium plate with a square window in the middle and a long and thin strip protruding from the upper part. The carbon paper diffusion layer is a carbon paper comprising a supported catalyst; the carbon paper diffusion layer is just placed in the square window of the electrode plate to form the working electrode 7. In the T-GDE three-chamber electrolytic cell, the carbon paper diffusion layer is close to one side of the air chamber flow channel groove plate 5 and is provided with a CO formed by an S-shaped diversion groove 15 of the air chamber flow channel groove plate 5 and four small windows of the first working electrode fixing plate 62A channel; CO 22CO is formed by reduction reaction of the carbon paper diffusion layer2Intermediate, CO2The intermediate enters a cathode chamber 4 arranged in the cathode chamber flow trough plate 3 through four small windows of a second working electrode fixing plate 8.
A hollow cathode chamber 4 is provided in the cathode chamber flow channel plate 3 for storing catholyte electrolyte (e.g., 0.5 MKHCO)3) And containing CO2An intermediate. Two holes communicated with the cathode chamber 4 are formed in one side of the cathode chamber circulation groove plate 3 from top to bottom, a gas circulation quick joint is installed in the lower hole, a liquid circulation self-locking joint (capable of being connected with an electrolyte circulation valve 10) is installed in the upper hole, and a hole communicated with the cathode chamber 4 is formed in the lower portion of the other side of the cathode chamber circulation groove plate and is provided with a liquid circulation self-locking joint; three holes communicated with the cathode chamber 4 are formed above the cathode chamber circulation groove plate 3, and two hollow screws with sealing rings and a gas circulation quick connector are respectively installed on the holes; gas-liquid (catholyte solution and CO)2) The self-locking joint is a self-locking device which can be inserted into the catheter to flow and cannot flow when the catheter is pulled out.
In the T-GDE three-chamber electrolytic cell, the cathode chamber 4 (i.e. the chamber inside the cathode chamber flow trough plate) is only required to be provided with the reference electrode 12, namely, the reference electrode 12 (a saturated Ag/AgCl electrode is selected) is inserted into a hollow screw with a sealing ring above the cathode chamber flow trough plate 3.
After a working electrode 7 fixed by a first working electrode fixing plate 6 and a second working electrode fixing plate 8 is placed on the air chamber flow channel groove plate 5, sealing is realized between the air chamber flow channel groove plate 5 and the cathode chamber flow groove plate 3 through a sealing gasket 9; and a window matched with the size of the cathode chamber 4 of the cathode chamber circulation groove plate 3 is arranged on the sealing gasket 9.
A concave part is arranged on the anode chamber circulation groove plate 1 to form an anode chamber; for storing anolyte (e.g., 0.5 MKOH). One side of the anode chamber circulation groove plate 1 is provided with two holes communicated with the anode chamber from top to bottom, the lower hole is provided with a gas circulation quick joint, the upper hole is provided with a liquid circulation self-locking joint (capable of connecting with an electrolyte circulation valve 10), and the lower surface of the other side is provided with a hole communicated with the anode chamber and provided with a liquid circulation self-locking joint; three holes communicated with the anode chamber are arranged above the anode chamber circulation groove plate 1, and two hollow screws with sealing rings and a gas circulation quick connector are respectively arranged on the three holes. Gas (which is not used for the time being) and liquid (anolyte) which are designed to be developed later are respectively introduced from below and discharged from above. The self-locking joint is a self-locking device which can be circulated when being inserted into a catheter and can not be circulated when the catheter is pulled out.
In the T-GDE three-chamber electrolytic cell, the anode chamber (i.e. the chamber inside the anode chamber flow cell plate) is only required to be provided with the counter electrode 11 (a platinum wire electrode is selected), namely, the counter electrode 11 is inserted into a hollow screw which is provided with a sealing ring and arranged above the anode chamber flow cell plate 1.
The cathode chamber circulation groove plate 3 and the anode chamber circulation groove plate 1 are separated by the proton exchange membrane 2, so that the anode and the cathode are close to each other as much as possible and do not interfere with each other, the mass transfer distance and the energy loss are effectively reduced, and the proton exchange membrane 2 is a Nafion117 membrane. And two sides of the proton exchange membrane 2 are respectively provided with a sealing gasket 9, and the cathode chamber circulation groove plate 3, the proton exchange membrane 2 and the anode chamber circulation groove plate 1 are attached together through the sealing gaskets 9, so that the sealing performance of the whole device is ensured. The cathode chamber 4 of the cathode chamber circulation groove plate 3 is the same as the anode chamber of the anode chamber circulation groove plate 1 in size; the sealing gasket 9 is formed by correspondingly cutting a silica gel sheet, and the sealing gasket 9 is provided with a window matched with the size of the cathode cavity 4 or the anode cavity.
And, above-mentioned cathode chamber circulation frid 3 and anode chamber circulation frid 1 all can link to each other with the peristaltic pump through the liquid circulation auto-lock joint that is equipped with, and constantly let in and renew the electrolyte solution in real time, ensure that reaction electrolyte solution concentration is the same, and the timely discharge of liquid reduction product prevents electrode poisoning and electrolyte pollution, still can use ion chromatography to detect the analysis through collecting.
The T-EC two-chamber electrolytic cell is constructed as shown in FIG. 2, and is composed of an auxiliary chamber plate (end plate 13), a proton exchange membrane 2, a cathode chamber flow trough plate 3 and an anode chamber flow trough plate 1. The most important difference from the T-GDE three-chamber electrolytic cell is that:
the side of the cathode chamber flow trough plate 3 departing from the anode chamber flow trough plate 1 is sealed with an auxiliary chamber plate (also called an end plate 13) through a sealing gasket 9. In addition, a working electrode 11 and a reference electrode 12 are placed in the cathode chamber 4, that is, an electrode clamp with carbon paper is inserted into a hollow screw with a sealing ring above the cathode chamber flow trough plate 3 as the working electrode 11, and a saturated Ag/AgCl electrode is inserted into another hollow screw with a sealing ring as the reference electrode 12. And, CO2And a gas circulation quick joint which is connected into the cathode chamber circulation groove plate 3 according to the principle of bottom inlet and top outlet.
The specific operation can be as follows:
taking an electrolytic cell with three chambers of T-GDE as an example
The electrolytic cell with three chambers of T-GDE is selected according to experimental requirements, 7 holes in a flow trough plate of an anode chamber are fixed by screws with caps with the length of 10cm, a Nafion117 membrane is clamped and placed above the flow trough plate of the anode chamber by two sealing gaskets, and the step determines whether the anode chamber and the cathode chamber permeate or not as the most critical. Then fixing the carbon paper diffusion layer on the electrode sheet to assemble a working electrode, and tightly arranging the two sides of the working electrode on the uppermost layer by using a working electrode fixing plate respectively. After the screw nails are respectively provided with the gaskets, the screw caps are screwed. Then, a counter electrode is inserted into the hollow screw with a sealing ring in the middle on the anode chamber flow trough plate, and a reference electrode is inserted into the hollow screw with a sealing ring on the cathode chamber flow trough plate.
Further, the gas circulation quick connector of the S-shaped runner groove plate of the gas chamber is connected with CO according to the principle of downward inlet and upward outlet2A gas. Finally, the liquid circulation self-locking joint of the cathode chamber circulation groove plate and the anode chamber circulation groove plate is connected with a peristaltic pump to update electrolyte solution in real time, and the cathode chamber flow is treatedThe through groove plate gas circulation quick joint is connected with a gas chromatography to detect and analyze the product on line in real time. The liquid product can be tested by periodically extracting the circulating educt and detecting the liquid product through ion chromatography.
The use principle is as follows: CO 22The gas chamber S-shaped flow channel groove plate is connected into the S-shaped flow channel groove plate of the S-shaped two layers of concave flow guide grooves according to the principle of downward inlet and upward outlet to form a flow guide channel, the residence time of the four small windows on the working electrode fixing plate which is in contact with the carbon paper diffusion layer is long enough, the small windows are fully diffused to the catalytic layer on the carbon paper, and the reduction reaction is carried out to form CO2An intermediate. At this time, the anode is oxidized to generate protons H, which diffuse to the cathode chamber through the Nafion117 membrane and contact with CO on the surface of the catalyst2The intermediates are combined to produce reduction products CO, formic acid and the like. And gas products generated after reduction are continuously diffused into the concave diversion trench of the S-shaped flow channel slot plate of the air chamber and are discharged from the upper opening. The liquid product is retained in the cathode chamber and discharged through the upper port of a peristaltic pump connected to the cathode chamber flow trough plate. Complete electrocatalysis of CO2And (4) reduction process.
Taking an electrolytic cell with two chambers of T-EC as an example
Selecting an electrolytic cell with two T-EC chambers according to experimental requirements, firstly, penetrating 7 holes on a flow trough plate of an anode chamber into screws with caps with the length of 10cm for fixation, and then clamping a Nafion117 membrane above the flow trough plate of the anode chamber by using two sealing gaskets, wherein the steps are the same as the assembly of the electrolytic cell with three T-GDE chambers. Then the electrode clamp is arranged on the hollow screw part with a sealing ring in the middle on the cathode chamber circulation groove plate, carbon paper sprayed with a catalyst is clamped, and the auxiliary chamber plate is arranged on the uppermost layer after a sealing gasket is arranged. Then, after the gaskets are respectively placed on the screws, the screw caps are screwed on. Then, a counter electrode is inserted into a hollow screw with a sealing ring in the middle on the anode chamber flow trough plate, and a reference electrode is inserted into another hollow screw with a sealing ring on the cathode chamber flow trough plate.
Further, the gas circulation quick joint of the cathode chamber circulation groove plate is connected with CO2A gas pipeline. Finally, the liquid circulation self-locking joint of the cathode chamber circulation groove plate and the anode chamber circulation groove plate is connected with a peristaltic pump to update electrolyte solution in real time, and the cathode chamber circulation groove plate and the anode chamber circulation groove plate are connected with each otherAnd a quick joint for gas circulation of the circulation groove plate is connected with a gas chromatography to detect and analyze the product on line in real time. The liquid product can be tested by periodically extracting the circulating educt and detecting the liquid product through ion chromatography.
The use principle is as follows: CO 22The gas circulation quick connector is connected to the cathode chamber circulation groove plate according to the principle of bottom-in and top-out, is firstly dissolved in electrolyte solution and then is diffused to the surface of a working electrode catalyst to generate reduction reaction to form CO2An intermediate. At this time, the anode is oxidized to generate protons H, which pass through the Nafion117 membrane and diffuse to the catalyst surface and CO2The intermediates are combined to produce reduction products CO, formic acid and the like. And gas products generated after reduction are continuously diffused and discharged from a quick joint for gas circulation above the cathode chamber circulation groove plate. The liquid product is retained in the cathode chamber and discharged through the upper port of a peristaltic pump connected to the cathode chamber flow trough plate. Complete electrocatalysis of CO2And (4) reduction process.
And (3) separating and detecting products: when the electrolysis is carried out under the set voltage condition, the gas chromatograph samples 5ul each time, the total inspection is carried out three times, and the product and the content are determined according to the position of the spectrogram peak of the gas chromatograph so as to detect the gas product. Meanwhile, collecting the catholyte circulated by the peristaltic pump at the same time interval, and detecting the liquid product by using ion chromatography.
In summary, the present invention provides a multifunctional electrolytic cell device for electrocatalytic carbon dioxide reduction; can select the frid equipment to realize the switching of two kinds of electrolytic cells according to the demand, wherein first air chamber S type runner frid middle has a type cross, forms four little windows for the gas that lets in forms disturbance dwell time long, and use carbon paper as the cooperation of gas diffusion layer and first air chamber S type runner frid, second piece catholyte chamber flow frid, strengthen the gas diffusion to carbon paper, reduce liquid to the air chamber and pass through. The second catholyte chamber flow trough plate and the third anolyte chamber flow trough plate are separated by a proton exchange membrane, so that the distances between the cathode and the anode can be greatly shortened and are not interfered with each other when the two plates are used in a matched manner, and the mass transfer distance and the energy loss are reduced. And the two liquid chamber circulation frid are all opened with the gas-liquid import and export, and external peristaltic pump can realize the real-time renewal of electrolyte, effectively avoids electrode poisoning, and the reduction product can in time be discharged simultaneously, realizes real-time on-line detection analysis through gas chromatography and ion chromatography detection means.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The electrolytic cell device for the multifunctional electrocatalytic carbon dioxide reduction is characterized by comprising an anode chamber circulation groove plate, a proton exchange membrane, a cathode chamber circulation groove plate and an end plate component which are sequentially arranged and sealed through a sealing gasket;
a concave part is arranged on the anode chamber circulation groove plate to form an anode chamber; the anode chamber circulation groove plate is respectively provided with a gas inlet, a gas outlet, a liquid inlet, a liquid outlet and two through holes provided with hollow screws, wherein one hollow screw is inserted into the counter electrode; the gas inlet and outlet are arranged to be in a lower part and in an upper part; the liquid in the anode chamber enters from bottom to top;
a hollow cathode chamber is arranged in the cathode chamber flow groove plate, a gas inlet and a gas outlet, a liquid inlet and a liquid outlet and two through holes provided with hollow screws are respectively arranged on the cathode chamber flow groove plate, and a reference electrode is inserted into one hollow screw; the gas and the liquid in the cathode chamber are all discharged from the bottom to the top;
the end plate component is an end plate or an end plate structure assembly which is provided with a carbon dioxide channel communicated with the cathode chamber and can be internally provided with a working electrode.
2. The multi-functional electrocatalytic carbon dioxide reduction cell unit as recited in claim 1, wherein when the end plate member is an end plate, the working electrode is inserted into another hollow screw of the cathode chamber flow cell plate, and when in operation, carbon dioxide is introduced into the gas inlet and outlet of the cathode chamber flow cell plate according to the principle of bottom inlet and top outlet.
3. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 1, wherein said end plate structure assembly is comprised of a gas chamber flow channel plate, a working electrode fixing plate and a working electrode;
two layers of concave diversion trenches are arranged on the air chamber flow channel groove plate: the gas diversion groove is arranged at the lower layer of the rectangular diversion groove; a baffle block is arranged in the gas diversion groove and used for prolonging the retention time of the gas in the gas diversion groove; the upper and lower parts of the two sides of the air chamber flow channel groove plate are respectively provided with a hole communicated with the air flow channel in the groove plate;
windows communicated with the gas diversion grooves are formed in the positions, contacting with the carbon paper diffusion layer of the working electrode, on the working electrode fixing plate;
the working electrode is fixed by the working electrode fixing plates on two sides and then is attached to the grooves on the periphery of the rectangular diversion trench, and the working electrode fixing plates on the outer side are flush with the edge surfaces of the air chamber runner channel plates.
4. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 3, wherein said gas channeling is an S-shaped channeling; the part of the S-shaped diversion trench, which is in contact with the carbon paper diffusion layer of the working electrode, is provided with a cross-like structure to form four small window runners; four small windows corresponding to the four small window runners in the S-shaped diversion trench are formed in the positions, contacting the carbon paper diffusion layer of the working electrode, of the working electrode fixing plate.
5. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 3, wherein said working electrode is composed of an electrode sheet and a carbon paper diffusion layer, said electrode sheet being a titanium plate having a window in the middle thereof in which the carbon paper diffusion layer is placed.
6. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 5, wherein said electrode sheets are provided at upper portions thereof with protruding elongated titanium plates; and a groove for placing the slender titanium plate is also arranged above the rectangular diversion trench on the air chamber flow channel slot plate.
7. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 1, wherein the anode chamber flow cell plate has two holes communicating with said anode chamber formed in the upper and lower portions of one side thereof, respectively, the lower hole being provided with a gas flow quick connector, the upper hole being provided with a liquid flow self-locking connector, and the other side having a hole communicating with said anode chamber formed in the lower portion thereof, the liquid flow self-locking connector being provided; three holes communicated with the anode chamber are formed above the anode chamber circulation groove plate, and two hollow screws with sealing rings and a gas circulation quick connector are respectively installed on the three holes; one of the hollow screws with the sealing ring is inserted into the counter electrode.
8. The multi-functional electrocatalytic carbon dioxide reduction electrolytic cell device as set forth in claim 1, wherein two holes communicating with said cathode chamber are respectively opened at upper and lower portions of one side of the cathode chamber flow cell plate, a gas flow quick connector is installed at a lower hole, a liquid flow self-locking connector is installed at an upper hole, a hole communicating with said cathode chamber is opened at a lower portion of the other side, and a liquid flow self-locking connector is installed; three holes communicated with the cathode chamber are arranged above the cathode chamber flow groove plate, two hollow screws with sealing rings and a gas flow quick connector are respectively arranged, and a reference electrode can be inserted into one hollow screw with a sealing ring.
9. A multi-functional electro-catalytic carbon dioxide reduction cell unit as claimed in claim 7 or 8, characterized in that the cathode chamber flow cell plate and/or the anode chamber flow cell plate are connected to the peristaltic pump by means of a self-locking joint for liquid flow provided.
10. The electrolyzer unit for multi-functional electrocatalytic carbon dioxide reduction according to claim 8 wherein the upper gas flow quick connector on the flow cell plate of the cathode chamber is connected to the gas chromatograph for real-time on-line detection and analysis of the gas products; and/or an upper liquid circulation self-locking joint on the cathode chamber circulation groove plate is connected with a lead-out device, and a circulating lead-out liquid is extracted at regular time to detect a liquid product through ion chromatography.
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| CN113373462A (en) * | 2021-05-21 | 2021-09-10 | 南京理工大学 | For electrochemical reduction of CO2Membrane type liquid flow electrolytic cell and testing process |
| CN114381745A (en) * | 2022-01-17 | 2022-04-22 | 上海喜运环保科技有限公司 | Electrolytic generator module based on zigzag flow channel formed by multilayer electrode combination |
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| CN114672832A (en) * | 2022-01-27 | 2022-06-28 | 西安交通大学 | Carbon dioxide electrolysis reactor capable of simultaneously serving as flow cell and membrane electrode electrolytic cell |
| CN114686908A (en) * | 2022-03-07 | 2022-07-01 | 华中科技大学 | Method for directly generating formic acid by efficiently electro-catalyzing reduction of carbon dioxide |
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| CN115341228A (en) * | 2022-08-15 | 2022-11-15 | 海德威科技集团(青岛)有限公司 | Device for preparing carbon monoxide by electrocatalysis |
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