CN212770994U - 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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- CN212770994U CN212770994U CN202021326931.8U CN202021326931U CN212770994U CN 212770994 U CN212770994 U CN 212770994U CN 202021326931 U CN202021326931 U CN 202021326931U CN 212770994 U CN212770994 U CN 212770994U
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Abstract
The utility model discloses a multifunctional electrolytic cell device for electrocatalysis 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 utility model discloses can select the frid equipment to realize the switching of two kinds of electrolytic cell according to the demand, wherein have a class cross in the middle of the S type runner frid of end plate structure subassembly, form four little windows for the gas that lets in forms disturbance dwell time long, and regard as gas diffusion layer and air chamber runner frid, cathode chamber circulation frid cooperation to use with carbon paper, strengthen the gas diffusion to carbon paper, reduce liquid air chamber seepage. 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 utility model relates to an electro-catalysis carbon dioxide reduction technical field relates to a multi-functional electro-catalysis 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 electrolyte is dissolvedThe change of the degree leads to low reaction efficiency and simultaneously the raw material gas CO2The 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.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems, the utility model relates to a multifunctional electrolytic cell device for electrocatalysis 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 above object, the utility model adopts the following technical scheme:
the utility model 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.
As an embodiment of the utility model, when the end plate part is the end plate, the working electrode is inserted to another cavity screw department of cathode chamber circulation frid, and the during operation, carbon dioxide advances according to the principle of going into down and going out from top to bottom inserts gaseous business turn over, export.
As an embodiment of the present invention, the end plate structure assembly is composed of an air 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 utility model, the working electrode comprises electrode slice and carbon paper diffusion layer, the electrode slice is the titanium plate that the centre was equipped with the window of placing the carbon paper diffusion layer.
As an embodiment of the utility model, the upper part of the electrode plate is provided with a protruding slender 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 utility model, 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, and the lower part 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 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 utility model, the upper part and the lower part of one side of the cathode chamber circulation groove plate are respectively provided with two holes communicated with the cathode 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 cathode chamber, and the 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 utility model, the cathode chamber circulation frid and/or the anode chamber circulation frid are connected with the peristaltic pump through the liquid circulation self-locking joint.
As an embodiment of the utility model, the last gas circulation quick-operation joint on the cathode chamber circulation frid is connected with the gas chromatography, to the real-time on-line measuring analysis of gas production.
As an embodiment of the utility model, last liquid circulation self-locking joint on the cathode chamber circulation frid links to each other with the eduction gear, and the circulation eduction liquid of regularly extracting detects the liquid product through ion chromatogram.
Compared with the prior art, the beneficial effects of the utility model reside in 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 a proton exchange membrane (such as a Nafion 117 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 embodiment of the invention;
FIG. 3 is a schematic structural view of a cathode gas chamber flow channel plate according to 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 problem, technical solution and advantageous effects to be solved by the present invention clearer and more obvious, the following description of the present invention with reference to the accompanying drawings and embodiments is provided for further details.
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.
The cathode chamber flow channel plate 3 is provided with a hollow cathode chamber 4 for storing catholyte electrolyte (e.g., 0.5M KHCO)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 arranged above the cathode chamber circulation groove plate 3, and two hollow screws with sealing rings and a gas circulation quick connector are respectively arranged(ii) a 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., 0.5M KOH). 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 Nafion 117 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 Nafion 117 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. And finally, connecting the liquid circulation self-locking joint of the cathode chamber circulation groove plate and the anode chamber circulation groove plate with a peristaltic pump, updating electrolyte solution in real time, and connecting the gas circulation quick joint of the cathode chamber circulation groove plate with a gas chromatography to perform real-time online detection and analysis on a product. 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 Nafion 117 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 Nafion 117 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. And finally, connecting the liquid circulation self-locking joint of the cathode chamber circulation groove plate and the anode chamber circulation groove plate with a peristaltic pump, updating electrolyte solution in real time, and connecting the fast joint of the cathode chamber circulation groove plate and the gas circulation fast joint of the anode chamber circulation groove plate with a gas chromatography to perform real-time online detection and analysis on products. 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 Nafion 117 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 utility model provides a multifunctional electrolytic cell device for electrocatalysis carbon dioxide reduction; the cell plates can be selected according to requirements to be assembled to realize the switching of two electrolytic cells, wherein a cross is arranged in the middle of the S-shaped flow channel cell plate of the first air chamber to form four small windows, so that the introduced gas has long disturbance retention time, and carbon paper is used as a gas diffusion layer to be matched with the S-shaped flow channel cell plate of the first air chamber and the flow channel plate of the second cathode liquid chamber, so that the diffusion of the gas to the carbon paper is enhanced, and the permeation of the liquid to the air chambers is reduced. 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 the specific embodiments of the 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 those 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 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.
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.
Priority Applications (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111733425A (en) * | 2020-07-08 | 2020-10-02 | 福建师范大学 | Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction |
| CN113957466A (en) * | 2021-11-08 | 2022-01-21 | 中国石油大学(华东) | Flow type electrolytic cell for photoelectrocatalysis reaction |
| CN114134521A (en) * | 2021-08-22 | 2022-03-04 | 南京理工大学 | For electrocatalysis of CO2Reduced through flow field membrane reactor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111733425A (en) * | 2020-07-08 | 2020-10-02 | 福建师范大学 | Electrolytic cell device of multi-functional electro-catalysis carbon dioxide reduction |
| CN114134521A (en) * | 2021-08-22 | 2022-03-04 | 南京理工大学 | For electrocatalysis of CO2Reduced through flow field membrane reactor |
| CN114134521B (en) * | 2021-08-22 | 2024-04-23 | 南京理工大学 | For electrocatalytic CO2Reduced flow field membrane reactor |
| CN113957466A (en) * | 2021-11-08 | 2022-01-21 | 中国石油大学(华东) | Flow type electrolytic cell for photoelectrocatalysis reaction |
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