CN112858421A - In-situ synchrotron radiation electrolytic cell for electrocatalysis system - Google Patents
In-situ synchrotron radiation electrolytic cell for electrocatalysis system Download PDFInfo
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Abstract
The invention provides a design method of a synchrotron radiation in-situ electrolytic cell suitable for an electrocatalysis system. The in-situ electrolytic cell consists of four parts, namely a working electrode side, a counter electrode side, a reference electrode side and an electrolytic cell cavity. The in-situ electrolytic cell is characterized by the detachability of the whole part, the flowability of gas-liquid two phases and the universality under normal temperature and pressure. The electrolytic cell has simple design and flexible operation: assembling the catalyst coating on the side monitoring window of the in-situ cell, irradiating the catalyst coating with synchrotron radiation X-rays in the reaction process, and then reflecting the catalyst coating to a fluorescence detector to effectively collect reaction signals of the whole system. The in-situ electrolytic cell has good universality, is suitable for any electro-catalytic system, and is a key technical means for monitoring the dynamic process of the catalytic system in real time and analyzing the structure-activity relationship.
Description
Technical Field
The invention relates to a design of an in-situ synchrotron radiation electrolytic cell which can be used for an electro-catalysis system and subsequent universal application.
Background
The analysis of the structure-activity relationship is a key scientific problem in a catalytic system, and the analysis of an active site and a real reaction path in an in-situ dynamic process is crucial to guiding and designing a novel and efficient catalyst. In situ characterization of many spectra enables in situ dynamic monitoring of catalytic reaction processes, such as: in-situ Raman spectroscopy, near-normal pressure in-situ XPS and the like; however, these characterizations are subject to many environmental disturbances and are therefore difficult to apply universally. The development of synchrotron radiation X-ray absorption fine structure spectroscopy (XAFS) technology offers great convenience for in situ dynamic monitoring. The technology has atom selectivity, higher resolution ratio on metal elements and insensitivity on light elements such as nitrogen, carbon, oxygen and the like, so that the technology can be used for testing in an atmosphere; in addition, local structure information around the absorbing atoms can be provided with subatomic resolution, and the electronic structure of the absorbing atoms in the catalyst and the adjacent coordination structure information can be analyzed. Therefore, it is necessary to monitor the dynamic process of the catalytic system using in situ XAFS to resolve the "structure-activity relationship". The design of a suitable, universal synchrotron radiation in-situ cell is a critical technical issue. The designed electrolytic cell needs to completely and truly reflect signals in an in-situ dynamic process, namely the reaction process in the in-situ cell is required to be real, the absorption of X rays is not interfered, and the fluorescence reflection is not influenced; in addition, the requirement of flexible disassembly of the whole system in the prior period is also met, including: replacement of catalyst coatings, flowing gas/liquid layers, etc.
Disclosure of Invention
The invention aims to provide a universal synchrotron radiation electrolytic cell for in-situ monitoring of an electro-catalytic system, which is suitable for any electro-catalytic system at normal temperature and normal pressure, and has the advantages of simple design, convenient manufacture and flexible operation; the device has the characteristics of field disassembly and gas-liquid flow.
In order to realize the purpose, the cavity material of the synchrotron radiation electrolytic cell of the universal in-situ monitoring electro-catalytic system provided by the invention is acid-resistant and alkali-resistant polytetrafluoroethylene, PINK and the like; the counter electrode is a platinum wire, a platinum sheet, a carbon rod and the like; the reference electrode is silver/silver chloride, saturated calomel and the like; the working electrode is a carbon paper or carbon sheet supported catalyst coating.
The invention provides a universal design method for a synchrotron radiation electrolytic cell of an in-situ monitoring electro-catalytic system,
the electrolytic cell comprises a hollow electrolytic cell cavity and a working electrode, wherein the working electrode comprises a sealing film, a conductive carrier layer and an electrocatalyst coating which are sequentially stacked, the conductive carrier layer is positioned in the middle of the sealing film, an annular sealing film is reserved at the peripheral edge of the conductive carrier layer, and the electrocatalyst coating is attached to the surface of one side, away from the sealing film, of the conductive carrier layer;
having a catalyst coating (working electrode), a counter electrode, a reference electrode and an electrolytic cell cavity;
the side wall surface of the electrolytic cell cavity is provided with a through hole, a working electrode covers the through hole outside the electrolytic cell cavity, the electrocatalyst coating is arranged facing one side of the through hole and is communicated with the inside of the electrolytic cell cavity through the through hole, and the sealing film layer of the working electrode is closely attached to the side wall surface outside the electrolytic cell cavity at the peripheral edge of the through hole;
electrolyte is filled in the cavity of the electrolytic cell, a counter electrode and a reference electrode are arranged in the cavity of the electrolytic cell, and the electrocatalyst coatings of the counter electrode, the reference electrode and the working electrode are all in the electrolyte;
one end of the air duct extends into the electrolyte, and the other end of the air duct is connected with an air source.
The sealing film is one of polyimide film (Kapton film) and transparent adhesive; the conductive carrier layer is one of carbon paper, carbon cloth and glass carbon sheet.
The upper end of the electrolytic cell cavity is provided with an opening, the inner wall surface of the opening is provided with internal threads, and a sealing cap with external threads is screwed at the opening; the counter electrode and the reference electrode are respectively connected with the electrochemical workstation through a lead through hole on the sealing cap by leads, and a conductive carrier layer of the working electrode is connected with the electrochemical workstation through the leads; the air duct is connected with an external air source through an air duct through hole on the sealing cap, and the sealing cap is provided with a through hole as an air outlet hole.
A liquid inlet hole is formed at the lower part or the bottom of the cavity; a liquid outlet hole is arranged at the middle upper part of the cavity.
An annular groove is arranged at the peripheral edge of the through hole covered with the working electrode, a sealing ring is placed in the annular groove, a gland is covered on one side of the working electrode, which is far away from the cavity, and the sealing film layer of the working electrode is pressed by the gland to seal the outer side wall surface of the electrolytic cell cavity at the peripheral edge of the through hole and the sealing film layer through the sealing ring;
the gland is of an annular structure with a through hole in the middle, the middle through hole of the gland and the through hole in the electrolytic cell cavity are projected on the surface of one side of the electrocatalyst coating after being compressed, and the projection of the middle through hole of the gland is positioned in the through hole projection area of the electrolytic cell cavity.
The edge all around in the gland has seted up more than 3 through-holes, and the edge all around in the electrolysis cell cavity through-hole that corresponds has seted up more than 3 blind holes of taking the internal thread, passes through the blind hole through the lead screw and is fixed in the gland on the electrolysis cell cavity.
The counter electrode is one of a carbon rod, a platinum sheet and a platinum wire; the reference electrode is one of a saturated calomel electrode and a silver/silver chloride electrode;
the lead is one of a platinum wire, a copper adhesive tape and an aluminum adhesive tape; the electrocatalyst is one or more than two of electrocatalysts containing metal elements;
the cavity has good chemical stability, and can be one or more of Polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK).
The in-situ electrolytic cell is characterized by the detachability of the whole part, the flowability of gas-liquid two phases and the universality under normal temperature and pressure. The electrolytic cell has simple design and flexible operation: assembling the catalyst coating on the side monitoring window of the in-situ cell, irradiating the catalyst coating with synchrotron radiation X-rays in the reaction process, and then reflecting the catalyst coating to a fluorescence detector to effectively collect reaction signals of the whole system. The in-situ electrolytic cell has good universality, is suitable for any electro-catalytic system, and is a key technical means for monitoring the dynamic process of the catalytic system in real time and analyzing the structure-activity relationship.
The invention has the following effects:
1. the whole cavity is resistant to high temperature, acid and alkali, and the selected materials are easy to process;
2. the working electrode side is simple and convenient to design, and the window and the catalyst carrier are both designed to be light elements, so that the absorption and reflection of X rays are not influenced;
3. the whole electrolytic cell is designed into a flow system, including liquid phase flow and gas phase flow, and is more consistent with a real system.
Drawings
FIG. 1 is a top view of an in situ XAFS electrolytic cell with four holes in the top for placement of electrodes and air inlet holes;
FIG. 2 is a plan view of the internal top seal end and aerator tube configuration;
FIG. 3 is a top view of the gland with four small holes;
FIG. 4 is a front view of an X-ray window of an in-situ XAFS electrolytic cell having the X-ray window centered, an annular sealing groove, four apertures;
FIG. 5 is an overall elevational view of an in situ XAFS electrolytic cell with gas inlet and outlet ports at the upper end and an X-ray window in the middle;
FIG. 6 is an overall side view of an in situ XAFS cell with a small hole at the lower end and another hole at the upper end for in situ flow of electrolyte;
FIG. 7 is an upper end thread seal cap;
FIG. 8 is an integrally assembled in situ XAFS electrolytic cell version with reference and counter electrodes inserted at the upper end and in contact with the electrolyte; the right side of the inside is an aerator pipe which is contacted with electrolyte, the left side is a working electrode side, the aerator pipe can be subdivided into a sealing film, a conductive substrate and a catalyst from left to right in sequence, and the working electrode side is contacted with the electrolyte.
Detailed Description
The following detailed description is given with reference to specific embodiments.
Example 1:
in situ XAFS monitoring of electrocatalytic oxygen reduction:
referring to fig. 8, the reference electrode and the counter electrode are inserted into the electrolyte from the upper end of the electrolytic cell, the aeration pipe is inserted into the electrolyte, and the catalyst coating is respectively as follows from outside to inside: the sealing film, the conductive carbon paper, the catalyst and the catalyst coating contact the electrolyte to form an integral loop.
The design method comprises the following steps:
1) a cavity body: because of the requirements of an electro-catalysis system (acid and alkali electrolytes), a high molecular polymer material with good chemical stability, high temperature resistance, strong acid resistance and alkali resistance is required to be selected as a cavity;
2) reference and counter electrode sides: the reference electrode and the electrode are arranged in a round hole formed in the upper part of the cavity and are in contact with the electrolyte;
3) the working electrode side: the device consists of a fastening end plate, a sealing film, a conductive carrier, a lead, a catalyst coating and a sealing gasket;
4) the upper part and the side surface of the cavity are respectively provided with a round hole and a square hole which can be connected with the working electrode side, the reference electrode side and the counter electrode side;
5) the working electrode side comprises a screw, an inner ring fastening end plate, an X-ray transmission film, a current collecting plate, a catalyst, a lead and a sealing washer;
6) the sealing washer can be arranged in a circular groove formed in the side surface of the cavity;
7) the wire can be arranged in the wire groove connected with the circular groove and is positioned at the upper part of the wire groove;
8) the side part of the counter electrode comprises a counter electrode, a sealing gasket and a fastening nut;
9) the reference electrode side comprises a reference electrode, a sealing gasket and a fastening nut;
10) the side parts of the working electrodes are multiple;
11) the lower part of the cavity is provided with an electrolyte through hole which is an inflow hole;
12) an electrolyte through hole is formed in the upper portion of the side face of the cavity and is a flow-out hole;
13) the insulating support plate at the top end of the cavity is provided with a gas input hole and is connected with an aeration pipe;
14) the insulating support plate at the top end of the cavity is provided with a gas output hole;
1. 1mg/cm2The Cu-N-C catalyst is uniformly coated on one side of the carbon paper;
adhering a kapton membrane to one side of the carbon paper which is not coated with the catalyst;
3. the sealing washer is arranged in the groove on the side surface of the cavity, and the platinum wire is arranged in the chute;
4. decorating the carbon paper pasted with the kapton film in the sealing washer and enabling the carbon paper to be in contact with the platinum wire;
5. pressing the working electrode side with a fastening end plate to perform sealing and contact functions, and fixing with screws;
6. the reference electrode and the working electrode are doped into the cavity from the upper end of the cavity to form a three-electrode system with the working electrode;
7. electrolyte is pumped from the bottom of the side surface of the cavity and flows out from the upper part of the side surface of the cavity to form a stable flowing system;
8.O2the gas is input from the top end of the cavity and simultaneously discharged from the top end to form a stable gas loop
9. The three electrode clamps of the electrochemical workstation (CHI) are correspondingly clamped on the counter electrode, the reference electrode and the working electrode respectively;
10. the operating potential was varied while the fluorescence signal was recorded.
Claims (8)
1. An in-situ synchrotron radiation electrolytic cell for electrocatalytic systems, characterized in that:
the electrolytic cell comprises a hollow electrolytic cell cavity and a working electrode, wherein the working electrode comprises a sealing film, a conductive carrier layer and an electrocatalyst coating which are sequentially stacked, the conductive carrier layer is positioned in the middle of the sealing film, an annular sealing film is reserved at the peripheral edge of the conductive carrier layer, and the electrocatalyst coating is attached to the surface of one side, away from the sealing film, of the conductive carrier layer;
the side wall surface of the electrolytic cell cavity is provided with a through hole, a working electrode covers the through hole outside the electrolytic cell cavity, the electrocatalyst coating is arranged facing one side of the through hole and is communicated with the inside of the electrolytic cell cavity through the through hole, and the sealing film layer of the working electrode is closely attached to the side wall surface outside the electrolytic cell cavity at the peripheral edge of the through hole;
electrolyte is filled in the cavity of the electrolytic cell, a counter electrode and a reference electrode are arranged in the cavity of the electrolytic cell, and the electrocatalyst coatings of the counter electrode, the reference electrode and the working electrode are all in the electrolyte;
one end of the air duct extends into the electrolyte, and the other end of the air duct is connected with an air source.
2. The electrolytic cell of claim 1 wherein:
the sealing film is one of polyimide film (Kapton film) and transparent adhesive; the conductive carrier layer is one of carbon paper, carbon cloth and glass carbon sheet.
3. The electrolytic cell of claim 1 wherein:
the upper end of the electrolytic cell cavity is provided with an opening, the inner wall surface of the opening is provided with internal threads, and a sealing cap with external threads is screwed at the opening; the counter electrode and the reference electrode are respectively connected with the electrochemical workstation through a lead through hole on the sealing cap by leads, and a conductive carrier layer of the working electrode is connected with the electrochemical workstation through the leads; the air duct is connected with an external air source through an air duct through hole on the sealing cap, and the sealing cap is provided with a through hole as an air outlet hole.
4. The electrolytic cell of claim 1 wherein:
a liquid inlet hole is formed at the lower part or the bottom of the cavity; a liquid outlet hole is arranged at the middle upper part of the cavity.
5. The electrolytic cell of claim 1 wherein:
an annular groove is arranged at the peripheral edge of the through hole covered with the working electrode, a sealing ring is placed in the annular groove, a gland is covered on one side of the working electrode, which is far away from the cavity, and the sealing film layer of the working electrode is pressed by the gland to seal the outer side wall surface of the electrolytic cell cavity at the peripheral edge of the through hole and the sealing film layer through the sealing ring;
the gland is of an annular structure with a through hole in the middle, the middle through hole of the gland and the through hole in the electrolytic cell cavity are projected on the surface of one side of the electrocatalyst coating after being compressed, and the projection of the middle through hole of the gland is positioned in the through hole projection area of the electrolytic cell cavity.
6. The electrolytic cell of claim 5 wherein:
the edge all around in the gland has seted up more than 3 through-holes, and the edge all around in the electrolysis cell cavity through-hole that corresponds has seted up more than 3 blind holes of taking the internal thread, passes through the blind hole through the lead screw and is fixed in the gland on the electrolysis cell cavity.
7. The electrolytic cell of claim 1 wherein:
the counter electrode is one of a carbon rod, a platinum sheet and a platinum wire; the reference electrode is one of a saturated calomel electrode and a silver/silver chloride electrode.
8. The electrolytic cell of claim 1 wherein:
the lead is one of a platinum wire, a copper adhesive tape and an aluminum adhesive tape; the electrocatalyst is one or more than two of electrocatalysts containing metal elements;
the cavity has good chemical stability, and can be one or more of Polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115096969A (en) * | 2022-06-20 | 2022-09-23 | 中国地质大学（北京） | Cadmium (II) ion detection method based on composite material modified electrode and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN207181355U (en) * | 2017-09-05 | 2018-04-03 | 北京中研环科科技有限公司 | A kind of electrocatalytic reaction pond in situ and include its test device |
| CN109470725A (en) * | 2018-09-10 | 2019-03-15 | 上海交通大学 | The synchrotron radiation in-situ testing device of catalyst in fuel cell catalyst layer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN207181355U (en) * | 2017-09-05 | 2018-04-03 | 北京中研环科科技有限公司 | A kind of electrocatalytic reaction pond in situ and include its test device |
| CN109470725A (en) * | 2018-09-10 | 2019-03-15 | 上海交通大学 | The synchrotron radiation in-situ testing device of catalyst in fuel cell catalyst layer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115096969A (en) * | 2022-06-20 | 2022-09-23 | 中国地质大学（北京） | Cadmium (II) ion detection method based on composite material modified electrode and application |
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Application publication date: 20210528 |