A multi-purpose electrochemical in-situ cell
By designing a multi-purpose electrochemical in-situ cell and integrating various characterization methods, the problems of single function and signal absorption of existing in-situ cells have been solved, and efficient and low-cost multi-functional in-situ characterization has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- UNIV OF SCI & TECH OF CHINA
- Filing Date
- 2023-07-14
- Publication Date
- 2026-07-14
AI Technical Summary
Existing in-situ pools have limited functionality, and the water layer severely absorbs infrared and X-ray signals, increasing experimental costs and complexity. Furthermore, multiple pools are required to combine various characterization methods.
A multi-purpose electrochemical in-situ cell is designed, employing sheet-shaped working electrodes of different materials to directly isolate the electrolyte and air, combining a metal mesh structure to enhance the signal, and integrating the functions of infrared spectroscopy, Raman spectroscopy, X-ray diffraction and synchrotron X-ray absorption spectroscopy, while avoiding interference from the water layer.
It reduces signal interference, improves data reliability and experimental convenience, reduces costs, enhances signal acquisition sensitivity, and enables simultaneous experiments using multiple characterization methods.
Smart Images
Figure CN116858905B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrochemical in-situ characterization technology, specifically relating to a multi-purpose electrochemical in-situ cell. Background Technology
[0002] In-situ characterization is a detection technique that has developed in recent years and plays an important role in exploring the mechanisms of heterogeneous catalysis. The most important characteristic of in-situ characterization is the ability to analyze specific reactions "online" using different instruments, observing the reaction process and the structure, morphology, and other properties of the catalyst in real time during the chemical reaction, which helps to understand the true reaction mechanism. After years of development, synchrotron infrared spectroscopy (SR-FTIR), Raman spectroscopy, X-ray diffraction (XRD), and synchrotron X-ray absorption spectroscopy (XAFS) have become some of the most important tools for researchers to study catalyst structural evolution and reaction mechanisms. Currently, corresponding in-situ cells have been developed for different characterization methods. These in-situ cells share the common feature that the working electrode is placed directly below a transparent light window, with a certain distance between the working electrode and the light window, and is filled with electrolyte during operation. Furthermore, individual in-situ cells are expensive to manufacture. If a multifunctional in-situ cell could be designed to avoid the absorption of X-rays or infrared radiation by the electrolyte under operating conditions, and to integrate multiple testing modes, it would greatly improve the convenience and sensitivity of current in-situ electrochemical detection. However, research technology in this area is currently lacking.
[0003] Currently, in-situ cells used for infrared spectroscopy (IR), Raman spectroscopy, X-ray diffraction (XRD), and synchrotron X-ray absorption spectroscopy (XAFS) are all quite expensive. However, for researchers, to fully understand a reaction mechanism, it is often necessary to combine multiple in-situ characterization methods. This necessitates preparing multiple in-situ cells simultaneously, increasing the economic burden and experimental complexity. Furthermore, most commercially available in-situ infrared and XRD cells currently use external reflection mode, meaning there is a water film between the working electrode and the window. The test light path must pass through the water layer, but the water layer severely absorbs infrared and X-rays, resulting in a significant weakening of the acquired signal. Summary of the Invention
[0004] The purpose of this invention is to provide a multi-purpose electrochemical in-situ cell that integrates infrared spectroscopy (IR), Raman spectroscopy (Raman), X-ray diffraction (XRD), and synchrotron X-ray absorption spectroscopy (XAFS) to solve the problems of limited functionality and severe absorption of infrared and X-rays by the water layer in existing in-situ electrochemical cells. Furthermore, in Raman and infrared testing modes, a metal mesh structure can be deposited on the working electrode. The nano-metal exhibits a surface enhancement effect, allowing for the acquisition of information on the adsorbed products and intermediate products of the electrocatalyst.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] A multi-purpose electrochemical in-situ cell includes a cell body and a top cover detachably connected to the cell body. A counter electrode and a reference electrode are installed on the side walls of the cell body. A through hole is formed in the center of the top cover. The center of the cell body has an upward-opening liquid storage reaction tank. The cell body has an inlet hole and an outlet hole communicating with the liquid storage reaction tank. An electrolyte inlet pipe is connected to the inlet hole, and an electrolyte outlet pipe is connected to the outlet hole. A sheet-shaped working electrode is covered above the liquid storage reaction tank. A pair of grooves are symmetrically formed on the outer side of the top surface of the cell body, and a spring electrode is placed in the groove. One end of the spring electrode contacts the bottom surface of the sheet-shaped working electrode. The spring electrode is a common commercial spring electrode, which can make good contact with the working electrode and avoid crushing the working electrode. In the multi-purpose electrochemical in-situ cell provided by this invention, the sheet-shaped working electrode acts as a viewing window, directly isolating the electrolyte and air, allowing light to directly contact the catalyst through the window, avoiding interference from the water layer on the signal. The material and design of the sheet-shaped working electrode vary depending on the different in-situ characterization methods, as detailed below:
[0007] When used for in-situ XRD and in-situ XAFS characterization, the sheet working electrode is made of glassy carbon sheet. Since glassy carbon is an amorphous carbon material, it has very low absorption of X-rays, making it suitable for X-ray-based in-situ XRD and in-situ XAFS characterization.
[0008] When used for synchrotron radiation in-situ infrared characterization, the sheet-like working electrode includes a substrate made of single-crystal silicon (Si). Single-crystal silicon has excellent light transmittance in the infrared band and is currently the most widely used infrared optical window material. A metal mesh-like region is first photolithographically etched into the central area of the single-crystal silicon substrate. This region serves as the sample loading area, and an electrocatalyst is then deposited onto it to serve as the in-situ testing area for the sample reaction. The biggest advantage of this design is that it allows the incident light to directly contact the sample, reducing signal loss. Furthermore, the unique rough nanoarray structure of the metal mesh can excite local plasmon resonances, leading to electromagnetic enhancement, which has a certain enhancement effect on Raman and infrared signals, and can greatly enhance the weak signals of reaction intermediates. In addition, a nano-metal film is chemically deposited or vacuum-deposited next to it. This area connects to the metal mesh-like region as a conductive area that contacts the spring electrode, and the entire electrode serves as the working electrode. More preferably, the metal mesh-like region and the nano-metal film are made of the same material, a noble metal or a transition metal. Further, the noble metal can be gold, silver, or platinum, etc.; the transition metal can be copper.
[0009] When used for synchrotron radiation in-situ Raman characterization, it is similar to the synchrotron radiation in-situ infrared characterization described above, except that the substrate material is sapphire or quartz, while other structures are the same. Since Raman spectrometers use lasers within the visible region, sapphire or quartz are commonly chosen as the Raman testing window material because quartz or high-grade sapphire have excellent light transmission properties.
[0010] As a preferred technical solution, to enhance the sealing of the tank, an annular shallow groove is formed around the periphery of the liquid storage reaction tank, and a sealing ring is placed inside the annular shallow groove. Furthermore, the bottom of the tank has a base with threaded holes, and the top cover and the base are connected by bolts.
[0011] The beneficial effects of this invention are as follows:
[0012] (1) The multipurpose electrochemical in-situ cell provided by the present invention is designed with a sheet-shaped working electrode. The sheet-shaped working electrode serves as a window to directly isolate the electrolyte and air. Before testing, the test sample is directly loaded onto the surface of the sheet-shaped working electrode, so that during the test, the light directly passes through the sheet-shaped working electrode and contacts the catalyst. The light path does not need to pass through the water layer, thus avoiding the interference of the water layer on the signal. This greatly reduces the disadvantages of the electrolyte's absorption and interference of X-rays and infrared rays, ensuring that the obtained data is true and reliable.
[0013] (2) This invention replaces different working electrode materials according to the characteristics of different characterization techniques, thereby designing an in-situ cell that integrates infrared spectroscopy (IR), Raman spectroscopy (Raman), X-ray diffraction (XRD) and synchrotron radiation X-ray absorption spectroscopy (XAFS), thus solving the problem of the single function of the current in-situ cell.
[0014] (3) The in-situ cell provided by the present invention does not have a specific optical path and window design, has low processing cost, is easy to use, and saves time and price costs.
[0015] (4) When the multi-purpose electrochemical in-situ cell provided by the present invention is used for in-situ characterization of synchrotron infrared and Raman, a metal mesh-like region is created in the middle of the working electrode, and the sample is coated in this region. This does not block the test light path, but can also enhance the Raman and infrared signals, thus having a surface enhancement effect, and can obtain information on the adsorbed products and intermediate products of the electrocatalyst. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the structure of the multi-purpose electrochemical in-situ cell provided by the present invention;
[0017] Figure 2 for Figure 1 Exploded view;
[0018] Figure 3 This is a schematic diagram of the pool structure;
[0019] Figure 4 A schematic diagram of the bottom structure of the sheet-like working electrode in a multi-purpose electrochemical in-situ cell used for synchrotron radiation in-situ infrared characterization.
[0020] Figure 5 for Figure 4 Enlarged view of section A in the middle;
[0021] Reference numerals: 1-Top cover, 101-Through hole, 2-Pool body, 201-Liquid storage reaction tank, 202-Groove, 203-Annular shallow groove, 3-Base, 301-Threaded hole, 4-Bolt, 5-Counter electrode, 6-Reference electrode, 7-Electrolyte inlet pipe, 8-Electrolyte outlet pipe, 9-Sheet working electrode, 10-Spring electrode, 11-Sealing ring, 12-Substrate, 13-Metal mesh area, 14-Nano metal film. Detailed Implementation
[0022] The present invention will be further described below with reference to embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments are not intended to limit the present invention. In addition, unless otherwise specified, the components in the following embodiments are conventional structures in the prior art, and therefore will not be described in detail.
[0023] In the description of this invention, it should be understood that the terms "upper", "lower", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations of this invention.
[0024] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.
[0025] refer to Figures 1 to 5 A multi-purpose electrochemical in-situ cell includes, from top to bottom, an upper cover 1, a cell body 2, and a base 3. The base 3 has a threaded hole 301, and the upper cover 1 and the base 3 are connected by bolts 4. A through hole 101 is provided in the middle of the upper cover 1 to allow light to pass through during detection, directly illuminating the sheet-like working electrode 9. The cell body 2 can be made of PEEK material, and a counter electrode 5 and a reference electrode 6 are installed on the side walls of the cell body 2. The middle of the cell body 2 has an upward-opening liquid storage reaction tank 201, and the cell body 2 has an inlet hole and an outlet hole communicating with the liquid storage reaction tank 201. The inlet hole is connected to an electrolyte inlet pipe 7, and the outlet hole is connected to an electrolyte outlet pipe 8. Electrolyte can be introduced into or discharged from the storage reaction tank 201. A sheet-shaped working electrode 9 covers the top of the storage reaction tank 201. A pair of grooves 202 are symmetrically formed on the outer side of the top surface of the tank body 2. A spring electrode 10 is placed in the grooves 202, with one end of the spring electrode 10 contacting the bottom surface of the sheet-shaped working electrode 9. To increase the sealing of the tank body, an annular shallow groove 203 is formed around the storage reaction tank 201, and a sealing ring 11 is placed in the annular shallow groove 203. In the multi-purpose electrochemical in-situ cell provided by this invention, the sheet-shaped working electrode 9 serves as a viewing window, directly isolating the electrolyte and air, allowing light to directly contact the catalyst through the window, avoiding interference from the water layer on the signal. The material and design of the sheet-shaped working electrode 9 vary depending on the in-situ characterization method, as detailed below:
[0026] In one embodiment, when the in-situ cell is used for in-situ XRD and in-situ XAFS characterization, the sheet-shaped working electrode 9 is made of glassy carbon sheet. Before use, an electrocatalyst is drop-coated or electrodeposited onto the glassy carbon sheet, and then the sheet is assembled with the catalyst-loaded side facing down for in-situ XRD and in-situ XAFS characterization.
[0027] In another embodiment, when the in-situ cell is used for synchrotron radiation in-situ infrared characterization, the sheet-like working electrode 9 includes a substrate 12 made of single-crystal silicon. A metal mesh region 13 is photolithographically etched in the middle region of the single-crystal silicon. This region serves as the sample loading region, on which an electrocatalyst is drop-coated to serve as the in-situ sample reaction region. A nano-metal film 14 is chemically deposited or vacuum-deposited next to this region. This region connects to the metal mesh region 13 as a conductive area and contacts the spring electrode 10. The entire electrode serves as the working electrode. Furthermore, the metal mesh region 13 and the nano-metal film 14 are made of the same material, a noble metal or transition metal; specifically, it can be gold, silver, platinum, copper, etc. In specific applications, those skilled in the art can select the appropriate metal according to actual needs.
[0028] This in-situ cell can also be used for synchrotron radiation in-situ Raman characterization. When used for synchrotron radiation in-situ Raman characterization, the structure of the in-situ cell is similar to that of the one used for synchrotron radiation in-situ infrared characterization, except that the substrate 12 is made of sapphire or quartz, while the other structures are the same.
[0029] Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
Claims
1. A multi-purpose electrochemical in-situ cell, characterized in that: The device includes a pool body and a top cover detachably connected to the pool body; the pool body has an upward-opening liquid storage reaction tank in the middle, and a sheet-shaped working electrode is covered above the liquid storage reaction tank; a pair of grooves are symmetrically opened on the outer side of the top surface of the pool body, and a spring electrode is placed in the groove, with one end of the spring electrode contacting the bottom surface of the sheet-shaped working electrode; a through hole is opened in the middle of the top cover; a counter electrode and a reference electrode are installed on the side wall of the pool body; The sheet-like working electrode includes a substrate, a metal mesh region for loading a sample is photolithographically formed in the center of the substrate, a nano-metal film is deposited on the outer periphery of the metal mesh region on the substrate, the nano-metal film is connected to the metal mesh region and is in contact with the spring electrode; the metal mesh region and the nano-metal film are made of the same material, which is a noble metal or a transition metal. The substrate is made of monocrystalline silicon, sapphire, or quartz.
2. The multi-purpose electrochemical in-situ cell according to claim 1, characterized in that: The precious metal is gold, silver, or platinum.
3. The multi-purpose electrochemical in-situ cell according to claim 1, characterized in that: The transition metal is copper.
4. The multipurpose electrochemical in-situ cell according to any one of claims 1 to 3, characterized in that: The pool body has an inlet hole and an outlet hole that are connected to the liquid storage reaction tank; the inlet hole is connected to an electrolyte inlet pipe, and the outlet hole is connected to an electrolyte outlet pipe.
5. The multi-purpose electrochemical in-situ cell according to claim 4, characterized in that: The pool body has an annular shallow groove formed around the liquid storage reaction tank, and a sealing ring is placed inside the annular shallow groove.
6. The multi-purpose electrochemical in-situ cell according to claim 4, characterized in that: The bottom of the pool has a base with threaded holes, and the top cover and the base are connected by bolts.