A high-applicability electrochemical in-situ detection combination device

Abstract

The utility model relates to electrochemistry detection equipment field, specifically is a kind of high applicability electrochemistry in situ detection combination device, including sample cell, work electrode slot is set up on sample cell side wall, detachably insert the work electrode plugboard of electrically conductive in work electrode slot, work electrode plugboard includes substrate, and it is equipped with clamping assembly, fixed component and connecting component on substrate, clamping assembly includes oppositely arranged upper clamping plate and lower clamping plate, upper clamping plate and lower clamping plate are configured to be able to slide along the surface of substrate, and corresponding detection through-hole is set up on upper clamping plate and lower clamping plate, the central axis of detection through-hole is collinear with the central axis of upper optical window, lower optical window, and connecting component includes electrode lead wire interface arranged on substrate.The utility model aims at improving the problem that existing device cannot be flexibly adapted to other spectral technology due to the imbalance of sample upper and lower surface reaction environment and reaction rate.

Description

Technical Field

[0001] This utility model relates to the field of electrochemical detection equipment, specifically a highly applicable electrochemical in-situ detection combined device. Background Technology

[0002] In electrochemical research, real-time, in-situ detection of dynamic processes at the electrode interface is crucial for elucidating reaction mechanisms. In-situ spectroscopic-electrochemical coupling technology, by integrating electrochemical reactions with spectroscopic characterization (such as UV-Vis spectroscopy, Raman spectroscopy, etc.), enables real-time tracking of species at the electrode interface, effectively overcoming the limitations of traditional offline characterization, which is often described as a "static snapshot."

[0003] To achieve complementary combinations of multiple spectroscopic techniques, existing technologies have made relevant attempts. For example, patent publication number CN120043984A discloses an in-situ electrochemical infrared spectroscopy-Raman spectroscopy coupling device, which combines the working electrode and the infrared optical window into one, using the attenuated total internal reflection principle to detect interface species. However, in order to achieve effective acquisition of infrared signals, this device forcibly fixes the sample to be tested to the surface of the infrared window at the bottom of the cell.

[0004] The sample-window contact structure described above, designed to adapt to a single infrared testing mode, has caused significant side effects. The tight contact between the sample's lower surface and the window severely hinders the flow of electrolyte at the interface, leading to uneven reactant concentrations on the lower surface. This, in turn, causes an imbalance in the reaction environment and reaction rate between the upper and lower surfaces, making it difficult to directly correlate the spectral data from the lower and upper surfaces, thus affecting the accuracy of the analysis. Furthermore, it prevents the device from flexibly adapting to other spectroscopic techniques (such as UV-Vis spectroscopy, fluorescence spectroscopy, and X-ray absorption spectroscopy). Utility Model Content

[0005] The present invention aims to provide a highly applicable electrochemical in-situ detection device to improve the problem that existing devices cannot flexibly adapt to other spectroscopic techniques due to the uneven reaction environment and reaction rate on the upper and lower surfaces of the sample.

[0006] To solve the above technical problems, the specific solution adopted by this utility model is as follows: It includes a sample cell, with a reference electrode and a counter electrode at the top, an electrolyte inlet and an electrolyte outlet on the side wall, an upper optical window and a lower optical window at the top and bottom of the sample cell respectively, with light-transmitting sheets mounted on the upper and lower optical windows, and a working electrode slot on the side wall of the sample cell. A conductive working electrode insert is detachably inserted into the working electrode slot. The working electrode insert includes a base plate, on which a clamping assembly, a fixing assembly, and a connecting assembly are provided. The clamping assembly is used to clamp and electrically connect the sample to be tested, and includes a relative... The upper and lower clamps are configured to slide relative to each other along the surface of the substrate. The gap between the upper and lower clamps is adjusted by clamping bolts to clamp or release the sample to be tested. Detection through holes are correspondingly opened on the upper and lower clamps to expose the sample to be tested in the electrolyte. The central axis of the detection through holes is collinear with the central axes of the upper and lower optical windows to form a detection channel through the sample cell. The fixing assembly is used to connect the working electrode insert plate and the sample cell. The connecting assembly includes an electrode lead interface provided on the substrate. The electrode lead interface is used to connect to the electrochemical workstation to form a working electrode circuit.

[0007] As a further optimization of a highly applicable electrochemical in-situ detection device: the sample cell has an H-shaped structure, which includes two vertical sections and a horizontal section located between the two vertical sections. The upper optical window and the lower optical window are respectively located at the top and bottom of the horizontal section. The working electrode slot is opened on the side wall of the horizontal section, and the reference electrode and the counter electrode are respectively located at the top of the two vertical sections.

[0008] As a further optimization of a highly applicable electrochemical in-situ detection device: the connecting surfaces at both ends of the horizontal section and the vertical section are both inclined, so that the distance between the two vertical sections gradually increases from the horizontal section upwards and downwards, so as to form an flared operating space above and below the horizontal section.

[0009] As a further optimization of a highly applicable electrochemical in-situ detection device: the electrolyte injection port is located at the top of one of the vertical sections, and the electrolyte discharge port is provided at the bottom of both vertical sections.

[0010] As a further optimization of a highly applicable electrochemical in-situ detection device: the transparent sheet and the sample cell are detachably connected by an installation component. The installation component includes a first assembly and a second assembly arranged opposite to each other, with the transparent sheet clamped between the first assembly and the second assembly. The first assembly has a pin at the position that contacts the second assembly, and the second assembly has a slot at the corresponding position. The first assembly and the second assembly are connected by the cooperation of the pin and the slot. The outer sides of the first assembly and the second assembly have external threads, and the inner sides of the upper optical window and the lower optical window have internal threads. The cooperation of the external threads and the internal threads enables the transparent sheet to be loaded and unloaded on the sample cell.

[0011] As a further optimization of a highly applicable electrochemical in-situ detection device: both the first and second assembly components are equipped with working ears.

[0012] As a further optimization of a highly applicable electrochemical in-situ detection device: an elastic protective pad is provided between the first and second components in the contact area with the light-transmitting sheet.

[0013] As a further optimization of a highly applicable electrochemical in-situ detection device: the fixing component includes fixing bolts on the substrate, which, through the cooperation of the fixing bolts with the threaded holes on the side wall of the sample cell, can fix the working electrode plate to the side wall of the sample cell.

[0014] As a further optimization of a highly applicable electrochemical in-situ detection device: a seal is provided in the connection area between the substrate and the working electrode slot, and an insulating layer is provided on the outer surface of the substrate.

[0015] As a further optimization of a highly applicable electrochemical in-situ detection device: the upper and lower clamps are slidably connected by sliders on the upper and lower clamps and grooves on the substrate.

[0016] Beneficial effects: This utility model sets the working electrode as a detachable working electrode insert plate, and places the sample to be tested inside the working electrode insert plate. The detection through holes opened on the upper and lower clamps allow the sample to be tested to fully contact the electrolyte. Moreover, the insert-type working electrode insert plate ensures that the upper and lower surfaces of the sample to be tested have similar reaction environments. The spectroscopic detection instrument can realize in-situ detection of the sample to be tested through the upper and lower optical windows. This device improves the problem that the device cannot flexibly adapt to other spectroscopic technologies due to the uneven reaction environment and reaction rate on the upper and lower surfaces of the sample.

[0017] The H-shaped sample cell design of this invention allows the spectroscopic instrument to perform in-situ detection of the sample at closer range, improving detection accuracy. Furthermore, the inclined design ensures ample operating space during actual installation of the spectroscopic probe, avoiding mechanical interference. The detachable light-transmitting plate design simplifies cleaning and replacement, preventing corrosion of the light-transmitting plate in a long-term electrochemical reaction environment, which can lead to low light transmission efficiency and affect the accuracy of spectroscopic detection. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the electrochemical in-situ detection combined device of this utility model; Figure 2 This is a cross-sectional view of the electrochemical in-situ detection combined device of this utility model; Figure 3 This is a schematic diagram of the working electrode insertion plate of this utility model; Figure 4 This is a top view of the upper clamping plate of this utility model; Figure 5 This is a schematic diagram of the installation components of this utility model.

[0019] The diagram shows the following markings: 1. Sample cell; 2. Reference electrode; 3. Working ear; 4. Transmitter; 5. Mounting assembly; 501. First assembly; 502. Second assembly; 6. Counter electrode; 7. External thread; 8. Internal thread; 9. Upper optical window; 10. Working electrode slot; 11. Fixing assembly; 12. Connecting assembly; 13. Base plate; 14. Working electrode insert plate; 15. Detection through hole; 16. Clamping assembly; 1601. Upper clamping plate; 1602. Lower clamping plate; 17. Threaded hole; 18. Lateral section; 19. Discharge port; 20. Vertical section; 21. Injection port; 22. Upper spectrometer; 23. Lower optical window; 24. Lower spectrometer; 25. Protective pad; 26. Clamping bolt; 27. Seal; 28. Slide groove; 29. ​​Slider; 30. Pin; 31. Slot; 32. Fixing bolt; 33. Electrode lead interface. Detailed Implementation

[0020] like Figure 1 and Figure 2As shown, a highly applicable electrochemical in-situ detection coupled device includes a sample cell 1, which is the main site of the electrochemical reaction. A reference electrode 2 and a counter electrode 6 are located at the top of the sample cell 1. These electrodes are commonly used in existing electrochemical reactions. An electrolyte inlet 21 and an electrolyte outlet 19 are located on the side wall of the sample cell 1, used for injecting and renewing the electrolyte. An upper optical window 9 and a lower optical window 23 are respectively located at the top and bottom of the sample cell 1, providing optical path channels for spectral detection. A light-transmitting plate 4 is mounted on the upper optical window 9 and the lower optical window 23, used for transmitting and filtering the detection light from the spectrometer. The above are conventional technical methods in the prior art and will not be elaborated further here.

[0021] The sample cell 1 has an H-shaped structure, which includes two vertical sections 20 and a horizontal section 18 located between the two vertical sections 20. The upper optical window 9 and the lower optical window 23 are respectively located at the top and bottom of the horizontal section 18. The working electrode slot 10 is opened on the side wall of the horizontal section 18. The reference electrode 2 and the counter electrode 6 are respectively located at the top of the two vertical sections 20. The design of the H-shaped sample cell 1 allows the upper spectrometer 22 located above the horizontal section 18 and the lower spectrometer 24 located below the horizontal section 18 to perform in-situ detection of the sample to be tested at a closer distance, thereby improving the detection accuracy. At the same time, the design of the H-shaped sample cell 1 keeps the upper optical window 9 and the lower optical window 23 away from the worktable surface, thereby avoiding frequent friction between the light transmittance sheet 4 and the worktable surface during daily use and extending the life of the light transmittance sheet 4.

[0022] The H-shaped sample cell 1 has inclined surfaces at both ends of the horizontal section 18 and the vertical section 20, causing the distance between the two vertical sections 20 to gradually increase from the horizontal section 18 upwards and downwards. This creates a flared operating space above and below the horizontal section 18. The flared operating space design facilitates the approach, alignment, and fixation of large or irregularly shaped spectroscopic probes, avoiding mechanical interference. The electrolyte injection port 21 is located at the top of one of the vertical sections 20, and the bottom of both vertical sections 20 is provided with an electrolyte discharge port 19. Valves are installed at both the electrolyte injection port 21 and the discharge port 19. The design of the two discharge ports 19 allows the electrolyte in the sample cell 1 to be completely discharged, preventing electrolyte residue from affecting the next experiment.

[0023] A working electrode slot 10 is provided on the side wall of the sample cell 1. A conductive working electrode plate 14 is detachably inserted into the working electrode slot 10. The working electrode slot 10 is used for precise guidance and installation of the working electrode plate 14. The working electrode plate 14 includes a substrate 13. A sealing element 27 is provided at the connection area between the substrate 13 and the working electrode slot 10. The sealing element 27 is used to seal the tiny gap between the working electrode plate 14 and the working electrode slot 10 to prevent electrolyte leakage. An insulating layer is provided on the outside of the substrate 13 to prevent the operator from accidentally touching the conductive substrate 13 and making contact when the device is powered on. The substrate 13 is provided with a clamping assembly 16, a fixing assembly 11, and a connecting assembly 12. The clamping assembly 16 is used to clamp and electrically connect the sample to be tested. The fixing assembly 11 is used to connect the working electrode plate 14 and the sample cell 1. The connecting assembly 12 is used to connect the electrochemical workstation to form a working electrode circuit. The working electrode plate 14 integrates the function of the working electrode and the sample clamping function into a detachable assembly.

[0024] like Figure 3 and Figure 4 As shown, the clamping assembly 16 includes an upper clamping plate 1601 and a lower clamping plate 1602 disposed opposite to each other. The upper clamping plate 1601 and the lower clamping plate 1602 are configured to slide relative to each other along the surface of the substrate 13. The upper clamping plate 1601 and the lower clamping plate 1602 are slidably connected to the sliding groove 28 on the substrate 13 by a slider 29 provided on the upper clamping plate 1601 and the lower clamping plate 1602. The distance between the upper clamping plate 1601 and the lower clamping plate 1602 is adjusted by a clamping bolt 26 to clamp or release the sample to be tested. The upper clamping plate 1601 and the lower clamping plate 1602 can mechanically fix the sample to be tested, such as a metal sheet or conductive glass. After the upper clamping plate 1601 and the lower clamping plate 1602 clamp the sample to be tested, it can ensure that the sample to be tested is electrically connected to the clamping assembly 16, and then form a working electrode circuit with the electrochemical workstation through the connecting assembly 12.

[0025] The upper clamping plate 1601 and the lower clamping plate 1602 are respectively provided with detection through holes 15. The detection through holes 15 are used to expose the sample to be tested in the electrolyte. When the clamping assembly 16 clamps the sample to be tested, the central area of ​​the sample to be tested that needs to be studied is exposed through the detection through holes 15. The central axis of the detection through holes 15 is collinear with the central axes of the upper optical window 9 and the lower optical window 23 to form a detection channel that penetrates the sample cell 1. The collinear detection channel can ensure that the detection optical path can directly act on the area where the sample to be tested reacts with the electrolyte.

[0026] The fixing assembly 11 includes a fixing bolt 32 disposed on the substrate 13. After the working electrode insert plate 14 is inserted into the working electrode slot 10, the fixing bolt 32 locks the working electrode insert plate 14 from the side to prevent it from loosening or shifting due to vibration or liquid flow during the experiment. Through the cooperation of the fixing bolt 32 with the threaded hole 17 on the side wall of the sample cell 1, the working electrode insert plate 14 can be fixed to the side wall of the sample cell 1. At the same time, the cooperation of the fixing bolt 32 with the threaded hole 17 can press the sealing member 27 to enhance the sealing effect of the sealing member 27.

[0027] The connection component 12 includes an electrode lead interface 33 disposed on the substrate 13. The electrode lead interface 33 is used to connect an electrochemical workstation to form a working electrode circuit. The electrode lead interface 33 connects the current lead of the external electrochemical workstation to the working electrode plug plate 14.

[0028] like Figure 5 As shown, the light-transmitting sheet 4 and the sample cell 1 are detachably connected by an installation assembly 5. The installation assembly 5 includes a first mounting part 501 and a second mounting part 502 arranged opposite to each other. The light-transmitting sheet 4 is clamped between the first mounting part 501 and the second mounting part 502. A pin 30 is provided on the first mounting part 501 at the position that contacts the second mounting part 502, and a slot 31 is provided at the corresponding position on the second mounting part 502. The first mounting part 501 and the second mounting part 502 are connected by the cooperation of the pin 30 and the slot 31. The installation assembly 5 securely clamps the brittle light-transmitting sheet 4 and connects it to the sample cell 1 as a whole. An elastic protective pad 25 is provided in the contact area between the first mounting part 501 and the second mounting part 502 and the light-transmitting sheet 4. The elastic protective pad 25 buffers the clamping force to prevent the light-transmitting sheet 4 from being crushed. At the same time, the elastic protective pad 25 can fill the small unevenness between the light-transmitting sheet 4 and the installation assembly 5 to assist in sealing.

[0029] The first assembly 501 and the second assembly 502 have external threads 7 on their outer sides, and internal threads 8 on the inner sides of the upper optical window 9 and the lower optical window 23. The mating of the external threads 7 and the internal threads 8 is designed to achieve a rigid seal and quick assembly / disassembly between the mounting assembly 5 and the sample cell 1. The axial pressure generated by tightening the threads ensures that the light-transmitting sheet 4 is uniformly pressed and achieves a reliable sealing effect, effectively preventing electrolyte leakage. At the same time, this detachable structure greatly facilitates the cleaning and replacement of the light-transmitting sheet 4 by the staff, improving the applicability of the device. Both the first assembly 501 and the second assembly 502 are equipped with working ears 3, which provide a force point for the staff to install and remove the light-transmitting sheet 4, making it easy for the staff to tighten the entire mounting assembly 5 by hand or with tools.

[0030] The method of using the highly applicable electrochemical in-situ detection combined device of this utility model is as follows: First, place the sample to be tested between the upper and lower clamping plates 1602 of the working electrode insert plate 14, and tighten the clamping bolts 26 to hold the sample and form an electrical connection; then, insert the working electrode insert plate 14 into the working electrode slot 10 on the side wall of the sample cell 1 and press it firmly with the fixing bolts 32; next, screw the mounting assembly 5 of the assembled light-transmitting plate 4 into the upper and lower optical windows 23, and connect the reference electrode 2, the counter electrode 6 and the working electrode lead to the electrochemical workstation; finally, introduce electrolyte through the injection port 21 until the sample cell 1 is filled, so that while starting the electrochemical reaction, the spectrometer can be used to collect in-situ spectral signals of the sample suspended in the detection channel through the upper and lower optical windows 23.

Claims

1. A highly applicable electrochemical in-situ detection coupled device, comprising a sample cell (1), a reference electrode (2) and a counter electrode (6) provided at the top of the sample cell (1), an electrolyte inlet (21) and an electrolyte outlet (19) provided on the side wall of the sample cell (1), an upper optical window (9) and a lower optical window (23) respectively opened at the top and bottom of the sample cell (1), and a light-transmitting plate (4) mounted on the upper optical window (9) and the lower optical window (23), characterized in that: A working electrode slot (10) is provided on the side wall of the sample cell (1). A working electrode insert plate (14) is detachably inserted into the working electrode slot (10). The working electrode insert plate (14) includes a base plate (13). A clamping assembly (16), a fixing assembly (11), and a connecting assembly (12) are provided on the base plate (13). The clamping assembly (16) is used to clamp and electrically connect the sample to be tested. The clamping assembly (16) includes an upper clamping plate (1601) and a lower clamping plate (1602) arranged opposite to each other. The upper clamping plate (1601) and the lower clamping plate (1602) are configured to slide relative to each other along the surface of the base plate (13). The upper clamping plate (1601) and the lower clamping plate (1602) are connected by clamping screws. The bolt (26) adjusts the spacing to clamp or release the sample to be tested. The upper clamp (1601) and the lower clamp (1602) are respectively provided with detection through holes (15). The detection through holes (15) are used to expose the sample to be tested in the electrolyte. The central axis of the detection through holes (15) is collinear with the central axis of the upper optical window (9) and the lower optical window (23) to form a detection channel through the sample cell (1). The fixing component (11) is used to connect the working electrode plate (14) and the sample cell (1). The connecting component (12) includes an electrode lead interface (33) provided on the substrate (13). The electrode lead interface (33) is used to connect the electrochemical workstation to form a working electrode circuit.

2. The highly applicable electrochemical in-situ detection coupled device according to claim 1, characterized in that: The sample cell (1) has an H-shaped structure. The H-shaped sample cell (1) includes two vertical parts (20) and a horizontal part (18) located between the two vertical parts (20). The upper optical window (9) and the lower optical window (23) are respectively located at the top and bottom of the horizontal part (18). The working electrode slot (10) is opened on the side wall of the horizontal part (18). The reference electrode (2) and the counter electrode (6) are respectively located at the top of the two vertical parts (20).

3. The highly applicable electrochemical in-situ detection coupled device according to claim 2, characterized in that: The connecting surfaces of the horizontal part (18) and the vertical part (20) are both inclined, so that the distance between the two vertical parts (20) gradually increases from the horizontal part (18) upwards and downwards, so as to form an flared operating space above and below the horizontal part (18).

4. The highly applicable electrochemical in-situ detection coupled device according to claim 2, characterized in that: The electrolyte injection port (21) is located at the top of one of the vertical parts (20), and the electrolyte discharge port (19) is provided at the bottom of both vertical parts (20).

5. The highly applicable electrochemical in-situ detection coupled device according to claim 1, characterized in that: The light-transmitting sheet (4) and the sample cell (1) are detachably connected by an installation component (5). The installation component (5) includes a first mounting part (501) and a second mounting part (502) arranged opposite to each other. The light-transmitting sheet (4) is held between the first mounting part (501) and the second mounting part (502). A pin (30) is provided on the first mounting part (501) at the position that contacts the second mounting part (502). A slot (31) is provided on the second mounting part (502) at the corresponding position. The first mounting part (501) and the second mounting part (502) are connected by the cooperation of the pin (30) and the slot (31). The first mounting part (501) and the second mounting part (502) are provided with external threads (7) on the outside. The upper optical window (9) and the lower optical window (23) are provided with internal threads (8) on the inside. The light-transmitting sheet (4) can be loaded and unloaded on the sample cell (1) by the cooperation of the external threads (7) and the internal threads (8).

6. The highly applicable electrochemical in-situ detection coupled device according to claim 5, characterized in that: Both the first assembly (501) and the second assembly (502) are provided with working ears (3).

7. The highly applicable electrochemical in-situ detection coupled device according to claim 5, characterized in that: An elastic protective pad (25) is provided between the first assembly (501) and the second assembly (502) in the contact area with the light-transmitting sheet (4).

8. The highly applicable electrochemical in-situ detection coupled device according to claim 1, characterized in that: The fixing assembly (11) includes a fixing bolt (32) provided on the substrate (13). By cooperating with the threaded hole (17) on the side wall of the sample cell (1), the working electrode plate (14) can be fixed to the side wall of the sample cell (1).

9. The highly applicable electrochemical in-situ detection coupled device according to claim 1, characterized in that: A seal (27) is provided in the connection area between the substrate (13) and the working electrode slot (10), and an insulating layer is provided on the outer surface of the substrate (13).

10. The highly applicable electrochemical in-situ detection coupled device according to claim 1, characterized in that: The upper clamping plate (1601) and the lower clamping plate (1602) are slidably connected by sliders (29) provided on the upper clamping plate (1601) and the lower clamping plate (1602) and by a groove (28) provided on the base plate (13).

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