In-situ electrochemical spectrum electrolytic cell, detection device and bubble removal method

Abstract

The present invention relates to the field of in-situ electrochemical spectroscopy, and discloses an in-situ electrochemical spectroscopy electrolytic tank, which comprises: a tank body, a liquid inlet part and a liquid outlet part are oppositely arranged on the side wall of the tank body, and the tank body is used for containing an electrolyte; the electrolyte circulating device is used for enabling the electrolyte to circularly flow to the liquid outlet part from the liquid inlet part in the cell body; the top cover is hermetically connected with the tank body; the working electrode is vertically arranged in the cell body; wherein the central part of the top cover is provided with a groove part, the bottom of the groove part is embedded with an optical window sheet, the working electrode is provided with a boss part, the boss part is provided with an upper end surface for bearing a test sample layer, and the groove part and the boss part are oppositely arranged up and down. The invention further discloses an in-situ electrochemical spectrum detection device and a method for removing bubbles on the surface of the working electrode. Bubbles are spontaneously separated from the surface of the working electrode, the interference of the bubbles on an electrochemical spectrum is effectively eliminated, and the quality of a spectrum signal is improved.

Description

Technical Field

[0001] This invention relates to the field of in-situ electrochemical spectroscopy technology, specifically to an in-situ electrochemical spectroscopy electrolytic cell, a detection device, and a bubble removal method. Background Technology

[0002] In-situ electrochemical spectroscopy is a technique developed by applying spectroscopic techniques to electrochemical research. It can directly obtain information at the molecular level about the interaction modes, adsorption orientation, and coverage of species on the electrode surface, in order to characterize and study electrochemical reaction processes at the solid-liquid interface. Raman spectroscopy, especially microconfocal Raman spectroscopy, is a commonly used spectroscopic technique in in-situ electrochemical spectroscopy.

[0003] Existing in-situ electrochemical spectroscopy is obtained using an in-situ electrochemical spectroscopy detection device, which includes an electrolytic cell and a Raman spectrometer. A working electrode is placed in the electrolytic cell, and a test sample layer is attached to the surface of the working electrode, where the expected chemical reaction occurs. Laser light emitted by the Raman spectrometer is incident on the surface of the working electrode and scattered. The Raman spectrometer collects the scattered light and performs spectral analysis to generate a Raman spectrum.

[0004] In existing technologies, some electrochemical reactions (such as water electrolysis) produce gases, which are adsorbed onto the surface of the working electrode in the form of bubbles. These bubbles are difficult to detach due to the strong adhesion between them and the working electrode. The bubbles adsorbed on the surface of the working electrode interfere with spectral detection. They not only reduce image quality but also change the refractive index of the medium in the detection optical path, causing the spectral signal collection area to deviate from the preset area and resulting in signal distortion. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem of bubbles adsorbed on the surface of the working electrode interfering with spectral detection in the prior art, and to provide an in-situ electrochemical spectral electrolysis cell, detection device and detection method, so as to realize that bubbles spontaneously detach from the surface of the working electrode during the in-situ electrochemical spectral detection process, thereby avoiding bubbles interfering with spectral detection.

[0006] To achieve the above objectives, the present invention provides an in-situ electrochemical spectroscopic electrolysis cell, comprising:

[0007] The pool body has an inlet and an outlet section arranged opposite each other on its side wall. The pool body is used to hold the electrolyte.

[0008] Electrolyte circulation device, which is used to continuously draw electrolyte from the outlet and feed it into the inlet, and to circulate the electrolyte from the inlet to the outlet in the tank.

[0009] The top cover, which is sealed to the pool body; and

[0010] The working electrode is vertically positioned within the pool body.

[0011] The top cover has a groove in the center, with an optical window embedded at the bottom. The working electrode has a boss at the top, with an upper surface for supporting the test sample layer. The groove and the boss are arranged opposite each other, with a gap between the bottom of the groove and the upper surface of the boss.

[0012] Preferably, the groove portion is a frustum shape that is wider at the top and narrower at the bottom, and the protrusion portion is a frustum shape that is narrower at the top and wider at the bottom.

[0013] Preferably, the in-situ electrochemical spectroscopic electrolytic cell further includes an instantaneous flow inlet pipe, which is used to pump electrolyte into the area between the groove and the boss.

[0014] Preferably, the electrolyte circulation device includes a circulation pipeline, a storage tank, and a circulation pump. The two ends of the circulation pipeline are connected to the inlet and outlet respectively, and the storage tank and circulation pump are both located on the circulation pipeline; and / or, the inlet and outlet are arranged on the same axis, and the axis is located between the groove and the boss.

[0015] Preferably, a gas collecting pipe is provided on the top cover, which is used to collect the gas generated in the electrolyte.

[0016] Preferably, a slot is provided on the side wall of the pool body for inserting a light intensity detection device, a reference electrode, or a counter electrode into the pool body.

[0017] A second aspect of the present invention provides an in-situ electrochemical spectroscopy detection device, comprising the above-mentioned in-situ electrochemical spectroscopy electrolytic cell and Raman spectrometer. The Raman spectrometer is used to emit incident light through an optical window onto the upper surface of the protrusion, collect scattered light from the upper surface of the protrusion, and generate a Raman spectrum by performing spectral analysis on the scattered light.

[0018] Preferably, the in-situ electrochemical spectroscopy detection device further includes a light intensity detection device disposed in the electrolyte, which is used to adjust the power of the incident light; and / or, the in-situ electrochemical spectroscopy detection device further includes a reference electrode and a counter electrode disposed in the electrolyte, wherein the working electrode, the reference electrode and the counter electrode are all connected to the electrode connector of an external electrochemical workstation through electrode leads.

[0019] A third aspect of the present invention provides a bubble removal method for removing bubbles from the surface of a working electrode in an in-situ electrochemical spectroscopic electrolysis cell, comprising the following steps:

[0020] S1. A narrow region is formed in the cell body of the in-situ electrochemical spectroscopic electrolysis cell, and one side of the narrow region is defined by the surface of the working electrode located in the cell body for carrying the test sample layer.

[0021] S2, to allow the electrolyte in the tank to circulate and flow through narrow areas.

[0022] Preferably, the bubble removal method is carried out using the above-mentioned in-situ electrochemical spectroscopic electrolysis cell, and the narrow region is formed by intervals.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The electrolyte is circulated in the cell by an electrolyte circulation device, and the circulating electrolyte carries away the bubbles that have detached from the working electrode in time.

[0025] (2) By setting the groove and the boss, a narrow area is formed between the groove and the boss. When the electrolyte flows through the narrow area, the Bernoulli effect will be formed. The Bernoulli effect increases the impact force and buoyancy of the electrolyte on the bubbles, and promotes the bubbles to detach from the surface of the working electrode.

[0026] (3) During the in-situ electrochemical spectroscopy detection process, the bubbles spontaneously detach from the working electrode surface and are promptly carried out, effectively avoiding the interference of bubbles on the electrochemical spectrum and improving the quality of the spectral signal.

[0027] (4) While forming the expected large flow rate in the local area above the working electrode, it is easy to control the electrolyte in the cell to maintain a small flow rate as a whole, prevent turbulence in the cell, and thus avoid the adverse effects of turbulence on the detection of electrochemical spectra.

[0028] (5) The in-situ electrochemical spectroscopic electrolytic cell and detection device can be obtained by improving the existing electrolytic cell and detection device without changing the existing optical path design. It has high compatibility and low manufacturing cost. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the structure of an in-situ electrochemical spectrophotometer in one embodiment;

[0030] Figure 2 This is a top view of an in-situ electrochemical spectroelectrolysis cell in one embodiment;

[0031] Figure 3 This is a schematic diagram of the electrolyte circulation device of an in-situ electrochemical spectroscopic electrolytic cell in one embodiment;

[0032] Figure 4 This is a schematic diagram of the structure of an in-situ electrochemical spectroscopic detection device in one embodiment;

[0033] Figure 5 These are in-situ electrochemical Raman spectra comparisons of the hydrogen evolution reaction;

[0034] Figure 6 This is a comparison of in-situ electrochemical Raman spectra of the oxygen evolution reaction.

[0035] The reference numerals in the attached figures are explained as follows:

[0036] 1-In-situ electrochemical spectroscopic electrolytic cell; 11-Cell body; 111-Inlet section; 112-Outlet section; 12-Electrolyte circulation device; 121-Circulation pipeline; 122-Storage tank; 123-Circulation pump; 13-Top cover; 131-Groove section; 14-Working electrode; 141-Protrusion section; 142-Bottom column; 15-Optical window; 16-Instantaneous flow rate inlet pipe; 17-Gas collection pipe; 18-Slot; 2-In-situ electrochemical spectroscopic detection device; 21-Raman spectrometer. Detailed Implementation

[0037] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0038] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," and "connect" 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; they can refer to the internal communication of two components or the interaction 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.

[0039] In the description of this invention, unless otherwise stated, the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use. They are used only for the convenience of describing this invention and simplifying the description, and are not intended to 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 limiting this invention.

[0040] Furthermore, if the present invention involves descriptions using terms such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features.

[0041] Reference Figures 1-3 The in-situ electrochemical spectroscopic electrolysis cell 1 provided by the present invention includes:

[0042] The pool body 11 has an inlet 111 and an outlet 112 arranged opposite to each other on its side wall. The pool body 11 is used to hold the electrolyte.

[0043] Electrolyte circulation device 12 is used to continuously draw out electrolyte from the outlet 112 and send it into the inlet 111, and make the electrolyte circulate from the inlet 111 to the outlet 112 in the tank body 11.

[0044] Top cover 13, top cover 13 is sealed to the pool body 11; and

[0045] The working electrode 14 is vertically disposed in the pool body 11;

[0046] The top cover 13 has a groove 131 in the center, and an optical window 15 is embedded at the bottom of the groove 131. The working electrode 14 has a boss 141 on the upper part, and the boss 141 has an upper end face for supporting the test sample layer. The groove 131 and the boss 141 are arranged opposite each other and there is a gap between the bottom of the groove 131 and the upper end face of the boss 141.

[0047] The in-situ electrochemical spectroscopic electrolytic cell 1 of the present invention achieves electrolyte circulation within the cell body 11 through an electrolyte circulation device 12, utilizing the circulating electrolyte to promptly carry away bubbles detached from the working electrode 14. The groove 131 and the protrusion 141 form a narrow region between them. When the electrolyte flows through this narrow region, a Bernoulli effect occurs, increasing the impact force and buoyancy of the electrolyte on the bubbles, thus promoting the detachment of bubbles from the surface of the working electrode 14. The reason why the Bernoulli effect increases the impact force and buoyancy of the electrolyte on the bubbles is as follows: due to the Bernoulli effect, the flow velocity in this narrow region increases, increasing the impact force on the bubbles; due to the Bernoulli effect, the hydraulic pressure in this narrow region decreases, causing the volume of bubbles adsorbed on the surface of the working electrode 14 to expand, thereby increasing the buoyancy of the electrolyte on the bubbles.

[0048] In one embodiment, the groove 131 is a frustum shape, wider at the top and narrower at the bottom, and the boss 141 is a frustum shape, narrower at the top and wider at the bottom. There is a gradually changing distance between the groove 131 and the boss 141, with the distance between the bottom of the groove 131 and the upper surface of the boss 141 being minimized. Since the test sample is placed on the upper surface of the boss 141, bubbles are generated and accumulate on the upper surface of the boss 141. When the electrolyte flows through the area between the bottom of the groove 131 and the upper surface of the boss 141, a more significant Bernoulli effect is formed, improving the bubble detachment effect.

[0049] In one embodiment, the in-situ electrochemical spectroscopic electrolytic cell 1 further includes an instantaneous flow rate inlet pipe 16, which is used to pump electrolyte into the area between the recess 131 and the boss 141. Before performing in-situ electrochemical spectroscopic detection, the surface of the working electrode 14 can be brushed through the instantaneous flow rate inlet pipe 16. This brushing is a pretreatment step and can be performed when a large number of bubbles have accumulated on the surface of the working electrode 14. Preferably, the electrolyte pumped by the instantaneous flow rate inlet pipe 16 forms turbulence, so as to generate a large impact force on the bubbles through turbulence, thereby causing the bubbles to break or detach from the surface of the working electrode 14. The instantaneous flow rate inlet pipe 16 includes an outlet and an inlet. The outlet is horizontally positioned and aligned with the area between the recess 131 and the boss 141, and the inlet is connected to a liquid storage device. A water pump for pumping electrolyte is also provided on the instantaneous flow rate inlet pipe 16.

[0050] Continue to refer to Figure 3 In one embodiment, the electrolyte circulation device 12 includes a circulation pipeline 121, a storage tank 122, and a circulation pump 123. The two ends of the circulation pipeline 121 are connected to the inlet 111 and the outlet 112, respectively. The storage tank 122 and the circulation pump 123 are both mounted on the circulation pipeline 121. The circulation pump 123 is, for example, a metering peristaltic pump. The storage tank 122 may also be equipped with a degassing unit, which removes air bubbles from the electrolyte by reducing gas solubility. Through this electrolyte circulation device 12, the electrolyte circulates between the tank 11 and the storage tank 122, and the electrolyte continuously flows over the working electrode 14 to promptly remove air bubbles that have detached from the surface of the working electrode 14.

[0051] The inlet section 111 and the outlet section 112 can be horizontally arranged circular or square tubes. Furthermore, the inlet section 111 and the outlet section 112 are coaxially arranged, and this axis is located within a narrow region between the groove section 131 and the boss section 141. This allows the electrolyte within the tank 11 to form a stable flow channel along the inlet section 111, the narrow region, and the outlet section 112, ensuring high fluidity of the electrolyte within this narrow region, thereby promoting the detachment of bubbles from the working electrode 14. Even further, the cross-sectional area of ​​this narrow region is smaller than the cross-sectional area of ​​the inlet section 111, further increasing the flow rate of the electrolyte flowing through this narrow region and further reducing the hydraulic pressure, thereby promoting the detachment of bubbles from the working electrode 14.

[0052] In one embodiment, the working electrode 14 is cylindrical in shape and vertically disposed within the pool body 11. The working electrode 14 includes a boss portion 141 and may also include a bottom column 142 located below the boss portion 141. The boss portion 141 is fixedly disposed on the bottom column 142, which is fixedly disposed at the bottom of the pool body 11. The bottom column 142 allows the boss portion 141 to be positioned at a preset height, thereby creating a desired distance between the boss portion 141 and the recessed portion 131. The boss portion 141 and the bottom column 142 can be integrally formed. The material of the boss portion 141 can be selected based on the working potential of the working electrode 14 and the material's corrosion resistance potential; for example, it can be glassy carbon, stainless steel, or titanium.

[0053] In one embodiment, the in-situ electrochemical spectroscopic electrolytic cell 1 further includes a reference electrode and a counter electrode disposed in the cell body 11. During spectroscopic detection, the reference electrode, the counter electrode, and the working electrode 14 are immersed together in the electrolyte. The reference electrode is used to provide a stable potential reference for measuring and comparing the potential of the working electrode 14. The counter electrode is used to form a circuit with the working electrode 14 and ensure that the electrochemical reaction occurs on the working electrode 14.

[0054] In one embodiment, a slot 18 is provided on the side wall of the pool body 11. The slot 18 is used to insert a light intensity detection device, a reference electrode, or a counter electrode into the pool body 11. The light intensity detection device, reference electrode, or counter electrode is sealed with the slot 18 to prevent electrolyte leakage inside the pool body 11. The slot 18 allows for convenient fixing of the light intensity detection device, reference electrode, or counter electrode, ensuring stable placement of the light intensity detection device, reference electrode, or counter electrode within the pool body 11. The number of slots 18 can be set to one or more as needed.

[0055] In one embodiment, a gas collecting pipe 17 is provided on the top cover 13 for collecting gases generated in the electrolyte. The gas collecting pipe 17 may be located on the edge portion outside the recessed portion 131 to better collect bubbles that detach from the surface of the working electrode 14 and rise to the edge portion of the top cover 13. Furthermore, an exhaust valve is provided on the gas collecting pipe 17 to control the opening or closing of the gas collecting pipe 17. By collecting bubbles that detach from the surface of the working electrode 14 and enter the electrolyte through the gas collecting pipe 17, interference from bubbles in the electrolyte to the in-situ electrochemical spectrum is further avoided.

[0056] Reference Figure 4 At the same time, refer to Figures 1-3The present invention also provides an in-situ electrochemical spectroscopic detection device 2, comprising the aforementioned in-situ electrochemical spectroscopic electrolytic cell 1 and a Raman spectrometer 21. The Raman spectrometer 21 is used to emit incident light through an optical window 15 onto the upper surface of the protrusion 141, collect scattered light from the upper surface of the protrusion 141, and generate a Raman spectrum by performing spectral analysis on the scattered light through a spectral analysis system within it. The in-situ electrochemical spectroscopic detection device 2 may further include a light intensity detection device disposed in the electrolyte, which is used to adjust the power of the incident light. When adjusting the power of the incident light, the light intensity detection device is placed in the optical path and used to detect the light intensity signals of the incident and reflected light. The power of the light source is adjusted according to the light intensity signals to ensure that the power of the light source meets the requirements of spectral detection. After adjustment, the light intensity detection device is removed from the optical path.

[0057] The Raman spectrometer 21 is preferably a microconfocal Raman spectrometer, which integrates confocal microscopy technology. It uses a laser as the excitation source and a tunable lens to focus the light onto the sample surface. The scattered light generated by the interaction of the laser with the sample surface is collected by the objective lens. Through a designed optical path dispersive system, part of the light enters the spectral analysis system to obtain Raman spectra, while the other part enters the confocal microscope, is collimated, and focused onto the sample surface by a reflecting mirror to form a high-resolution optical image. Therefore, the microconfocal Raman spectrometer can not only obtain Raman spectra but also acquire optical images reflecting the micro-region morphology.

[0058] In one embodiment, the light intensity detection device includes a retractable bracket and a light intensity sensor. The light intensity sensor is fixed to the retractable bracket. By adjusting the retractable bracket, the light intensity sensor can be placed or moved out of the optical path above the working electrode 14. The retractable bracket can be conveniently inserted into the cell body 11 through slots 18 provided on the side wall of the cell body 11. The reference electrode and counter electrode can be attached to the retractable bracket to conveniently fix the reference electrode and counter electrode without adding other components for fixing the reference electrode and counter electrode, and the number of slots 18 can be reduced. The reference electrode and counter electrode can also extend into the electrolyte inside the cell body 11 through corresponding slots 18 provided on the side wall of the cell body 11, and be fixed through corresponding slots 18. The working electrode 14, reference electrode, and counter electrode are all connected to the electrode connector of an external electrochemical workstation through electrode leads.

[0059] The method for in-situ electrochemical spectroscopic detection based on the above-described in-situ electrochemical spectroscopic detection device 2 may include the following steps:

[0060] Provide the above-mentioned in-situ electrochemical spectroscopic detection device 2;

[0061] A test sample layer is attached to the upper end face of the boss portion 141. The test sample layer is, for example, a catalyst active layer.

[0062] The in-situ electrochemical spectroscopic electrolytic cell 1 is filled with electrolyte, and the electrolyte circulation device 12 is operated so that the electrolyte flows from the inlet 111 to the outlet 112 in the cell body 11. The electrolyte flowing in the cell body 11 forms a Bernoulli effect in the narrow area between the groove 131 and the boss 141, which promotes the detachment of bubbles from the surface of the working electrode 14. The bubbles that detach from the working electrode 14 are carried out by the electrolyte in time, avoiding the interference of bubbles on the spectral detection.

[0063] Adjust the test parameters of the light source, such as wavelength and power;

[0064] Electrochemical reactions are carried out using in-situ electrochemical spectroscopic electrolysis cell 1. Specifically, the working electrode 14, the reference electrode, and the counter electrode are connected to the corresponding electrode connectors in the external electrochemical workstation, and the electrochemical workstation is adjusted to the open circuit potential measurement mode.

[0065] After the electrochemical reaction has proceeded for a predetermined time, in-situ electrochemical spectra are obtained by Raman spectrometer 21. Detection can be performed at different overpotentials to obtain in-situ electrochemical spectra at different overpotentials.

[0066] The specific method for adjusting the test parameters such as wavelength and power of the light source is as follows: place the light intensity sensor in the area above the working electrode 14 so that it is in the optical path, select the wavelength of the laser light source, and adjust the power of the light source. When the light intensity signal detected by the light intensity sensor reaches or exceeds the preset threshold, the test parameters such as wavelength and power of the light source are adjusted. Then, move the light intensity sensor out of the optical path to prevent the light intensity sensor from interfering with the subsequent spectral detection.

[0067] During the spectral detection process, the in-situ electrochemical spectroscopy detection device 2 enables bubbles to spontaneously detach from the surface of the working electrode 14 and be promptly carried out by the flowing electrolyte, effectively eliminating the interference of bubbles on the electrochemical spectrum and improving the quality of the spectral signal.

[0068] The following will combine Figure 5 and Figure 6 The advantages of this in-situ electrochemical spectrometry detection device 2 will be further explained.

[0069] Reference Figure 5 , Figure 5The diagram shows a comparison of in-situ electrochemical Raman spectra of the hydrogen evolution reaction. The example uses the in-situ electrochemical Raman spectrum obtained with the in-situ electrochemical spectrometer 2 of this invention, while the comparative example uses the in-situ electrochemical Raman spectrum obtained with a commercially available in-situ electrochemical spectrometer 2. The testing conditions are identical in both cases: the working electrode 14 is a glassy carbon electrode, the electrolyte is a 1 mol / L KOH solution, the sample layer is the same batch of NiFe-LDH catalyst active layer with the same catalyst dosage, the optical path is identical, the electrochemical reaction time is identical, and the light source wavelength, power, exposure time, and integration times are identical. The overpotential relative to the reversible hydrogen electrode is -0.3V. For the hydrogen evolution reaction, in the comparative example, due to bubble interference, the characteristic peaks at wavenumbers λ1 and λ2 are not obvious, especially the characteristic peak at λ2, which almost disappears. The peak value at λ1 is 475 cm⁻¹. -1 The corresponding Ni-O bond vibration of NiFe-LDH has a peak value of 661 cm⁻². -1 The corresponding A of NiFe-LDH 1g Vibration mode. In the embodiment, due to the elimination of bubble interference, the characteristic peaks at λ1 and λ2 were significantly enhanced, especially the characteristic peak λ2, which was not observed in the comparative example, was detected. Figure 5 The spectral comparison results verified that the in-situ electrochemical spectroscopy detection device 2 provided by the present invention improves the quality of the spectral signal, thereby improving the signal-to-noise ratio.

[0070] Reference Figure 6 , Figure 6 The diagram shows a comparison of in-situ electrochemical Raman spectra of the oxygen evolution reaction. The example uses the in-situ electrochemical Raman spectrum obtained with the in-situ electrochemical spectrometer 2 of this invention, while the comparative example uses the in-situ electrochemical Raman spectrum obtained with a commercially available in-situ electrochemical spectrometer 2. The testing conditions are identical in both cases: the working electrode 14 is a glassy carbon electrode, the electrolyte is a 1 mol / L KOH solution, the sample layer is the same NiFe-LDH catalyst active layer prepared in the same batch, and the catalyst dosage, optical path, electrochemical reaction time, light source wavelength, power, exposure time, and integration times are all identical. The overpotential relative to the reversible hydrogen electrode is 1.4 V. For the hydrogen evolution reaction, in the comparative example, due to bubble interference, the characteristic peaks at wavenumbers λ1 and λ3 are not obvious, especially the peak at λ3, which almost disappears. The peak value at λ3 is 316 cm⁻¹. -1 This corresponds to the lattice vibrations of NiFe-LDH. In the embodiments, due to the elimination of bubble interference, the characteristic peaks at λ1 and λ3 were significantly enhanced, especially the characteristic peak λ3, which was not observed in the comparative example, was detected. Figure 6The spectral comparison results also verify that the in-situ electrochemical spectroscopy detection device 2 provided by the present invention improves the quality of the spectral signal, thereby improving the signal-to-noise ratio.

[0071] comprehensive Figure 5 and Figure 6 It is understood that the in-situ electrochemical spectroscopy detection device 2 of the present invention effectively eliminates the interference of bubbles on the electrochemical spectrum by synchronously removing bubbles on the surface of the working electrode 14 during the spectral detection process, thereby improving the quality of the spectral signal and thus improving the signal-to-noise ratio.

[0072] This invention also provides a bubble removal method for removing bubbles from the surface of the working electrode in an in-situ electrochemical spectroscopic electrolysis cell, comprising the following steps:

[0073] S1. A narrow region is formed in the cell body 11 of the in-situ electrochemical spectroscopic electrolysis cell, and one side of the narrow region is defined by the surface of the working electrode 14 located in the cell body 11 for carrying the test sample layer.

[0074] S2, to circulate the electrolyte in the tank 11 and flow through the narrow area.

[0075] In one embodiment, the bubble removal method is performed using the in-situ electrochemical spectroelectrolysis cell 1 described above, wherein the narrow region is formed by the interval.

[0076] This bubble removal method can also create a Bernoulli effect in this narrow region, promoting the detachment of bubbles from the working electrode surface. The bubbles that detach from the working electrode are promptly carried out by the electrolyte, avoiding interference from the bubbles with the spectral detection.

[0077] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An in-situ electrochemical spectroscopic electrolytic cell (1), characterized in that, include: A pool body (11) has an inlet (111) and an outlet (112) arranged opposite to each other on its side wall. The pool body (11) is used to hold electrolyte. Electrolyte circulation device (12) is used to continuously draw the electrolyte from the outlet (112) and send it into the inlet (111), and to make the electrolyte circulate from the inlet (111) to the outlet (112) in the pool body (11); Top cover (13), said top cover (13) being sealed to said pool body (11); and Working electrode (14), which is vertically disposed in the pool body (11); The top cover (13) has a groove (131) in the center, and an optical window (15) is embedded at the bottom of the groove (131). The working electrode (14) has a boss (141) on its upper part, and the boss (141) has an upper surface for supporting the test sample layer. The groove (131) and the boss (141) are arranged opposite each other, and there is a gap between the bottom of the groove (131) and the upper surface of the boss (141).

2. The in-situ electrochemical spectroscopic electrolytic cell (1) according to claim 1, characterized in that, The groove (131) is a frustum shape that is wider at the top and narrower at the bottom, and the protrusion (141) is a frustum shape that is narrower at the top and wider at the bottom.

3. The in-situ electrochemical spectroscopic electrolytic cell (1) according to claim 1, characterized in that, The in-situ electrochemical spectroscopic electrolytic cell (1) further includes an instantaneous flow inlet pipe (16), which is used to pump electrolyte into the area between the groove (131) and the boss (141).

4. The in-situ electrochemical spectroscopic electrolytic cell (1) according to claim 1, characterized in that, The electrolyte circulation device (12) includes a circulation pipeline (121), a storage tank (122), and a circulation pump (123). The two ends of the circulation pipeline (121) are connected to the inlet (111) and the outlet (112), respectively. The storage tank (122) and the circulation pump (123) are both mounted on the circulation pipeline (121); and / or The liquid inlet (111) and the liquid outlet (112) are arranged on the same axis, and the axis is located between the groove (131) and the boss (141).

5. The in-situ electrochemical spectroscopic electrolytic cell (1) according to claim 1, characterized in that, The top cover (13) is provided with a gas collecting pipe (17), which is used to collect the gas generated in the electrolyte.

6. The in-situ electrochemical spectroscopic electrolytic cell (1) according to claim 1, characterized in that, The side wall of the pool body (11) is provided with a slot (18), which is used to insert a light intensity detection device, a reference electrode or a counter electrode into the pool body (11).

7. An in-situ electrochemical spectroscopic detection device (2), characterized in that, The device includes an in-situ electrochemical spectroelectrolysis cell (1) and a Raman spectrometer (21) as described in any one of claims 1-6. The Raman spectrometer (21) is used to emit incident light through the optical window (15) to the upper surface of the protrusion (141), collect the scattered light from the upper surface of the protrusion (141), and perform spectral analysis on the scattered light to generate a Raman spectrum.

8. The in-situ electrochemical spectroscopic detection device (2) according to claim 7, characterized in that, The in-situ electrochemical spectroscopy detection device (2) further includes a light intensity detection device disposed in the electrolyte, the light intensity detection device being used to adjust the power of the incident light; and / or, the in-situ electrochemical spectroscopy detection device (2) further includes a reference electrode and a counter electrode disposed in the electrolyte, the working electrode (14), the reference electrode and the counter electrode being connected to the electrode connector of an external electrochemical workstation via electrode leads.

9. A method for removing bubbles, used to remove bubbles from the surface of the working electrode in an in-situ electrochemical spectroscopic electrolysis cell, characterized in that, Includes the following steps: S1. A narrow region is formed in the cell body (11) of the in-situ electrochemical spectroscopic electrolysis cell, and one side of the narrow region is defined by the surface of the working electrode (14) located in the cell body (11) for carrying the test sample layer. S2, to circulate the electrolyte in the pool (11) and flow through the narrow area.

10. The bubble removal method according to claim 9, characterized in that, The bubble removal method is carried out using the in-situ electrochemical spectroelectrolysis cell (1) according to any one of claims 1-6, wherein the narrow region is formed by the interval.

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