An in-situ microscopic spectroscopy system and method for a liquid-phase catalytic gas generation device

Abstract

The present invention discloses an in-situ microscopic spectroscopy system and method for a liquid-phase catalytic gas generation device, belonging to the field of liquid-phase in-situ microscopic spectroscopy detection. The system includes a laser, a Raman optical module, a spectrometer, a microscope, a flexible transparent window, and an electrochemical reaction cell; the electrochemical reaction cell is located on the stage of the microscope, and a flexible transparent window is provided at the top of the electrochemical reaction cell. By applying a force on the flexible transparent window film, the transparent window is made to approach the sample as much as possible, so that a microscopic objective lens with a short working distance and a large numerical aperture can be used to improve the collection efficiency of the spectral signal; in addition, due to the arc-shaped bending structure at the front end of the flexible window, the bubbles generated during the catalytic process can also float to the surroundings along the arc-shaped surface under the action of buoyancy, solving the problem that the bubbles accumulate on the glass window and affect the operation of the objective lens.

Description

Technical Field

[0001] The present invention relates to the field of in-situ microscopic spectroscopy detection in liquid phase, and particularly to an in-situ microscopic spectroscopy system and method for a liquid-phase catalytic gas generation device. Technical Background

[0002] With the increasing urgency of energy issues and the demand for low-carbon emissions, the development of new energy is imminent. Among various new energies, hydrogen energy, as a recognized clean energy, stands out. Electro / photoelectrolysis of water, as an important hydrogen production method, has been widely studied. In order to study the catalytic hydrogen production process, it is particularly important to perform real-time detection and analysis of the catalytic process. Among various detection means, spectroscopic detection has become an important detection means due to its many advantages such as non-contact, non-destructive, fast, sensitive, and accurate.

[0003] Currently, there are mainly two liquid-phase microscopic spectroscopy detection schemes: One scheme is to directly immerse the microscopic objective lens into the reaction solution using an immersion objective lens for spectral excitation and collection. In this scheme, the objective lens will directly contact various reaction solutions, which is likely to contaminate the lens and affect subsequent use. In addition, operations such as pressurizing and ventilating the reaction cell cannot be performed. The other scheme is to perform spectral excitation and collection above the liquid surface using a long working distance microscopic objective lens. This can avoid lens contamination, and by installing a transparent window above the reaction cell, problems such as pressurizing and ventilating can also be solved. However, due to the small numerical aperture of the long working distance microscopic objective lens, the spectral collection efficiency is very low, and the measured spectral signal is very weak, affecting the detection accuracy. In addition, it has also been found in actual use that the bubbles generated during the catalytic process will accumulate on the transparent window or the lens surface, thus affecting microscopic imaging and spectral acquisition. Summary of the Invention

[0004] The present invention proposes to use a flexible transparent polymer organic film as an optical window. Due to the bendable characteristics of the flexible polymer film itself, a force can be applied to the film to make the transparent window as close as possible to the sample, so that a microscopic objective lens with a short working distance and a large numerical aperture can be used, thereby improving the collection efficiency of spectral signals. In addition, due to the arc-shaped bending structure at the front end of the flexible window, the bubbles generated during the catalytic process can also float to the surrounding along the arc-shaped surface under the action of buoyancy, solving the problem that the bubbles accumulate on the glass window and affect the operation of the objective lens.

[0005] The present invention provides an in-situ microscopic spectroscopy system and method for a liquid-phase catalytic gas generation device. Through the design of a special microscopic spectroscopy acquisition scheme, this microscopic spectroscopy system can solve the problem of spectral signal collection during the spectral detection of the catalytic gas generation reaction due to the accumulation of bubbles on the surface of the glass window, and at the same time can significantly improve the spectral collection efficiency by using a microscopic objective lens with a short working distance and a large numerical aperture, enhancing the intensity of the detected signal.

[0006] The technical solution of the present invention is as follows:

[0007] An in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device, comprising a laser, a Raman optical module, a spectrometer, a microscope, a flexible transparent window, and an electrochemical reaction cell;

[0008] The electrochemical reaction cell is located on the stage of the microscope, and a flexible transparent window is provided at the top of the electrochemical reaction cell; a movable imaging device is provided in the optical path of the microscope for observing the microscopic image of the sample surface when adjusting the stage of the microscope;

[0009] The laser emitted by the laser exits from the laser output port of the Raman optical module, is reflected by the third reflector onto the optical path of the microscope; the light returned along the original path by the third reflector returns to the Raman optical module again from the laser output port, and then exits from the Raman signal output port and is received by the spectrometer.

[0010] As a preference of the present invention, the flexible transparent window is in an arc-shaped curved surface under the pressure of the microscopic objective lens.

[0011] As a preference of the present invention, the microscopic objective lens adopts an immersion microscopic objective lens with a high numerical aperture.

[0012] As a preference of the present invention, a refractive index matching liquid is contained in the arc-shaped curved surface of the flexible transparent window, and the refractive index of the refractive index matching liquid matches the refractive index of the reaction liquid in the electrochemical reaction cell, which can be selected according to the actual situation.

[0013] The working process of the above system is as follows: The laser emitted by the laser is incident on the Raman optical module, and after being reflected by the narrowband filter, the first reflector, the second reflector, the first edge filter, and the third reflector in sequence, it enters the microscope. After being focused by the immersion microscopic objective lens, it irradiates the sample through the flexible transparent window to generate Raman signals. Then, the Raman signals and the reflected laser are collected by the objective lens into the microscope, returned to the Raman optical module after being reflected by the third reflector, filtered by the first edge filter to remove the reflected laser, focused by the lens, and filtered again by the second edge filter and then enter the spectrometer. Finally, spectral analysis of the signal light in the spectrometer can obtain Raman signals. Among them, the illumination light in the microscope and the second push-pull beam splitter can provide an illumination light source for bright-field imaging of the sample surface, and the first push-pull beam splitter and the camera are used to receive the microscopic image of the sample surface for optical microscopic imaging.

[0014] Compared with the prior art, the advantages of the present invention are:

[0015] Compared with a glass window, due to its bendable property, a flexible transparent window allows the microscope objective not to worry about the window hindering the descent of the microscope objective during the focusing process. Therefore, a microscope objective with a short working distance and a high numerical aperture can be used to improve the spectral collection efficiency.

[0016] In addition, due to the arc-shaped bending structure of the transparent window, the generated bubbles can easily float along the arc surface to the surroundings under the action of buoyancy, solving the problem that the gas generated by electrocatalysis accumulates on the flat glass window, thus affecting microscopic imaging and spectral acquisition.

[0017] Meanwhile, the special shape of the bending structure can be utilized to add a liquid with a refractive index matching that of the reaction solution to the concave upper surface of the bending structure, so as to immerse the immersion microscope objective with a high numerical aperture in the liquid ring, further improving the spectral collection efficiency. Description of the Drawings

[0018] Figure 1 It is a schematic diagram of an in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device. Detailed Embodiments

[0019] The present invention will be further described below with reference to the drawings.

[0020] An in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device proposed by the present invention mainly consists of a laser, a Raman optical module, a spectrometer, a microscope (including imaging and illumination), a flexible transparent window, and an electrochemical reaction cell. The basic structure is shown in the appendix Figure 1 .

[0021] In this embodiment, by setting a movable imaging device in the optical path of the microscope, imaging and illumination functions can be realized, which are used to observe the microscopic image of the sample surface when adjusting the stage of the microscope.

[0022] The imaging device includes a first push-pull beam splitter, a second push-pull beam splitter, a camera, and an illumination light source; the first push-pull beam splitter and the second push-pull beam splitter are arranged in sequence on the laser incident optical path of the microscope, the camera is arranged on the reflection optical path of the first push-pull beam splitter, and is used to receive the microscopic image of the sample surface; the illumination light source is arranged on the reflection optical path of the second push-pull beam splitter, and is used to provide an illumination light source for bright-field imaging of the sample surface.

[0023] In this embodiment, the Raman optical module includes a narrowband filter, a first mirror, a second mirror, a first edge filter, a second light source filter, and a lens; the narrowband filter, the first mirror, the second mirror, and the first edge filter form a first optical path, and the laser emitted by the laser passes through the first optical path and is reflected by the first edge filter to a third mirror; the first edge filter, the lens, and the second light source filter form a second optical path, and the light returning along the original path from the third mirror passes through the first edge filter and exits from the second optical path and is received by the spectrometer.

[0024] The working process of the whole system will be described below with reference to the attached Figure 1 Drawings:

[0025] Place the prepared electrochemical reaction cell with the sample on the stage under the microscope, and add an appropriate amount of refractive index matching liquid above the flexible transparent window so that the microscopic objective lens can be immersed in the matching liquid after focusing.

[0026] Turn on the illumination light source and the camera, and place the first push-pull beam splitter and the second push-pull beam splitter in the optical path system of the microscope. At this time, bright-field microscopic imaging of the sample surface can be performed through the microscope. Select a microscopic objective lens with an appropriate magnification, and adjust the focusing knob of the microscope to make the microscopic image of the sample surface clear. At this time, the sample will be near the focal plane of the microscopic objective lens.

[0027] Turn on the laser, and direct the laser into the Raman optical module. Filter out the stray lines in the laser through the narrowband filter. Then, the laser is reflected by the first mirror, the second mirror, the first edge filter, and the third mirror in sequence and enters the microscope. Among them, the laser after being reflected by the second mirror should be incident on the first edge filter at a small angle as much as possible to ensure that it will not have too much impact on the filtering effect of the first edge filter, for example, not greater than 10°. In addition, an attenuation sheet can be inserted at any position in the optical path before the first edge filter to adjust the power of the incident laser.

[0028] The above-mentioned laser incident on the microscope is focused on the sample surface through the microscopic objective lens. At this time, the laser spot can be observed on the camera. Move the stage under the microscope horizontally through the knob on the microscope to move the position to be measured on the sample to the laser spot. Then, adjust the focusing knob of the microscope again to focus the laser on the surface of the sample to be measured. After that, move the first push-pull beam splitter and the second push-pull beam splitter out of the microscopic optical path to avoid affecting the collection of the laser and the Raman signal light. At this time, the illumination light and the camera will lose their functions.

[0029] The laser focused on the surface of the sample to be tested will interact with the sample to produce Raman scattering. The Raman signal light and the laser scattered / reflected back by the sample surface will be collected by the microscope objective at the same time and returned to the third reflector along the original optical path. After being reflected by the third reflector, it will be incident on the Raman optical module. Among them, the microscope objective should try to select an objective with a high numerical aperture to improve the light collection efficiency. At this time, the microscope objective lens will contact the flexible transparent window and bend it. This bending structure can reduce the accumulation of bubbles at the front end of the lens and prevent bubbles from affecting spectral excitation and collection. In this embodiment, the numerical aperture can be selected according to the magnification, brand, and type of the objective lens.

[0030] The signal light incident on the Raman optical module is filtered out of the laser signal by the first edge filter, and then the noise light is filtered out again by the second edge filter after being focused by the lens. Finally, the signal light is incident on the slit of the spectrometer, and the spectrometer performs spectral analysis and data processing to obtain the in-situ microscopic Raman spectrum signal of the sample surface.

[0031] In addition, for samples with fluorescent luminescence characteristics, the above system can also be used for in-situ microscopic fluorescence spectrum testing by simply recalculating the horizontal coordinates of the spectral data.

[0032] The above examples are only specific embodiments of the present invention. Obviously, the present invention is not limited to the above examples, and many variations are possible. All variations that can be directly derived or associated with the contents disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. An in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device, characterized in that It includes a laser, a Raman optical module, a spectrometer, a microscope, a flexible transparent window, and an electrochemical reaction cell; The electrochemical reaction cell is located on the stage of the microscope, and a flexible transparent window is provided on the top of the electrochemical reaction cell; A movable imaging device is provided in the optical path of the microscope for observing the microscopic image of the sample surface when adjusting the stage of the microscope; The laser emitted by the laser exits from the laser exit of the Raman optical module, is reflected by the third mirror and enters the microscope optical path; The light returning along the original path from the third mirror returns to the Raman optical module again from the laser exit, then exits from the Raman signal output port and is received by the spectrometer; The flexible transparent window is in an arc-shaped surface under the pressure of the microscopic objective lens; The arc-shaped surface of the flexible transparent window contains a refractive index matching liquid, and the refractive index of the refractive index matching liquid matches the refractive index of the reaction liquid in the electrochemical reaction cell.

2. The in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device according to claim 1, wherein The microscopic objective lens uses an immersion microscopic objective lens with a high numerical aperture.

3. The in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device according to claim 1, characterized in that, The imaging device includes a first push-pull beam splitter, a second push-pull beam splitter, a camera, and an illumination light source; The first push-pull beam splitter and the second push-pull beam splitter are arranged in sequence on the laser incident optical path of the microscope, and the camera is arranged on the reflected optical path of the first push-pull beam splitter for receiving the microscopic image of the sample surface; The illumination light source is arranged on the reflected optical path of the second push-pull beam splitter for providing an illumination light source for bright-field imaging of the sample surface.

4. An in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device according to claim 1 or 3, characterized in that, The Raman optical module includes a narrow-band filter, a first mirror, a second mirror, a first edge filter, a second light source filter, and a lens; The narrow-band filter, the first mirror, the second mirror, and the first edge filter form a first optical path, and the laser emitted by the laser passes through the first optical path and is reflected by the first edge filter to the third mirror; The first edge filter, the lens, and the second light source filter form a second optical path, and the light returning along the original path from the third mirror passes through the first edge filter and exits from the second optical path and is received by the spectrometer.

5. The in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device according to claim 4, wherein The optical path angle between the second mirror and the first edge filter is less than 30 degrees.

6. The in-situ microscopic spectroscopy system for a liquid-phase catalytic gas generation device according to claim 4, characterized in that, An attenuation sheet for adjusting the incident laser power is provided on the first optical path.

7. A spectral testing method for an in-situ microscopic spectroscopy system of a liquid-phase catalytic gas generation device according to claim 3, characterized in that, It includes: Turn on the laser, move the imaging device to the microscope optical path, the laser emitted by the laser is incident on the Raman optical module, and successively passes through the narrow-band filter, the first mirror, the second mirror, the first edge filter, and the third mirror and then enters the microscope and irradiates the sample surface; Observe the laser spot through the camera, adjust the position of the stage to move the position to be measured on the sample to the laser spot, and then adjust the focusing knob of the microscope to focus the laser on the surface of the sample to be measured; After the debugging is completed, move the imaging device out of the microscope optical path and turn off the camera and the illumination light source; The laser emitted from the laser is focused by the microscope objective lens and irradiated onto the sample through the flexible transparent window to generate a Raman signal. The Raman signal and the reflected laser are then collected by the objective lens into the microscope, reflected by the third reflector and returned to the Raman optical module. The reflected laser is filtered out by the first edge filter and then focused by the lens. It is then filtered twice by the second edge filter and enters the spectrometer. Finally, the signal light is spectrally analyzed in the spectrometer.

8. The spectral testing method of the in-situ microscopic spectroscopy system for a liquid-phase catalytic gas production device according to claim 7, characterized in that, During the debugging process, the objective lens of the microscope is lowered, the flexible transparent window is deformed into an arc-shaped surface, and a refractive index matching liquid is added into the arc-shaped surface; The bubbles generated by the sample to be tested during the electrochemical catalysis process float to the two sides of the objective lens along the curved surface under the action of buoyancy.

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