Electrochemical imaging apparatus and electrochemical imaging method
By using an annular beam control mechanism to modulate the emitted light of the light source in the electrochemical imaging device, ensuring surface plasmon resonance is stimulated at any azimuth angle, the problem of poor imaging resolution in the prior art is solved, and electrochemical imaging with higher quality and resolution is achieved.
Patent Information
- Application Number
- CN202311135505.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-01
- Publication Date
- 2025-03-04
AI Technical Summary
The imaging resolution of existing electrochemical imaging devices is poor, making it difficult to effectively record microscopic information of electrochemical reactions.
An electrochemical imaging device is designed, and the annular beam control mechanism is used to modulate the emitted light of the light source into incident light that can excite surface plasmon resonance at any azimuth angle. The light emitted from the electrochemical reaction cell is received through the optical imaging system, and microscopic information of the electrochemical reaction is recorded.
The imaging quality and resolution of the electrochemical imaging device are improved, the tailing phenomenon caused by single-direction light is avoided, and the interface light intensity distribution and reaction kinetics process can be recorded more clearly during the electrochemical reaction.
Smart Images
Figure CN119555779A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of electrochemical imaging, and in particular to an electrochemical imaging device and an electrochemical imaging method. Background Art
[0002] Electrochemistry is the science that studies the charge and electron transfer changes that occur at the interface formed by electronic conductors and ionic conductors. With the rise of research on microscale materials and energy technologies, the research methods and theoretical models of electrochemical analysis have begun to penetrate into the single particle and single molecule level, and obtaining microscopic dynamic information at the electrochemical interface has become a research hotspot.
[0003] Electrochemical devices and optical imaging devices are usually combined to form an electrochemical imaging device to study the microscopic phenomena of electrochemical interfaces. Since the microscopic processes of electrochemical interfaces are extremely fast and the changes are small, a highly sensitive surface plasmon resonance microscope (SPRM) has been developed and widely used.
[0004] However, the imaging resolution of the electrochemical imaging device in the related art is poor. Summary of the invention
[0005] Based on this, it is necessary to provide an electrochemical imaging device and an electrochemical imaging method to address the problem of poor imaging resolution of electrochemical imaging devices in related technologies.
[0006] An electrochemical imaging device, comprising:
[0007] an electrochemical reaction cell; and,
[0008] The optical imaging system includes an illumination module and a shooting element. The illumination module includes a light source and an annular light beam control mechanism. The annular light beam control mechanism is configured to modulate the emitted light of the light source and then inject it into the electrochemical reaction cell. The light modulated by the annular light beam control component can excite surface plasmon resonance at any azimuth angle. The shooting element is used to receive the light emitted by the electrochemical reaction cell.
[0009] The electrochemical imaging device provided by the present application undergoes an electrochemical reaction in an electrochemical reaction cell, and generates incident light through an optical imaging system to be incident on the electrochemical reaction cell, surface plasmon resonance occurs at the interface of the electrochemical reaction cell, and surface plasmon (SP) surface waves are generated. The incident light is emitted after stimulating the surface plasmon resonance through the electrochemical reaction cell, and the optical imaging system then receives the emitted light, thereby recording microscopic information of the electrochemical reaction, such as the light intensity distribution at the interface during the electrochemical reaction, so as to infer the reaction kinetics and the catalytic activity, site distribution, structure-performance relationship and other information of the materials in the process. Among them, the annular beam control mechanism modulates the emission light emitted by the light source into incident light that can excite surface plasmon resonance at any azimuth angle. It can be understood that the incident light is irradiated into the electrochemical reaction cell, and can excite uniform surface plasmon resonance at the reaction interface where the electrochemical reaction occurs. At the same time, the intensity of the reflected light reflected by the incident light at the reaction interface changes, and the microscopic information of the electrochemical reaction is recorded by detecting the reflected light. The setting of incident light that can excite surface plasmon resonance at any azimuth angle can avoid the tailing phenomenon of the image formed by a single direction of light, thereby improving the imaging quality of the reflected output light, improving the resolution, and facilitating the collection of effective microscopic information.
[0010] In one embodiment, the light source emits linearly polarized light;
[0011] The annular light beam control mechanism comprises a modulation component, which is arranged between the light source and the electrochemical reaction cell and is used for modulating the linearly polarized light emitted by the light source into a linearly polarized light beam in the shape of an annular belt.
[0012] In one embodiment, the annular light beam control mechanism includes an adjusting device, which is disposed between the modulation component and the electrochemical reaction cell, and is used to convert the linearly polarized light beam in the shape of an annular band into P-polarized light.
[0013] In one embodiment, the modulation component includes a first galvanometer and a second galvanometer arranged in sequence along the light output path of the light source, the first galvanometer is configured to be able to rotate around an axis parallel to a first direction, and the second galvanometer is configured to be able to rotate around an axis parallel to a second direction, wherein the first direction and the second direction intersect with each other, and the light beam adjusted by the first galvanometer and the second galvanometer is in a high-speed rotation state.
[0014] In one embodiment, the annular light beam control mechanism includes a first lens, which is disposed between the second galvanometer and the electrochemical reaction cell to transmit the light beam in a high-speed rotating state to the electrochemical reaction cell in the form of parallel light.
[0015] In one of the embodiments, the modulation component includes a diffractive optical element, and the diffractive optical element is used to adjust the light beam so that the light beam is in a ring-shaped shape.
[0016] In one embodiment, the annular beam control mechanism includes a conical lens arranged between the modulation component and the electrochemical reaction cell, and the conical lens is configured to be movable relative to the modulation component along the propagation direction of the beam to adjust the incident angle of the beam projected onto the electrochemical reaction cell.
[0017] In one embodiment, the electrochemical imaging device comprises an electrochemical workstation;
[0018] The electrochemical reaction cell includes a conductive cover glass with a coating, a reaction electrode and an electrolyte disposed on the conductive cover glass. The reaction electrode is disposed in the electrolyte and is connected to the electrochemical workstation. An electrochemical circuit is formed between the reaction electrode, the electrolyte and the electrochemical workstation.
[0019] In one embodiment, the reaction electrode includes a reference electrode, a working electrode and a counter electrode, and the reference electrode, the working electrode and the counter electrode undergo an electrochemical reaction in the electrolyte.
[0020] According to another aspect of the present application, an electrochemical imaging method using the above electrochemical imaging device is provided, and the electrochemical imaging method comprises the following steps:
[0021] Modulating the emitted light of the light source into a ring-shaped light beam;
[0022] adjusting the incident angle of the light beam distributed in an annular shape;
[0023] Converting the annular light beam into P polarized light;
[0024] Projecting the annular light beam converted into P-polarized light to the electrochemical reaction cell;
[0025] The light scattered by the electrochemical reaction cell is received by the photographing element. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 Schematic diagram of the structure of the electrochemical imaging device in some embodiments of the present application.
[0027] Figure 2 for Figure 1 Schematic diagram of the structure of the modulation component of the electrochemical imaging device shown.
[0028] Figure 3 This is a schematic diagram of the structure of an electrochemical imaging device in another embodiment of the present application.
[0029] Description of reference numerals:
[0030] Electrochemical imaging device 100;
[0031] Electrochemical reaction cell 1; conductive cover glass 11; electrolyte 12; catalytic material 13; reference electrode 14; counter electrode 15; hydrophobic film 16;
[0032] Optical imaging system 2; light source 21; annular beam control mechanism 22; modulation component 220; first galvanometer 221; second galvanometer 222; first focusing lens 223; diffractive optical element 224; second focusing lens 225; conical lens 226; adjustment device 227; first driving member 228; second driving member 229; first lens 23; medium 24; shooting element 25; second lens 26; third lens 27; electrochemical workstation 3; reflector 4. DETAILED DESCRIPTION
[0033] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present application, so the present application is not limited by the specific embodiments disclosed below.
[0034] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.
[0035] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of this application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.
[0036] In this application, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.
[0037] In the present application, unless otherwise clearly specified and limited, a first feature being “above” or “below” a second feature may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, a first feature being “above”, “above”, and “above” a second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. A first feature being “below”, “below”, and “below” a second feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is lower in level than the second feature.
[0038] It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it may be directly on the other element or there may be a central element. When an element is considered to be "connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. The terms "vertical", "horizontal", "upper", "lower", "left", "right" and similar expressions used herein are for illustrative purposes only and are not intended to be the only implementation method.
[0039] The present application provides an electrochemical imaging device 100 and an electrochemical imaging method for detecting and obtaining microscopic information of electrochemical reactions, such as the light intensity distribution at the interface during the electrochemical reaction, so as to infer the reaction kinetics and the active site distribution of the material itself. On the one hand, it provides data for reaction mechanism and kinetics research, and on the other hand, it can provide reaction activity information of active materials to guide the synthesis of chemical materials.
[0040] See also Figure 1 As shown, Figure 1 The schematic diagram of the structure of the electrochemical imaging device 100 in some embodiments of the present application is shown. The electrochemical imaging device 100 includes an electrochemical reaction cell 1 and an optical imaging system 2. An electrochemical reaction to be observed occurs in the electrochemical reaction cell 1. The optical imaging system 2 emits incident light to the electrochemical reaction cell 1. The incident light is emitted through the electrochemical reaction cell 1. The optical imaging system 2 then receives the emitted light, so that the information carried by the emitted light records the microscopic information of the observed electrochemical reaction.
[0041] like Figure 1 As shown, the optical imaging system 2 of the present application includes an illumination module and a photographing element 25, wherein the illumination module is used to emit incident light to the electrochemical reaction cell 1, and the photographing element 25 is used to receive the outgoing light emitted by the electrochemical reaction cell 1. In some embodiments, the illumination module includes a light source 21 and an annular beam control mechanism 22, wherein the annular beam control mechanism 22 is configured to modulate the emitted light of the light source 21 and then emit it to the electrochemical reaction cell 1.
[0042] It can be understood that the annular beam control mechanism 22 is disposed between the light source 21 and the electrochemical reaction cell 1, and is located on the propagation path of the incident light emitted by the light source 21, and can modulate the incident light. The light modulated by the annular beam control mechanism 22 can excite surface plasmon resonance at any azimuth angle. In other words, when the modulated incident light is irradiated into the electrochemical reaction cell 1, the incident light can excite uniform surface plasmon resonance at the reaction interface where the electrochemical reaction occurs. At the same time, the intensity of the outgoing light reflected by the incident light at the reaction interface changes, and then the reflected outgoing light is received by the shooting element 25 for imaging, and the image collected by the shooting element 25 is analyzed to obtain the microscopic information of the electrochemical reaction, and the image obtained by the shooting element 25 has the advantages of high resolution, clear imaging, and avoidance of the tailing phenomenon.
[0043] It can be understood that the setting that can excite surface plasmon resonance at any azimuth angle avoids the problems of low imaging quality such as tailing and shadowing caused by the surface propagation of surface plasmon resonance at all azimuth angles, thereby improving the resolution of the image collected by the electrochemical imaging device 100 and further improving the imaging quality of the electrochemical imaging device 100.
[0044] See also Figure 1As shown, the light source emits linearly polarized light, and the annular beam control mechanism 22 includes a modulation component 220 and an adjustment device 227. The modulation component 220 is arranged between the light source 21 and the electrochemical reaction cell 1, and is used to modulate the linearly polarized light emitted by the light source 21 into a linearly polarized light beam in a high-speed rotating state, that is, the illumination light emitted by the light source 21 in a single direction is modulated into an illumination light that rotates 360° at a high speed through the modulation component 220, and the light beam is rotated for an integer number of cycles within the exposure time of the shooting element, so that the image captured by the illumination light is similar to the image captured by the annular beam, and the high-speed rotating illumination light can be regarded as an annular illumination beam. The adjustment device 227 is arranged between the modulation component 220 and the electrochemical reaction cell 1, and the adjustment device 227 is used to convert the light beam in a high-speed rotating state into P-polarized light. Thus, the light beam incident to the electrochemical reaction cell 1 can excite surface plasmon resonance at any azimuth angle, and the problem of parabolic tailing of the detection image formed by irradiation with light in a single direction along the propagation direction of the plasma wave can be avoided. In other words, by setting the modulation component 220 and the adjustment device 227, the light beam incident to the electrochemical reaction cell 1 can excite surface plasmon resonance at any azimuth angle, and a uniform detection image can be obtained in all directions, thereby improving the imaging quality and resolution of the detection image. This makes it easier to perform imaging analysis on samples with more complex morphologies, and realizes quantitative analysis of sample properties during the electrochemical reaction process.
[0045] like Figure 1 As shown, in some embodiments, the optical imaging system 2 also includes a second lens 26 and a third lens 27, and the second lens 26 and the third lens 27 are sequentially arranged between the light source 21 and the modulation component 220, and are used to modulate the emitted light of the light source 21 into parallel light and incident on the modulation component 220. In some embodiments, the second lens 26 can be set as a positive lens, and the third lens 27 can be set as a negative lens. Under the modulation of the second lens 26 and the third lens 27, the emitted light of the light source 21 can be converted into parallel light and incident on the modulation component 220, so as to improve the quality of the light incident on the modulation component 220, thereby facilitating the modulation component 220 to modulate it to form a high-quality light beam.
[0046] In some embodiments, see Figure 2As shown, the modulation component 220 includes a first galvanometer 221, a second galvanometer 222 and a first focusing lens 223 which are sequentially arranged along the light output path of the light source 21, the first galvanometer 221 is arranged to be able to rotate around an axis parallel to the first direction, and the second galvanometer 222 is arranged to be able to rotate around an axis parallel to the second direction, wherein the first direction and the second direction intersect with each other, and the emission light emitted by the light source 21 passes through the first galvanometer 221 and the second galvanometer 222 in sequence, and the first galvanometer 221 and the second galvanometer 222 rotate at high speed around an axis parallel to the first direction and an axis parallel to the second direction, respectively, to realize the deflection of the emission light, wherein the first galvanometer 221 and The reflection angle of the second galvanometer 222 can be controlled by a controller, and the deflected emission light is finally output through the first focusing lens 223, so that the light beam adjusted by the first galvanometer 221 and the second galvanometer 222 is in a high-speed rotating state, and can be output from the first focusing lens 223 to the adjusting device 227, and excite surface plasmon resonance in the electrochemical reaction cell, combined with the exposure time of the shooting element to rotate the light beam for an integer number of cycles, so that the light beam can excite surface plasmon resonance at all azimuths in the electrochemical cell, that is, the image captured by the high-speed rotating illumination light is similar to the image captured by the annular beam, achieving the effect of annular beam illumination. And by using the first galvanometer 221 and the second galvanometer 222 to realize the deflection of the emission light and output the light beam in a high-speed rotating state, the volume of the electrochemical imaging device can be relatively reduced, and the miniaturized design of the electrochemical imaging device can be realized.
[0047] In some embodiments, the modulation component 220 further includes a first driving member 228, a second driving member 229, and a controller electrically connected to the first driving member 228 and the second driving member 229, wherein the first driving member 228 is connected to the first galvanometer 221, and can drive the first galvanometer 221 to rotate around an axis parallel to the first direction, and the second driving member 229 is connected to the second galvanometer 222, and can drive the second galvanometer 222 to rotate around an axis parallel to the second direction. The controller is used to control the rotation speed of the output end of the first driving member 228 and the second driving member 229, respectively, so as to control the rotation speed of the first galvanometer 221 and the rotation speed of the second galvanometer 222, respectively, and then adjust the incident angle and azimuth of the light beam incident to the electrochemical reaction cell 1, realize the incident light rotation illumination, and then combine with the adjustment device 227 to adjust the light beam in a high-speed rotating state to be converted into P polarized light, so that the light beam incident to the electrochemical reaction cell 1 can excite surface plasmon resonance at any azimuth.
[0048] In some embodiments, the adjustment device 227 is configured as a vortex half-wave plate. It is understandable that the polarization state of the laser is related to the azimuth angle. When the light incident to the electrochemical reaction cell 1 rotates to form a ring-shaped beam under the modulation of the modulation component 220, the polarization state of the light is also constantly changing. Therefore, the simple rotating light illumination will cause the surface plasmon resonance signal to be extremely uneven, and the vortex half-wave plate can convert the linearly polarized laser incident at any azimuth angle into P-polarized light, ensuring that the surface plasmon resonance signal at the interface of the electrochemical reaction cell 1 is uniform, eliminating the influence of the polarization state change on the imaging quality.
[0049] In some embodiments, Figure 1 As shown, the annular beam control mechanism 22 also includes a first lens 23 disposed between the second galvanometer 222 and the electrochemical reaction cell 1, and a medium 24 disposed between the first lens 23 and the electrochemical reaction cell 1. The first lens 23 focuses the light beam in a high-speed rotating state onto the back focal plane of the first lens 23, and then propagates to the electrochemical reaction cell in the form of parallel light through the medium 24. In some embodiments, the first lens 23 acts as an objective lens, and the medium 24 can be set as a mirror oil, which can achieve a high numerical aperture, meet the surface plasmon (SP) excitation conditions, and achieve high-efficiency signal collection and high spatial resolution. The first lens 23 is used to focus the annular light beam to the electrochemical reaction cell 1, so that the light beam can irradiate the location where the electrochemical reaction occurs in the electrochemical reaction cell 1, and excite the surface plasmon resonance, so that the shooting element 25 can receive the light with microscopic information of the electrochemical reaction emitted by the electrochemical reaction cell 1. Combined with the setting of the medium 24 disposed between the first lens 23 and the electrochemical reaction cell 1, the electrochemical reaction phenomenon can be observed more clearly, that is, the image obtained by the shooting element 25 is clearer.
[0050] Reference Figure 3 As shown, Figure 3 2 is a schematic diagram of the structure of the electrochemical imaging device 100 in another embodiment of the present application. In this embodiment, the modulation component 220 includes a diffractive optical element 224 and a second focusing lens 225. The diffractive optical element 224 is used to adjust the light beam so that the light beam is annular. The annular light beam is focused by the second focusing lens 225 into a ring-shaped light spot with a focus located at the back focal plane position of the first lens 23. It can be understood that the back focal plane position of the first lens 23 is the conjugate position where the electrochemical reaction occurs in the electrochemical reaction cell 1. In other words, the diffractive optical element 224 is used to convert the outgoing light emitted by the light source 21 into an annular light beam propagating along a certain cone angle direction, and then the annular light beam is focused to the position of the back focal plane of the first lens 23, that is, to the position of the electrochemical reaction cell 1, through the second focusing lens 225, so as to achieve the modulation of the light beam in annular shape and irradiate the light beam into the electrochemical reaction cell 1.
[0051] like Figure 3 As shown, in this embodiment, the annular beam control mechanism 22 includes a cone lens 226 disposed between the modulation component 220 and the electrochemical reaction cell 1, and the cone lens 226 is configured to be movable relative to the modulation component 220 along the beam propagation direction, so as to change the incident angle of the light beam incident to the electrochemical reaction cell 1, and the cone lens 226 can be adjusted to move relative to the modulation component 220 along the beam propagation direction, so that the light spot formed by the light beam incident on the electrochemical reaction cell 1 satisfies the resonance excitation angle, thereby realizing plasma resonance. It can be understood that the adjustment device 227 is disposed between the cone lens 226 and the electrochemical reaction cell 1, and the ring-shaped light beam passing through the cone lens 226 is adjusted by the adjustment device 227, so that the light of any azimuth angle of the ring-shaped light beam can be converted into P polarized light, thereby realizing that any azimuth angle of the light beam incident on the electrochemical reaction cell 1 can excite surface plasma resonance. In other words, by adjusting the conical lens 226, the light spot with an annular distribution focused on the electrochemical reaction cell 1 can be adjusted to meet the resonance excitation angle of the surface plasmon resonance, thereby achieving the excitation of the surface plasmon wave at any azimuth angle of 360°.
[0052] See also Figure 1 and Figure 3 As shown, the electrochemical imaging device 100 also includes an electrochemical workstation 3, and the electrochemical reaction cell 1 includes a conductive cover glass 11, a reaction electrode, and an electrolyte 12 disposed on the conductive cover glass 11. The reaction electrode is disposed in the electrolyte 12 and is connected to the electrochemical workstation 3. An electrochemical circuit is formed between the reaction electrode, the electrolyte 12, and the electrochemical workstation 3. The reaction electrode includes a reference electrode 14, a working electrode, and a counter electrode 15. The reference electrode 14, the working electrode, and the counter electrode 15 undergo an electrochemical reaction in the electrolyte 12, that is, an interfacial electrochemical reaction is performed using a three-electrode system. The electrochemical workstation 3 is used to energize the counter electrode 15, the reference electrode 14, and the working electrode to cause an electrochemical reaction to occur in the electrochemical reaction cell 1. In some embodiments, the electrochemical workstation 3 is electrically connected to a controller, and the controller can be used to control the opening and closing of the electrochemical workstation 3.
[0053] In some embodiments, the controller is also electrically connected to the shooting element 25, and controls the opening and closing of the shooting element 25. It is understandable that when the electrochemical imaging device 100 of the present application needs to be used, the electrochemical workstation 3 and the shooting element 25 are turned on by the controller. In some embodiments, the modulation component 220 is controlled by the controller to modulate the emitted light of the light source 21 into a ring-shaped light beam, and then the ring-shaped light beam is converted into P-polarized light by the adjustment device 227. The P-polarized light is irradiated into the electrochemical reaction cell 1 to excite plasma resonance, and then the reflected light is captured by the shooting element 25 to form an image, thereby realizing the imaging information collection of the microscopic phenomenon of the electrochemical reaction interface.
[0054] In some embodiments, a Pt electrode is used as the counter electrode 15, a silver / silver chloride electrode is used as the reference electrode 14, a gold layer is plated on the side of the conductive cover glass 11 facing the electrolyte 12, and the gold layer is used as the working electrode to connect the electrochemical workstation 3 to form an electrochemical system loop.
[0055] In some embodiments, a hydrophobic film 16, such as a hydrophobic polydimethylsiloxane film, is attached to the conductive cover glass 11 coated with a gold layer. The hydrophobic film 16 is provided with a plurality of holes, and active electrocatalytic materials 13, such as silver nanowires, are deposited in the holes to facilitate electrochemical reactions in the electrochemical reaction cell 1.
[0056] In some embodiments, the lighting module and the camera element 25 can be arranged on both sides of the electrochemical reaction cell 1, the lighting module is arranged on one side of the electrochemical reaction cell 1 close to the electrolyte 12, and the camera element 25 is arranged on the other side of the electrochemical reaction cell 1. The annular P-polarized light modulated and emitted by the lighting module passes through the electrochemical reaction cell 1 and propagates to the camera element 25, and is collected by the camera element 25. That is, transmitted bright field imaging can be achieved.
[0057] In some embodiments, the electrochemical imaging device 100 also includes a reflector 4, which is disposed between the electrochemical reaction cell 1 and the shooting element 25, and is used to reflect light scattered by the electrochemical reaction cell 1 to the shooting element 25. The setting of the reflector 4 enables the shooting element 25 to be disposed on one side of the optical imaging system 2, thereby reducing the axial size of the electrochemical imaging device 100, that is, realizing a miniaturized design of the electrochemical imaging device 100.
[0058] The present application also provides an electrochemical imaging method including the above-mentioned electrochemical imaging device 100, and the electrochemical imaging method includes the following steps: modulating the emitted light of the light source 21 into a ring-shaped light beam through the modulation component 220. In some embodiments, the incident angle of the light spot of the ring-shaped light beam irradiated on the electrochemical reaction cell 1 can be adjusted by the conical lens 226. The ring-shaped light beam also passes through the adjustment device 227, and the ring-shaped light beam is converted into P-polarized light by the adjustment device 227. The ring-shaped light beam converted into P-polarized light is then projected to the electrochemical reaction cell 1 through the first lens 23 arranged between the adjustment device 227 and the electrochemical reaction cell 1. The P-polarized light projected to the electrochemical reaction cell 1 excites surface plasmon resonance in the electrochemical reaction cell 1. The light beam after the surface plasmon resonance is reflected to the shooting element 25, and the light scattered by the electrochemical reaction cell 1 is received by the shooting element 25.
[0059] In some embodiments, the photographing element 25 can be set as a camera. When the camera receives the light emitted by the electrochemical reaction cell 1, the exposure time of the camera can be adjusted to an integer multiple of the rotation period of the first galvanometer 221 and the second galvanometer 222 to form a photographed image equivalent to the lighting effect of the annular lighting light. It can be understood that the camera exposure speed is much lower than the galvanometer speed. The light beam rotates an integer number of cycles within the camera exposure time, that is, an annular scan is realized, the photographing effect of the annular light beam illumination is achieved, and the changes in the electrochemical process of the interface are recorded.
[0060] In some embodiments, the controller can be used to control the first driving member 228 and the second driving member 229 to respectively adjust the rotation periods of the first galvanometer 221 and the second galvanometer 222, so that the light beams passing through the first galvanometer 221 and the second galvanometer 222 have different azimuth angles when irradiating the electrochemical reaction cell 1, and then use a camera to capture images of the electrochemical reaction under lighting conditions with different azimuth angles, and post-process the images to obtain the electrochemical interface image illuminated by the annular light beam.
[0061] The electrochemical imaging device 100 and the electrochemical imaging method provided in the present application can study the microscopic phenomena of the electrochemical interface. On the one hand, they can provide data for the reaction mechanism and kinetics research, and on the other hand, they can provide the reaction activity information of the active material and guide the synthesis of the material. The annular beam control mechanism 22 of the electrochemical imaging device 100 provided in the present application modulates the emission light emitted by the light source 21 into incident light that can excite surface plasmon resonance at any azimuth angle. The incident light is irradiated into the electrochemical reaction cell 1, and can excite uniform surface plasmon resonance at the reaction interface where the electrochemical reaction occurs, so that the imaging caused by the uneven surface plasmon resonance at various azimuth angles will have problems of low imaging quality such as tailing and shadow, and thus a clearer image can be formed. In other words, the electrochemical imaging device 100 provided in the present application can improve the imaging quality of the reflected output light, improve the resolution of the formed image, and facilitate the collection of effective microscopic information. It is possible to perform imaging analysis on samples with more complex morphology, and realize quantitative analysis of sample properties during electrochemical reactions.
[0062] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0063] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.
Claims
1. An electrochemical imaging device, characterized in that: The electrochemical imaging device comprises: an electrochemical reaction cell; and, The optical imaging system includes an illumination module and a shooting element. The illumination module includes a light source and an annular beam control mechanism. The annular beam control mechanism is configured to modulate the emitted light of the light source and then inject it into the electrochemical reaction cell. The light modulated by the annular beam control mechanism can excite surface plasmon resonance at any azimuth angle. The shooting element is used to receive the light emitted by the electrochemical reaction cell.
2. The electrochemical imaging device according to claim 1, characterized in that: The light source emits linearly polarized light; The annular light beam control mechanism comprises a modulation component, which is arranged between the light source and the electrochemical reaction cell and is used for modulating the linearly polarized light emitted by the light source into a linearly polarized light beam in a high-speed rotating state.
3. The electrochemical imaging device according to claim 2, characterized in that: The annular light beam control mechanism comprises an adjusting device, which is arranged between the modulation component and the electrochemical reaction cell, and is used for converting the linearly polarized light beam in a high-speed rotating state into P-polarized light.
4. The electrochemical imaging device according to claim 2, characterized in that: The modulation component includes a first galvanometer and a second galvanometer arranged in sequence along the light output path of the light source, the first galvanometer is configured to be able to rotate around an axis parallel to a first direction, and the second galvanometer is configured to be able to rotate around an axis parallel to a second direction, wherein the first direction and the second direction intersect with each other, and the light beam adjusted by the first galvanometer and the second galvanometer is in a high-speed rotation state.
5. The electrochemical imaging device according to claim 4, characterized in that: The annular light beam control mechanism comprises a first lens, which is arranged between the second galvanometer and the electrochemical reaction cell to transmit the light beam in a high-speed rotating state to the electrochemical reaction cell in the form of parallel light.
6. The electrochemical imaging device according to claim 2, characterized in that: The modulation component comprises a diffractive optical element, and the diffractive optical element is used to adjust the light beam so that the light beam is in a ring-shaped shape.
7. The electrochemical imaging device according to claim 4, characterized in that: The annular beam control mechanism includes a conical lens arranged between the modulation component and the electrochemical reaction cell, and the conical lens is configured to be movable relative to the modulation component along the propagation direction of the beam to adjust the incident angle of the beam projected onto the electrochemical reaction cell.
8. The electrochemical imaging device according to claim 1, characterized in that: The electrochemical imaging device comprises an electrochemical workstation; The electrochemical reaction cell includes a conductive cover glass with a coating, a reaction electrode and an electrolyte disposed on the conductive cover glass. The reaction electrode is disposed in the electrolyte and is connected to the electrochemical workstation. An electrochemical circuit is formed between the reaction electrode, the electrolyte and the electrochemical workstation.
9. The electrochemical imaging device according to claim 7, characterized in that: The reaction electrode comprises a reference electrode, a working electrode and a counter electrode, and the reference electrode, the working electrode and the counter electrode undergo an electrochemical reaction in the electrolyte.
10. An electrochemical imaging method using the electrochemical imaging device according to any one of claims 1 to 9, characterized in that: The electrochemical imaging method comprises the following steps: Modulating the emitted light of the light source into a ring-shaped light beam; adjusting the incident angle of the light beam distributed in an annular shape; Converting the annular light beam into P polarized light; Projecting the annular light beam converted into P-polarized light to the electrochemical reaction cell; The light scattered by the electrochemical reaction cell is received by the photographing element.