A detection device based on electron paramagnetic in-situ online electrochemical flat cell

Abstract

This utility model relates to an in-situ online electrochemical flat cell detection device based on electron paramagnetism, comprising an installation unit including a base; an electron paramagnetic spectrometer mounted on the base, the electron paramagnetic spectrometer having a test chamber; a liquid storage unit including a first liquid storage bottle, a second liquid storage bottle, and a third liquid storage bottle, the first liquid storage bottle for storing cleaning liquid, the second liquid storage bottle for storing samples, and the third liquid storage bottle for storing a trapping agent; a pipeline unit including a first pipeline, a second pipeline, and a third pipeline; and an in-situ electrochemical flat cell unit including a fixing component, an electrode wiring component, a resonant quartz tube, and a flat cell component, the electron paramagnetic spectrometer being used to detect samples within the flat cell component. This utility model can detect signals such as real free radicals in real time, automatically regulate electrolyte circulation for continuous sample injection and testing, truly achieving in-situ testing, reducing the operational difficulty of experiments, and improving experimental efficiency.

Description

Technical Field

[0001] This utility model relates to the field of electron paramagnetic detection technology, and in particular to an in-situ online electrochemical flat cell detection device based on electron paramagnetism. Background Technology

[0002] Electron paramagnetic resonance (EPR) is a magnetic resonance technique derived from the magnetic moments of unpaired electrons. It is an important tool for studying the unpaired electronic states in compounds or minerals, used for qualitative and quantitative detection of unpaired electrons in atoms or molecules and for exploring the structural characteristics of their surrounding environment. In principle, an electron is a fundamental particle with mass and a negative charge. It can undergo two types of motion: orbiting around the atomic nucleus and spinning along its central axis. This motion generates torque, producing current and magnetic moments. In an external magnetic field, the degenerate electron spin energy levels split. If an electromagnetic wave of a suitable frequency is applied perpendicular to the external magnetic field, electrons in lower spin energy levels can absorb the energy of the electromagnetic wave and transition to higher energy levels, resulting in the paramagnetic resonance absorption phenomenon. The main applications of electron paramagnetic resonance (EPR) spectroscopy in mineralogy are twofold: first, to study the isomorphic substitutions, order-disorder relationships, chemical bonds, lattice parameters, and local symmetry of paramagnetic impurity ions (concentrations below 1%) in minerals, such as transition metal ions and rare earth element ions; and second, to investigate the type, concentration, and properties of electron-hole centers related to point defects. EPR spectroscopy also plays an important role in mineral color research. Existing EPR spectra consist of a radiation source, resonant cavity, sample holder, signal receiver, amplifier, and recorder. The EPR spectrum of a mineral can provide information on the lattice position, valence state, local symmetry, concentration, and crystal field parameters of impurities with paramagnetic centers, thereby enabling the study of ground-state electronic structure and chemical bond properties, and explaining certain physical properties of the mineral.

[0003] However, unpaired free electrons are extremely small and have very short lifetimes. Sampling and dividing samples often requires specific capture solvents and other methods. Existing electron paramagnetic resonance (EPR) spectrometers, during detection, can only accommodate a uniform magnetic field space with a diameter of 6 mm and a height ranging from 22 mm to 40 mm within the resonant cavity. Microwave resonant cavities contain a strong magnetic field of 0.3 T, and the microwave frequency is 9.5 GHz in the X-band. Therefore, the limitation of existing techniques lies in the difficulty of performing in-situ online detection in sample solutions, thus hindering real-time and in-situ online detection of the electronic structure and chemical reaction processes of substances. Utility Model Content

[0004] Therefore, the technical problem to be solved by this utility model is to overcome the shortcomings of the prior art and provide a detection device based on electron paramagnetic in-situ online electrochemical flat cell, which can provide a detection device for EPR electron paramagnetic electrochemical scientific research and industrial online detection.

[0005] To solve the above-mentioned technical problems, this utility model provides a detection device based on electron paramagnetic in-situ online electrochemical flat cell, comprising, The mounting unit includes a base; An electron paramagnetic spectrometer, mounted on the base, the electron paramagnetic spectrometer having a test cavity; The liquid storage unit includes a first liquid storage bottle, a second liquid storage bottle, and a third liquid storage bottle. The first liquid storage bottle is used to store cleaning liquid, the second liquid storage bottle is used to store samples, and the third liquid storage bottle is used to store capture agents. A piping unit, comprising a first pipe, a second pipe, and a third pipe; An in-situ electrochemical flat cell unit includes a fixing component, an electrode wiring component, a resonant quartz tube, and a flat cell assembly. The electrode wiring component, the fixing component, and the resonant quartz tube are arranged sequentially along the axial direction of the in-situ electrochemical flat cell unit. The resonant quartz tube and the flat cell assembly are housed in a test chamber, and the flat cell assembly is coaxially disposed within the resonant quartz tube. The flat cell assembly includes a sample channel and a flat cavity. The flat cavity is interconnected with the sample channel. The projection of the flat cavity along the axial direction of the resonant quartz tube is rectangular. The inlet end of the flat cell assembly is connected to a second storage bottle through a first channel, and the inlet end of the flat cell assembly is also connected to a third storage bottle through a second channel. The outlet end of the flat cell assembly is connected to the second storage bottle through a third channel. An electron paramagnetic spectrometer is used to detect the sample within the flat cell assembly.

[0006] In one embodiment of this utility model, the flat cavity is disposed in the middle of the sample channel.

[0007] In one embodiment of the present invention, the fixing component includes a positioning seat, a fixing sleeve and a fastening nut arranged coaxially, the positioning seat is provided with a positioning block and the test cavity is provided with a positioning groove that matches the positioning block.

[0008] In one embodiment of the present invention, the electrode wiring assembly includes a clamping sleeve, an electrode, and an electrode terminal block. The clamping sleeve has an axially arranged mounting hole, and the electrode terminal block is fitted into the mounting hole. The number of mounting holes matches the number of electrode terminal blocks, and the clamping sleeve is connected to the fastening nut.

[0009] In one embodiment of this utility model, there are three electrode terminals and three mounting holes.

[0010] In one embodiment of this utility model, an output pipe is further provided between the sample pipe and the third pipe, and an avoidance hole is also provided on the clamping sleeve along the axial direction for the output pipe to pass through.

[0011] In one embodiment of this utility model, a circulating liquid control valve is further included. Two circulating liquid control valves are provided and are respectively disposed in the first pipe and the second pipe to control the flow of liquid in the first pipe and the second pipe.

[0012] In one embodiment of the present invention, a first pump body is further included, which is connected to the second liquid storage bottle to draw the sample from the second liquid storage bottle into the sample pipeline.

[0013] In one embodiment of the present invention, a second pump body is further included, which is connected to the third storage bottle to draw the capture agent into the sample pipeline.

[0014] In one embodiment of the present invention, the installation unit further includes a first support frame and a second support frame disposed on both sides of the base. The first support frame is used to place the first pump body and the second pump body, and the second support frame is used to place the liquid storage bottle unit.

[0015] The above-mentioned technical solution of this utility model has the following advantages compared with the prior art: This invention discloses an in-situ online electrochemical flat cell detection device based on electron paramagnetism, comprising an installation unit, an electron paramagnetic spectrometer, a liquid storage unit, a piping unit, and an in-situ electrochemical flat cell unit. The in-situ electrochemical flat cell unit includes a fixing assembly, an electrode wiring assembly, a resonant quartz tube, and a flat cell assembly. This device ensures airtight gas flow and performs detection based on the voltammetric electrochemical reaction principle, enabling in-situ online testing of organic solutions and water-soluble samples in an electron paramagnetic resonant cavity and detection of free radical signals. During in-situ online testing, it supports both static reaction testing and dynamic reaction testing with circulating sample flow, meeting the needs of EPR electron paramagnetic electrochemical research. This invention can detect real free radical signals in real time, automatically controlling electrolyte circulation for continuous sample injection and testing, truly achieving in-situ testing, reducing experimental difficulty, and improving experimental efficiency. Attached Figure Description

[0016] To make the content of this utility model easier to understand, the present utility model will be further described in detail below with reference to specific embodiments and accompanying drawings.

[0017] Figure 1 This is a schematic diagram of the overall structure of the detection device according to a preferred embodiment of the present invention.

[0018] Figure 2 This is a partial structural schematic diagram of the detection device according to a preferred embodiment of the present invention.

[0019] Figure 3 This is a bottom view schematic diagram of a partial structure of the detection device according to a preferred embodiment of the present invention.

[0020] Figure 4 This is a first-view structural schematic diagram of the flat pool assembly according to a preferred embodiment of the present invention.

[0021] Figure 5 This is a second-view structural schematic diagram of the flat pool assembly according to a preferred embodiment of the present invention.

[0022] Figure 6 This is a schematic diagram of the sample channel and flat cavity of a preferred embodiment of the present invention.

[0023] Explanation of reference numerals in the accompanying drawings: 10. Base; 11. First support frame; 12. Second support frame; 2. Electron paramagnetic spectrometer; 31. First storage bottle; 32. Second storage bottle; 33. Third storage bottle; 41. First pipe; 42. Second pipe; 43. Third pipe; 44. Output pipe; 5. Fixing assembly; 50. Positioning seat; 501. Positioning block; 51. Fixing sleeve; 52. Fastening nut; 6. Electrode wiring assembly; 60. Clamping sleeve; 61. Electrode terminal; 7. Resonant quartz tube; 8. Flat cell assembly; 80. Sample pipe; 81. Flat cavity; 82. First inlet; 83. Second inlet; 84. Outlet end; 91. First pump body; 92. Second pump body; 93. Circulating liquid control valve. Detailed Implementation

[0024] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments are not intended to limit the present invention.

[0025] In the field of electrochemical detection, cyclic voltammetry is the fundamental theoretical principle for studying electrochemistry. It can be used to detect changes in free radicals during the operation of electrochemical electrodes and samples in real time. Samples are usually tested using aqueous solutions, but polar solutions such as water absorb the electric field of microwaves and convert it into heat, thus blocking the absorption of the magnetic field of microwaves by free radicals. Therefore, precise control is required through microfluidics so that the resonant cavity of the electron paramagnetic spectrometer can be tuned.

[0026] Reference Figure 1 and Figure 2 As shown, this utility model discloses an in-situ online electrochemical flat cell detection device based on electron paramagnetism, including an installation unit. The installation unit includes a base 10, which can provide support for carrying the detection device.

[0027] The detection device also includes an electron paramagnetic spectrometer 2 installed on the base 10, the electron paramagnetic spectrometer 2 having a test cavity.

[0028] The detection device further includes a liquid storage unit 3, which comprises a first liquid storage bottle 31, a second liquid storage bottle 32, and a third liquid storage bottle 33. The first liquid storage bottle 31 is used to store cleaning liquid, the second liquid storage bottle is used to store samples, and the third liquid storage bottle 33 is used to store a capture agent. The cleaning liquid includes, but is not limited to, pure water; the samples include, but are not limited to, electrolytes, and may also be organic solutions and aqueous solutions.

[0029] Furthermore, the detection device also includes a pipeline unit, which includes a first pipeline 41, a second pipeline 42, and a third pipeline 43.

[0030] The detection device further includes an in-situ electrochemical flat cell unit, which comprises a fixing component 5, an electrode wiring component 6, a resonant quartz tube 7, and a flat cell component 8. Furthermore, the electrode wiring component 6, the fixing component 5, and the resonant quartz tube 7 are arranged sequentially along the axial direction of the in-situ electrochemical flat cell unit.

[0031] The resonant quartz tube 7 and the flat cell assembly 8 are housed within the test cavity. The resonant quartz tube 7 has a hollow interior. Specifically, the flat cell assembly 8 is coaxially disposed within the resonant quartz tube 7, with the axis of the flat cell assembly 8 overlapping the axis of the resonant quartz tube 7. This arrangement improves the uniformity of sample distribution, resulting in more accurate test results.

[0032] Furthermore, the flat cell assembly 8 includes a sample channel 80 and a flat cavity 81, the flat cavity 81 being interconnected with the sample channel 80, and the projection of the flat cavity 81 along the axial direction of the resonant quartz tube 7 being rectangular.

[0033] Furthermore, the inlet end of the flat cell assembly 8 is connected to the second storage bottle 32 via the first pipe 41, and the inlet end of the flat cell assembly 8 is also connected to the third storage bottle 33 via the second pipe 42. In detail, the inlet end includes a first inlet 82 and a second inlet 83, with the first pipe 41 connected to the first inlet 82 and the second pipe 42 connected to the second inlet 83. The outlet end 84 of the flat cell assembly 8 is connected to the second storage bottle 32 via the third pipe 43. Thus, through the cooperation of the pipe unit, the flat cell assembly 8, and the storage unit 3, a circulating liquid flow channel can be formed, enabling dynamic reaction testing of the circulating electrolyte. The electron paramagnetic spectrometer 2 is used to detect the sample within the flat cell assembly 8.

[0034] Therefore, this invention protects an in-situ online electrochemical flat cell detection device based on electron paramagnetism, comprising an installation unit, an electron paramagnetic spectrometer, a liquid storage unit, a piping unit, and an in-situ electrochemical flat cell unit. The in-situ electrochemical flat cell unit includes a fixing assembly, an electrode wiring assembly, a resonant quartz tube, and a flat cell assembly. This device ensures airtight gas flow and performs detection based on the voltammetric electrochemical reaction principle, enabling in-situ online testing of organic solutions and water-soluble samples in an electron paramagnetic resonant cavity and detection of free radical signals. During in-situ online testing, it supports both static reaction testing and dynamic reaction testing with circulating sample flow, meeting the needs of EPR electron paramagnetic electrochemical research. This invention can detect real free radical signals in real time, automatically controlling electrolyte circulation for continuous sample injection and testing, truly achieving in-situ testing, reducing experimental difficulty, and improving experimental efficiency.

[0035] The flat cavity 81 is disposed in the middle region of the sample conduit 80, and the spatial width of the flat cavity 81 along the radial direction of the resonant quartz tube 7 is 0.1-0.7 mm. As a preferred embodiment, the spatial width of the flat cavity 81 along the radial direction of the resonant quartz tube 7 can be set to 0.65-0.75 mm. This configuration makes it less likely for microwaves within the resonant cavity to be absorbed by the aqueous solution, thereby improving the accuracy of the detection results.

[0036] As a preferred implementation method, combined with Figure 4 as well as Figure 5As shown, the fixing assembly 5 includes a positioning seat 50, a fixing sleeve 51, and a fastening nut 52 arranged coaxially. The positioning seat 50, the fixing sleeve 51, and the fastening nut 52 are arranged sequentially along the axial direction of the resonant quartz tube 7 so that the in-situ electrochemical flat cell unit can be assembled into the test chamber through the fixing assembly 5. In addition, in order to improve the stability of the installation and ensure the stability and accuracy of the experimental process, the positioning seat 50 is provided with a positioning block 501, and the test chamber is provided with a positioning groove that matches the positioning block 501, so that the positioning block 501 can be confined in the positioning groove during installation.

[0037] Furthermore, referring to Figure 4 As shown, the electrode wiring assembly 6 includes a clamping sleeve 60 and electrode terminals 61. The clamping sleeve 60 has mounting holes along the axial direction, and the electrode terminals 61 are fitted into the mounting holes. It should be noted that the number of mounting holes matches the number of electrode terminals 61. The clamping sleeve 60 is connected to the fastening nut 52, and the clamping sleeve 60 and the fastening nut 52 are coaxially arranged.

[0038] In this embodiment, there are three electrode terminals 61, and correspondingly, there are also three mounting holes, each of which is configured to mount one electrode terminal 61.

[0039] In detail, an output pipe 44 is provided between the sample pipe 80 and the third pipe 43, and an axial clearance hole is provided on the clamping sleeve 60 for the output pipe 44 to pass through. Thus, by integrating the flat cell assembly 8 and the electrode terminal assembly 6, and in conjunction with the clamping sleeve 60 and internal sealing rings, the three electrodes are ensured to be insulated from the sample liquid when energized.

[0040] To improve the sample delivery efficiency, the detection device further includes a first pump body 91, which is connected to the second storage bottle 32 via the first pipe 41 to draw the sample from the second storage bottle 32 into the sample pipe 80. Specifically, the first pump body 91 includes, but is not limited to, a peristaltic pump.

[0041] To improve the capture efficiency of the capture agent, the detection device further includes a second pump body 92, which is connected to the third reservoir bottle 33 via the second conduit 42 to draw the capture agent from the third reservoir bottle 33 into the sample conduit 80. Specifically, the second pump body 92 includes, but is not limited to, a syringe pump.

[0042] In this way, by configuring a peristaltic pump and a syringe pump separately, and controlling the flow rate of the syringe pump at 0-100 μL / min, the microfluidic method can continuously mix the capture agent reagent, ensuring that all signals such as free radicals generated by the in-situ electrochemical reaction are captured, and ensuring that no detection signal is missed.

[0043] To facilitate control of the sample flow within the pipeline unit, the detection device is also equipped with a circulating liquid control valve 93, combined with... Figure 2 As can be seen, there are two circulating fluid control valves 93, which are respectively disposed in the first pipe 41 and the second pipe 42 to control the flow of liquid in the first pipe 41 and the flow of liquid in the second pipe 42.

[0044] As a preferred embodiment, refer to Figure 1 As shown, the installation unit also includes a first support frame 11 and a second support frame 12 disposed on both sides of the base 10. The first support frame 11 is used to place the first pump body 91 and the second pump body 92, and the second support frame 12 is used to place the liquid storage bottle unit.

[0045] It should be noted that, in order to facilitate operation by the experimenter, the detection device also includes a human-machine interface set on the first support frame 11.

[0046] As a preferred embodiment, for ease of testing operations, the first pipe 41, the second pipe 42, and the third pipe 43 are all made of flexible tubing.

[0047] To avoid affecting the sample, the sample channel 80 and the flat cavity 81 are made of high-purity quartz.

[0048] The working principle and process of this device are as follows: Pure water is placed in the first storage bottle 31, and half a bottle of test electrolyte is pre-filled in the third storage bottle 33. The third storage bottle 33 contains a free radical scavenger. The free radical scavenger is injected into the sealing soft stopper of the third storage bottle 33 through a free radical scavenger injection needle, isolating oxygen throughout the process. The sample peristaltic pump is started to draw electrolyte from the third storage bottle 33 into the capillary tube, filling the sample tube 80 and the flat cavity 81 with electrolyte and circulating it for at least one cycle to ensure that there are no air bubbles in the tube. The electron paramagnetic spectrometer 2 is started for normal standby operation to test whether the tuning is normal. If it is normal, the next test operation is performed. The electrode terminal 61 is energized or connected to the electrochemical workstation. According to the operating principle of cyclic voltammetry, the corresponding configuration is performed. The electron paramagnetic spectrometer 2 is started to continuously run at certain intervals (e.g., 60s, 120s, or 240s). According to the running time, the free radical scavenger is added to the sample tube 80 by starting the free radical scavenger injection pump to complete the corresponding number of consecutive test operations.

[0049] In the description of the embodiments of this utility model, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set" and "connection" 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 mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0050] In the description of this utility model, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this utility model, "a plurality of" means two or more, unless otherwise explicitly specified.

[0051] In this utility model, unless otherwise explicitly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical 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. For those skilled in the art, the specific meaning of the above terms in this utility model can be understood according to the specific circumstances.

[0052] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the protection scope of this invention.

Claims

1. A detection device based on electron paramagnetic in-situ online electrochemical flat cell, characterized in that: include, The mounting unit includes a base; An electron paramagnetic spectrometer, mounted on the base, the electron paramagnetic spectrometer having a test cavity; The liquid storage unit includes a first liquid storage bottle, a second liquid storage bottle, and a third liquid storage bottle. The first liquid storage bottle is used to store cleaning liquid, the second liquid storage bottle is used to store samples, and the third liquid storage bottle is used to store capture agents. A piping unit, comprising a first pipe, a second pipe, and a third pipe; An in-situ electrochemical flat cell unit includes a fixing component, an electrode wiring component, a resonant quartz tube, and a flat cell assembly. The electrode wiring component, the fixing component, and the resonant quartz tube are arranged sequentially along the axial direction of the in-situ electrochemical flat cell unit. The resonant quartz tube and the flat cell assembly are housed in a test chamber, and the flat cell assembly is coaxially disposed within the resonant quartz tube. The flat cell assembly includes a sample channel and a flat cavity. The flat cavity is interconnected with the sample channel. The projection of the flat cavity along the axial direction of the resonant quartz tube is rectangular. The inlet end of the flat cell assembly is connected to a second storage bottle through a first channel, and the inlet end of the flat cell assembly is also connected to a third storage bottle through a second channel. The outlet end of the flat cell assembly is connected to the second storage bottle through a third channel. An electron paramagnetic spectrometer is used to detect the sample within the flat cell assembly.

2. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 1, characterized in that: The flat cavity is located in the middle of the sample channel.

3. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 1 or 2, characterized in that: The fixing assembly includes a positioning seat, a fixing sleeve, and a fastening nut arranged coaxially. The positioning seat is provided with a positioning block, and the test cavity is provided with a positioning groove that matches the positioning block.

4. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 3, characterized in that: The electrode wiring assembly includes a clamping sleeve, an electrode, and an electrode terminal block. The clamping sleeve has an axially arranged mounting hole, and the electrode terminal block is fitted into the mounting hole. The number of mounting holes matches the number of electrode terminal blocks. The clamping sleeve is connected to the fastening nut.

5. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 4, characterized in that: The electrode terminals are provided in three places, and the mounting holes are also provided in three places.

6. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 4, characterized in that: An output pipe is provided between the sample pipe and the third pipe, and an axial clearance hole is provided on the clamping sleeve for the output pipe to pass through.

7. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 1, characterized in that: It also includes circulating fluid control valves, two of which are respectively installed in the first pipe and the second pipe to control the flow of liquid in the first pipe and the second pipe.

8. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 1, characterized in that: It also includes a first pump body, which is connected to the second storage bottle to draw the sample from the second storage bottle into the sample pipeline.

9. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 8, characterized in that: It also includes a second pump body, which is connected to the third reservoir bottle to draw the capture agent into the sample pipeline.

10. The in-situ online electrochemical flat cell detection device based on electron paramagnetism according to claim 9, characterized in that: The installation unit further includes a first support frame and a second support frame disposed on both sides of the base. The first support frame is used to place the first pump body and the second pump body, and the second support frame is used to place the liquid storage unit.

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