CN114858893A - Anti-interference nuclear magnetic resonance in-situ electrochemical coupling device and use method thereof - Google Patents
Anti-interference nuclear magnetic resonance in-situ electrochemical coupling device and use method thereof Download PDFInfo
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- CN114858893A CN114858893A CN202210539924.3A CN202210539924A CN114858893A CN 114858893 A CN114858893 A CN 114858893A CN 202210539924 A CN202210539924 A CN 202210539924A CN 114858893 A CN114858893 A CN 114858893A
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Abstract
The invention discloses an anti-interference nuclear magnetic resonance in-situ electrochemical coupling device and a using method thereof. The existing in-situ devices are connected with an external electrochemical workstation by using wires, the electrochemical data are controlled to be input and transmitted by the loaded energy supply control assembly, an external electromagnetic field is isolated by using a wireless technology, and external electromagnetic interference caused by wired connection in the traditional method is avoided, so that the peak resolution of the nuclear magnetic resonance spectrum can be improved to over 240 percent compared with the traditional wired connection; in addition, the wireless connection enables the terminal not to be limited by a computer, and is beneficial to assembly, reutilization and maintenance of the in-situ combination device.
Description
Technical Field
The invention relates to the field of nuclear magnetic resonance instruments, in particular to an anti-interference nuclear magnetic resonance in-situ electrochemical coupling device and a using method thereof.
Background
The nuclear magnetic resonance spectroscopy has extremely high spectral resolution and is widely applied to the analysis and structural identification of chemical substance compositions at present. Also, in the electrochemical field, nuclear magnetic resonance spectroscopy has been used to detect various electrochemically generated products. However, in the conventional method, a delay error is generated in the process from the obtaining of the electrochemical product and the intermediate to the sending of the electrochemical product and the intermediate into a nuclear magnetic resonance spectrometer for detection, so that the spectral line information of the intermediate of the reaction cannot be accurately obtained, and the study on the characteristics of the electrochemical process is influenced.
Therefore, the in-situ detection technology for the combination of nuclear magnetic resonance spectroscopy and electrochemistry is created, a specially-made electrode is inserted into a specially-made in-situ nuclear magnetic tube and is connected to an external electrochemical workstation through an electric wire, while the electrochemical workstation is used for electrolysis, a nuclear magnetic resonance spectrometer is used for monitoring the sample in real time, the method can detect the components of the electrochemical products almost without time delay, and can also observe intermediate products which can not be observed in situ, and the method is widely applied in the field of electrochemical research, but because of the need of wire connection, even through keep apart the interference through the wave filter, still lead to the outside electromagnetic field of nuclear magnetic resonance spectrometer to avoid through the electric wire direct action in nuclear magnetic resonance spectrometer detection area, influence the inside magnetic field of nuclear magnetic resonance spectrometer, and then make the resolution ratio decline of signal, the circular telegram also can cause the acquisition signal unstable simultaneously.
Disclosure of Invention
The method aims at the problems that the detection precision of the nuclear magnetic resonance spectrum is influenced by electromagnetic interference under the complex electromagnetic environment and the like. An embodiment of the present application is directed to providing an anti-interference nmr in-situ electrochemical coupling apparatus and a method for using the same to solve the technical problems mentioned in the background section above.
In a first aspect, an embodiment of the present application provides an anti-interference nmr in-situ electrochemical coupling device, which includes a connecting rod, an energy supply control assembly, and a three-core shielding wire connected to the energy supply control assembly, the connecting rod is hollow and can accommodate the three-core shielding wire to pass through, three copper wires in the three-core shielding wire are respectively connected to a reference electrode, a working electrode, and an auxiliary electrode, a nuclear magnetic tube fixing post and an electrode fixing post coaxial with the connecting rod are disposed at a terminal of the connecting rod, the nuclear magnetic tube fixing post is used for fixing a nuclear magnetic tube, the reference electrode, the working electrode, and the auxiliary electrode are fixed on the electrode fixing post and connected to the three-core shielding wire in the electrode fixing post, the energy supply control assembly includes a control module, a data conversion module, a current detection module, a wireless communication module, and a power supply module, the data conversion module, an operational amplifier, the current detection module, the wireless communication module, and the power supply module are respectively connected to the control module, the working electrode and the reference electrode are connected with the data conversion module sequentially through the three-core shielding wire and the operational amplifier, the control module is used for calculating a corrected voltage value according to the voltage of the reference electrode and outputting the corrected voltage value to the working electrode, a current path is formed between the working electrode and the auxiliary electrode, the auxiliary electrode is connected with the current detection module and the data conversion module through the three-core shielding wire, the control module calculates voltage difference data collected by the current detection module to obtain current data, and the current data are sent to the terminal through the wireless communication module.
Preferably, the data conversion module comprises an analog-to-digital converter and a digital-to-analog converter, the working electrode is connected with the digital-to-analog converter, the digital-to-analog converter is used for converting the corrected voltage value into an analog signal and outputting the analog signal to the working electrode, the reference electrode is connected with the analog-to-digital converter, the current detection module is connected with the analog-to-digital converter, and the analog-to-digital converter is used for converting the voltage signal transmitted by the reference electrode and the current signal output by the current detection module into a digital signal and transmitting the digital signal to the control module.
Preferably, the three-core shielded wire comprises an upper three-core shielded wire and a lower three-core shielded wire, the connecting rod comprises an upper connecting rod and a lower connecting rod which respectively accommodate the upper three-core shielded wire and the lower three-core shielded wire to pass through, and the upper connecting rod and the lower connecting rod are connected through threads.
Preferably, the bottom of the electrode fixing column is provided with a reserved hole for allowing the reference electrode, the working electrode and the auxiliary electrode to pass through.
Preferably, the working electrode is made of conductive glass material, and the reference electrode and the auxiliary electrode are arranged around the insulating surface at two sides of the working electrode.
Preferably, the nuclear magnetic tube fixing column, the electrode fixing column and the lower connecting rod are integrally formed, a gap is formed between the nuclear magnetic tube fixing column and the electrode fixing column, a step is formed between the nuclear magnetic tube fixing column and the lower connecting rod, the nuclear magnetic tube is formed by coaxially splicing round tubes with different diameters, and the tube wall above the nuclear magnetic tube can be sleeved in the gap.
Preferably, the energizing control assembly is housed in a housing that is integrally formed with the upper connecting rod.
Preferably, the wireless communication module is a bluetooth module, the power supply module comprises a battery module and a charging management module, the charging management module is connected with the battery module and used for controlling charging and discharging of the battery module, and the battery module is connected with the control module to provide power supply.
Preferably, the electrochemical data acquisition device further comprises a display module, wherein the display module is connected with the control module and is used for displaying the electrochemical data.
In a second aspect, an embodiment of the application further provides a use method of the anti-interference nmr in-situ electrochemical combination apparatus, including the following steps:
1) manufacturing a working electrode, connecting the working electrode, a reference electrode and an auxiliary electrode with a lower three-core shielding wire, and respectively fixing the working electrode, the reference electrode and the auxiliary electrode on an electrode fixing column; the lower three-core shielding wire penetrates out of the lower connecting rod and is connected with the upper three-core shielding wire, the upper three-core shielding wire penetrates out of the upper connecting rod, the upper connecting rod and the lower connecting rod are fixedly connected, and the upper three-core shielding wire is connected with the energy supply control assembly to complete the assembly of the device;
2) placing the electrolyte to be tested in a nuclear magnetic tube, fixing the nuclear magnetic tube in a gap between a nuclear magnetic tube fixing column and an electrode fixing column, inserting the nuclear magnetic tube fixing column into a gauge matched with a nuclear magnetic resonance spectrometer, and adjusting the positions of an auxiliary electrode and a reference electrode to enable the auxiliary electrode and the reference electrode to just reach the upper boundary of a corresponding detection area on the gauge matched with the nuclear magnetic resonance spectrometer;
3) placing the upper connecting rod, the lower connecting rod, the nuclear magnetic tube fixing column, the electrode fixing column and the nuclear magnetic tube into a sample inlet of a nuclear magnetic resonance spectrometer, and fixing the device on the nuclear magnetic resonance spectrometer through a step between the lower connecting rod and the nuclear magnetic tube fixing column;
4) adopt terminal and energy supply control module to carry out wireless connection to transmit the electrochemistry parameter of setting for energy supply control module, treat that nuclear magnetic resonance spectrometer's collection parameter sets up the completion back, begin the electrolysis by terminal control, and control nuclear magnetic resonance spectrometer and gather the wave spectrum, pass through wireless communication with current data transmission for the terminal after the electrolysis is accomplished.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the remote communication technology, avoids the external electromagnetic field from directly reaching the detection area of the nuclear magnetic resonance spectrometer through a wire, and the peak resolution of the nuclear magnetic resonance spectrometer can be improved to over 240 percent.
(2) The invention can use different voltages to electrolyze a sample in a detection area of the nuclear magnetic resonance spectrometer, the conductive glass electrode can be inserted into the detection area to realize the real-time monitoring of the spectral line of the electrochemical reaction, the matched energy supply control component is used for inputting electrolysis parameters to carry out the electrochemical experiment, and simultaneously, the electrochemical data obtained by the experiment is transmitted to the computer terminal, so that the in-situ electrochemical research is realized under the condition of shielding the interference of an external electromagnetic field, and the high-resolution nuclear magnetic resonance spectral line can be obtained in real time.
(3) The invention can shield the interference of the external electromagnetic field to the magnetic field in the nuclear magnetic resonance spectrometer and simultaneously can shield the interference of the external electromagnetic field to the field locking signal required in the field frequency interlocking function of the nuclear magnetic resonance spectrometer, so that the field frequency interlocking function can play a better role, the effect of keeping the magnetic field stable after the long-time electrolysis is carried out by using the invention is achieved, and the high-resolution nuclear magnetic resonance spectral line can be continuously acquired for a long time.
(4) The wired part of the anti-interference nuclear magnetic resonance in-situ electrochemical combined device is fully shielded by using the nuclear magnetic resonance cavity, and electrochemical data are transmitted to the terminal by adopting a wireless communication technology, so that the influence of a complex electromagnetic field around an instrument on a magnetic field in a nuclear magnetic resonance spectrometer is reduced, and a spectral line with high resolution is obtained. The whole device is convenient to assemble, can be repeatedly used without being disassembled after being assembled, improves the experimental research efficiency, is convenient to carry, and is favorable for loading and disassembling on a nuclear magnetic resonance spectrometer; the electrode fixing column is designed in the device, so that the electrode can be conveniently inserted into the nuclear magnetic tube, and the experimental research difficulty is reduced.
Drawings
The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and together with the description serve to explain the principles of the invention. Other embodiments and many of the intended advantages of embodiments will be readily appreciated as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numerals designate corresponding similar parts.
FIG. 1 is a schematic structural diagram of an anti-interference NMR in-situ electrochemical coupling apparatus according to an embodiment of the present disclosure;
FIG. 2 is a block diagram of a power supply control component of the anti-jamming NMR in-situ electrochemical apparatus according to an embodiment of the present disclosure;
FIG. 3 is a schematic structural diagram of an upper connecting rod of the anti-interference NMR in-situ electrochemical coupling apparatus according to the embodiment of the present application;
FIG. 4 is a schematic structural diagram of a lower connecting rod of the anti-interference NMR in-situ electrochemical coupling apparatus according to the embodiment of the present application;
fig. 5 is a schematic structural diagram of an electrode fixing column of an anti-interference nmr in-situ electrochemical coupling apparatus according to an embodiment of the present application;
FIG. 6 is a schematic diagram of the connection of the electrode part of the anti-interference NMR in-situ electrochemical apparatus according to the embodiment of the present application;
FIG. 7 is a schematic diagram of a coupling of an anti-interference NMR in situ electrochemical apparatus with a NMR tube according to an embodiment of the disclosure;
FIG. 8 shows NMR spectroscopy lock field line states using an anti-interference NMR in situ electrochemical apparatus of an embodiment of the present application;
FIG. 9 shows the NMR spectrum lock field line state of the conventional method (directly using electric wires to connect the electrochemical workstation), in which the exposed line outside the NMR spectrum cavity is 1.6 m, and the dashed line frame shows the interference wave of the lock field signal affected by the external electromagnetic field;
FIG. 10 shows NMR one-dimensional H of 0.05M p-phenol solution electrolyzed by examples and comparative examples of the present application 1 Spectral line, electrolysis time 1 hour, using solvent 0.1M dilute sulfuric acid diluted with D2O containing TMS internal standard, using working electrode as catalyst coated with polyaniline film on the described conductive glass, using one-dimensional H with Presat pressurized water in sequence 1 A sequence of spectra in which the peak at 6.79ppm is the reactant peak, 6.86ppm is the product peak, the peripheral gray peak is the peak when electrolyzed using a conventional electrochemical workstation, and the internal black peak is the peak when electrolyzed for the examples of this application;
FIG. 11 shows NMR one-dimensional H of 0.05M p-phenol solution when electrolyzing the solutions in examples and comparative examples of the present application 1 The electrolytic time of the spectral line is 1 hour, the peak of the spectral line is the peak of the internal standard substance TMS which is positioned at 0ppm, similarly, the peripheral gray peak is the peak when the traditional electrochemical workstation is used for electrolysis, and the internal black peak is the peak when the electrochemical workstation is used for electrolysis;
FIG. 12 is a comparison of the full widths at half maximum of the product peak, reactant peak, internal standard peak after electrolysis for the examples and comparative examples of the present application, the full width at half maximum being used to measure NMR spectral resolution;
FIG. 13 is a comparison of electrochemical data for examples of the present application and comparative examples;
reference numerals: 1. a battery chamber; 2. controlling the communication room; 3. a first reserved port; 4. a charging reserved port; 5. an upper connecting rod; 7. an electrode; 6. a lower connecting rod; 8. a second reserved port; 9. an upper three-core shield wire; 10. an internal thread; 11. a third reserved port; 12. a lower three-core shield wire; 13. an external thread; 14. an electrode fixing column; 15. fixing a nuclear magnetic tube; 16. a reference electrode reserved opening; 17. a working electrode reserved opening; 18. an auxiliary electrode reserved opening; 19. a reference electrode; 20. an auxiliary electrode; 21. a working electrode; 22. copper glue; 23. a first copper wire; 24. a second copper wire; 25. a third copper wire; 26. a nuclear magnetic tube; 30. an energy supply control assembly; 31. a control module; 32. a current detection module; 33. a wireless communication module; 34. a display module; 35. a battery module; 36. and a charging management module.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the related invention are shown in the drawings. It should be noted that the dimensions and sizes of the elements in the figures are not to scale and the sizes of some of the elements may be highlighted for clarity of illustration.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
Referring to fig. 1-7, an embodiment of the present application provides an anti-interference nmr in-situ electrochemical coupling device, which includes a connecting rod, an energy supply control assembly 30, and a three-core shielding wire connected to the energy supply control assembly 30, where the energy supply control assembly 30 is accommodated in a housing, and the housing and the connecting rod are both made of nonmagnetic plastic. The connecting rod is hollow and can accommodate a three-core shielding wire to pass through, the three-core shielding wire is connected with the electrode 7, specifically, a first copper wire 23, a second copper wire 24 and a third copper wire 25 in the three-core shielding wire are respectively connected with the reference electrode 19, the working electrode 21 and the auxiliary electrode 20, the tail end of the connecting rod is provided with a nuclear magnetic tube fixing column 15 and an electrode fixing column 14 which are coaxial with the connecting rod, the nuclear magnetic tube fixing column 15 is used for fixing the nuclear magnetic tube 26, the reference electrode 19, the working electrode 21 and the auxiliary electrode 20 are fixed on the electrode fixing column 14 and are connected with the three-core shielding wire in the electrode fixing column 14, the energy supply control assembly 30 comprises a control module 31, a data conversion module, a current detection module 32, a wireless communication module 33, a display module 34 and a power supply module, the data conversion module, the operational amplifier, the current detection module 32, the wireless communication module 33, the display module 34 and the power supply module are respectively connected with the control module 31, the working electrode 21 and the reference electrode 19 are connected with the data conversion module sequentially through the three-core shielding wire and the operational amplifier, the control module 31 is used for calculating a corrected voltage value according to the voltage of the reference electrode 19 and outputting the corrected voltage value to the working electrode 21, a current path is formed between the working electrode 21 and the auxiliary electrode 20, the auxiliary electrode 20 is connected with the current detection module 32 and the data conversion module through the three-core shielding wire, the control module 31 calculates voltage difference data collected by the current detection module 32 to obtain current data, and the current data are sent to a terminal through the wireless communication module 33. Specifically, the data conversion module includes an analog-to-digital converter (ADC) and a digital-to-analog converter (DAC), the working electrode 21(WE) is connected to the digital-to-analog converter, the digital-to-analog converter is configured to convert the corrected voltage value into an analog signal and output the analog signal to the working electrode 21, the reference electrode 19(RE) is connected to the analog-to-digital converter, the auxiliary electrode 20(CE) is sequentially connected to the analog-to-digital converter and the current detection module 32, the analog-to-digital converter is configured to convert the voltage signal transmitted by the reference electrode 19 and the current signal output by the current detection module 32 into a digital signal and transmit the digital signal to the control module 31, and the display module 34 is configured to display electrochemical data such as current data.
Specifically, control module 31 selects the microprocessor chip that has analog-to-digital converter and digital-to-analog converter integrated function for use, can adopt STM32F103ZET6, also can substitute with ordinary microprocessor chip collocation analog-to-digital converter and digital-to-analog converter. Because the electrochemical supply current is small, the control module 31 can be directly used for supplying power to the three electrodes 7, the DAC pin is used for controlling the voltage to be used as an output end, the operational amplifier is used for enabling the voltage of the reference electrode 19 to follow the working electrode 21, the auxiliary electrode 20 is connected with the current detection module 32, the current detection module 32 can use a current amplification chip, such as the LTC6101 of the sub-Deno, and the output is connected with the ADC pin of the microprocessor chip for reading; the wireless communication module 33 is a bluetooth module and is used for connecting with the control module 31 for remote communication, in other embodiments, the wireless communication module 33 may also adopt wireless communication modes such as a wifi module. The power supply module includes a battery module 35 and a charging management module 36, the charging management module 36 is connected to the battery module 35 for controlling charging and discharging of the battery module 35, and the battery module 35 is connected to the control module 31 for supplying power. The battery module 35 adopts a 3.7V lithium battery to supply power for other functional modules. The charge management module 36 is used to manage the charging of the rechargeable battery, and the intermediate diode prevents the current from flowing backwards.
In a specific embodiment, referring to fig. 3 and 4, the three-core shielded wire includes an upper three-core shielded wire 9 and a lower three-core shielded wire 12, the connecting rod includes an upper connecting rod 5 and a lower connecting rod 6 for respectively receiving the upper three-core shielded wire 9 and the lower three-core shielded wire 12 to pass through, the battery chamber 1 and the control communication chamber 2 are provided in the housing, and the housing is integrally formed with the upper connecting rod 5. The control communication room 2 is provided with a charging reserved port 4, a first reserved port 3 for connecting a power supply module and a control module 31 is arranged between the battery room 1 and the control communication room 2, and a second reserved port 8 for connecting an upper three-core shielding wire 9 and the control communication room 2 is arranged between the control communication room 2 and the upper connecting rod 5. The lower part of the upper connecting rod 5 is provided with an internal thread 10 for assembly, the upper part of the lower connecting rod 6 is provided with a third reserved opening 11 for the lower three-core shielding wire 12 to pass through, and an external thread 13 for assembly is arranged, the size of the external thread is matched with the internal thread 10, and the upper connecting rod 5 is in threaded connection with the lower connecting rod 6. Nuclear-magnetism pipe fixed column 15 and electrode fixed column 14 and lower part connecting rod 6 integrated into one piece are equipped with the space between nuclear-magnetism pipe fixed column 15 and the electrode fixed column 14, form the step between nuclear-magnetism pipe fixed column 15 and the lower part connecting rod 6, and nuclear-magnetism pipe 26 is the coaxial concatenation of the pipe of different diameters and forms, and the pipe wall above nuclear-magnetism pipe 26 can be located in the space by the cover.
In a specific embodiment, referring to fig. 5, the bottom of the electrode fixing column 14 is provided with a reserved hole for allowing the reference electrode 19, the working electrode 21 and the auxiliary electrode 20 to pass through, which are the reserved hole 16 for the reference electrode, the reserved hole 17 for the working electrode and the reserved hole 18 for the auxiliary electrode.
In a specific embodiment, referring to fig. 6, the working electrode 21 is made of a conductive glass material, and the reference electrode 19 and the auxiliary electrode 20 are disposed around the insulating surface on both sides of the working electrode 21. Specifically, the working electrode 21 is formed by fixing two pieces of long-strip single-sided conductive glass in a manner that insulating surfaces are close to each other by using a double-sided adhesive tape and binding the two pieces of long-strip single-sided conductive glass by using a copper tape 22, the working electrode is fixed at the middle position by the electrode fixing column 14, and the second copper wire 24 of the lower three-core shielding wire 12 is placed on the copper tape 22. The reference electrode 19 and the auxiliary electrode 20 are respectively welded with the first copper wire 23 and the third copper wire 25 of the lower three-core shielding wire 12, the reference electrode 19, the working electrode 21 and the auxiliary electrode 20 are fixed on the reference electrode reserved opening 16, the working electrode reserved opening 17 and the auxiliary electrode reserved opening 18 of the electrode fixing column 14, the reference electrode 19 can adopt a silver wire electrode 7, the auxiliary electrode 20 can adopt a platinum wire electrode 7, and the reference electrode 19 and the auxiliary electrode 20 are located on the insulating surfaces of two sides of the working electrode 21.
Referring to fig. 7, the nuclear magnetic pipe 26 is formed by splicing a conventional nuclear magnetic pipe 26 with an upper end of 10mm and a conventional nuclear magnetic pipe 26 with a lower end of 5mm, and the nuclear magnetic pipe 26 is fixed on the nuclear magnetic pipe fixing post 15 of the lower connecting rod 6 in use. The device as a whole, except for the nuclear magnetic tube 26, can be assembled for reuse without disassembly, and is convenient to load and unload on a nuclear magnetic resonance spectrometer.
The embodiment of the application achieves the function of an electrochemical workstation by a special circuit board, uses a three-core shielding wire to be connected with the electrode 7 of the nuclear magnetism detection area, meanwhile, the electrode fixing column 14 is integrated to achieve the positioning effect of a rotor of a common nuclear magnetic resonance spectrometer, the electrochemical signals are transmitted by adopting a wireless communication technology, the voltage follower formed by an operational amplifier is used for isolating the interference between the electrochemical signals and the wireless signals, and because the circuit board can be tightly attached to the nuclear magnetic resonance entrance, the conductive wires are all positioned in the shielding cavity of the nuclear magnetic resonance spectrometer, so that the external electromagnetic interference is prevented from entering the nuclear magnetic internal acquisition area through the lead, meanwhile, because of the integrated design and wireless communication form, it is not limited to computer terminal, the electrochemical signal can be received and recorded by a terminal control device with a wireless function, such as a mobile phone, and the like, so that the application scene is richer, and the electrochemical signal is portable and has the characteristic of repeated use after assembly.
The embodiment of the application further provides a using method of the anti-interference nuclear magnetic resonance in-situ electrochemical combined device, which is characterized by comprising the following steps:
1) manufacturing a working electrode 21, connecting the working electrode 21, a reference electrode 19 and an auxiliary electrode 20 with the lower three-core shielding wire 12, and respectively fixing the working electrode 21, the reference electrode 19 and the auxiliary electrode 20 on the electrode fixing column 14; the lower three-core shielding wire 12 penetrates out of the lower connecting rod 6 and is connected with the upper three-core shielding wire 9, the upper three-core shielding wire 9 penetrates out of the upper connecting rod 5, the upper connecting rod 5 and the lower connecting rod 6 are fixedly connected, and the upper three-core shielding wire 9 is connected with the energy supply control assembly 30 to complete the assembly of the device;
2) placing the electrolyte to be tested in a nuclear magnetic tube 26, fixing the nuclear magnetic tube 26 in a gap between a nuclear magnetic tube fixing column 15 and an electrode fixing column 14, inserting the nuclear magnetic tube fixing column 15 into a gauge matched with a nuclear magnetic resonance spectrometer, and adjusting the positions of an auxiliary electrode 20 and a reference electrode 19 to enable the auxiliary electrode 20 and the reference electrode 19 to just reach the upper boundary of a corresponding detection area on the gauge matched with the nuclear magnetic resonance spectrometer;
3) placing the upper connecting rod 5, the lower connecting rod 6, the nuclear magnetic tube fixing column 15, the electrode fixing column 14 and the nuclear magnetic tube 26 into a sample inlet of a nuclear magnetic resonance spectrometer, and fixing the device on the nuclear magnetic resonance spectrometer through a step between the lower connecting rod 6 and the nuclear magnetic tube fixing column 15;
4) adopt terminal and energy supply control module 30 to carry out wireless connection to transmit the electrochemistry parameter of setting for energy supply control module 30, treat that nuclear magnetic resonance spectrometer's collection parameter sets up the completion back, begin the electrolysis by terminal control, and control nuclear magnetic resonance spectrometer and gather the wave spectrum, transmit electrochemistry data for the terminal through wireless communication after the electrolysis is accomplished.
Specifically, the assembly process of the anti-interference nuclear magnetic resonance in-situ electrochemical combined device is as follows:
firstly, preparing two working electrodes 21 of long strip-shaped single-sided conductive glass, fixing the working electrodes in a mode that insulating surfaces are close to each other by using double-sided adhesive tapes, winding the outer part of the upper part of the conductive glass for a circle by using copper adhesive tapes 22 to finally manufacture the working electrodes 21, placing copper wires of the lower three-core shielding wire 12 on the copper adhesive tapes 22, winding and wrapping the copper wires for two circles by using polytetrafluoroethylene tapes for insulation treatment and fixing. The auxiliary electrode 20 and the reference electrode 19 are respectively welded on the third copper wire 25 and the first copper wire 23 of the lower three-core shielding wire 12; and then inserting a reference electrode 19, a working electrode 21 and an auxiliary electrode 20 into the reference electrode reserved opening 16, the working electrode reserved opening 17 and the auxiliary electrode reserved opening 18 of the electrode fixing column 14 respectively, so that the auxiliary electrode 20 and the reference electrode 19 are attached to the insulating surfaces of the two sides of the working electrode 21 respectively, and the reserved openings can be fixed by 401 quick-drying adhesive, so that the assembly of the lower half part is completed.
The lower three-core shielding wire 12 penetrates through the third reserved opening 11 to be welded with the upper three-core shielding wire 9, and then the upper three-core shielding wire 9 penetrates through the upper connecting rod 5 to pass through the second reserved opening 8; finally, the internal thread 10 of the upper connecting rod 5 is connected with the external thread 13 of the lower connecting rod 6, the upper three-core connecting and shielding wire can be fixed to the first reserved opening 3 by hot melt adhesive, and then the upper three-core connecting and shielding wire is connected to the energy supply control assembly 30 through welding, and the assembly of the device is completed. The whole assembly process should be noted from bottom to top to avoid the distortion of the three-core shielding wire in the assembly process.
The process for manufacturing the nuclear magnetic tube 26 is as follows:
taking a conventional nuclear magnetic pipe 26 with the caliber of 10mm and a conventional nuclear magnetic pipe 26 with the caliber of 5mm, wherein the length of the conventional nuclear magnetic pipe 26 with the caliber of 10mm at the upper end is the length of the nuclear magnetic pipe fixing column 15 minus 1cm, and can be 4 cm; the length of the conventional nuclear magnetic pipe 26 with the diameter of 5mm at the lower end is 1cm from the tail end of the nuclear magnetic pipe fixing column 15 to the lower boundary of the detection area of the nuclear magnetic resonance spectrometer, and the length can be changed according to the sizes of different nuclear magnetic resonance spectrometers so as to fit each device; as shown in fig. 7, a conventional nuclear magnetic pipe 26 with a diameter of 10mm is used as an inlet of the nuclear magnetic pipe 26, a conventional nuclear magnetic pipe 26 with a diameter of 5mm is used as a position of a detection area to splice the two, and the conventional nuclear magnetic pipe 26 with the diameter of 5mm and the conventional nuclear magnetic pipe 26 with the diameter of 110mm become coaxial cylinders after splicing.
The experimental route of the anti-interference nuclear magnetic resonance in-situ electrochemical combined device used for monitoring spectral line signals and electrochemical signals in electrochemical reaction in real time by using a nuclear magnetic resonance spectrometer under the condition of a complex electromagnetic field is as follows:
(1) injecting electrolyte to be tested into the nuclear magnetic tube 26 by a liquid-transferring gun, as shown in fig. 7, making the electrolyte to be tested submerge in the black testing area, coating the catalyst to be tested on the conductive sides of the two sides of the working electrode 21, wherein the area of the catalyst is 1cm at the bottom of the working electrode 21, inserting the nuclear magnetic tube 26 with the sample from the nuclear magnetic tube fixing column 15 when the catalyst is stable, inserting the nuclear magnetic fixing column part into a gauge matched with a nuclear magnetic resonance spectrometer for measurement, making the auxiliary electrode 20 and the reference electrode 19 just reach the upper boundary of the testing area of the nuclear magnetic resonance spectrometer, so as to prevent the metal electrode 7 from entering the testing area to influence the magnetic field uniformity of the testing area, thereby influencing the spectral resolution, at the moment, because the working electrode 21 is inserted into the liquid to occupy the testing area space, the liquid level can rise, thereby contacting the auxiliary electrode 20 and the reference electrode 19, and ensuring the smooth reaction, meanwhile, the purposes of using less electrolyte, enabling the relative concentration of reaction products to be larger and observing the products to be more obvious are achieved, and finally, the relative position between the electrode 7 and the detection area is adjusted by adopting a gauge matched with a nuclear magnetic resonance spectrometer.
(2) The nuclear magnetic tube 26 of the device is inserted into the connecting rod part along the sample injection pipeline from the sample injection port of the nuclear magnetic resonance spectrometer until the splicing position of the nuclear magnetic tube fixing column 15 and the thick and thin cylinder of the lower connecting rod 6 is just clamped at the position of the rotary clamping port of the nuclear magnetic resonance spectrometer, so that the device plays a role in fixing the detection area and supporting the device.
(3) Carry out wireless connection through computer terminal and energy supply control module 30 to use software to carry out electrochemistry parameter setting and transmit to energy supply control module 30, if: parameters such as electrolysis voltage and electrolysis time; after the acquisition parameters of the nuclear magnetic resonance spectrometer are set, the nuclear magnetic resonance spectrometer is controlled by the computer terminal to start electrolysis, the nuclear magnetic resonance spectrometer is controlled to acquire wave spectrums, after the electrolysis is finished, the energy supply control assembly 30 sends electrochemical data to the computer terminal, and Matlab and other software can be used for drawing to form an electrochemical electrolysis curve.
(4) After the experiment is accomplished, take out the device from the nuclear magnetic resonance spectrometer along the inlet tube, use distilled water to wash working electrode 21, auxiliary electrode 20 and reference electrode 19, dry the back and charge through charging reserve mouth 4 to equipment, can carry out the next time after the completion and use, can slightly polish auxiliary electrode 20 and reference electrode 19 with abrasive paper before using.
The invention replaces the traditional wire connection with wireless communication, can remove the influence of external complex electromagnetic field on the magnetic field in the instrument, and can remove the interference of the metal electrode 7 on the magnetic field by placing the working electrode 21 made of conductive glass in the detection area, thereby improving the resolution of the atlas, realizing the real-time monitoring of the intermediate substance and the product generated on the surface of the working electrode 21 under the requirement of high resolution, and when the requirement of resolution is extremely high, the working electrode 21 can be adjusted to be at the same height with the auxiliary electrode 20 and the reference electrode 19 and placed on the upper edge of the detection area, thereby improving the resolution of the atlas.
The following will illustrate the effect of the present invention in-situ nuclear magnetic detection by combining the examples and comparative examples:
in this embodiment, the anti-interference nmr in-situ electrochemical coupling apparatus of the present invention is used in combination with nmr spectroscopy, and compared with the conventional electrochemical workstation and nmr spectroscopy, the above-mentioned steps are performed by using 0.05M p-phenol electrooxidation, the computer and the apparatus are connected, a pipette is used to put 550 μ L of sample into the nmr 26, the solvent is 0.1M sulfuric acid prepared by using D2O containing TMS internal standard, the apparatus is set to be in potentiostatic electrolysis mode, and the voltage is 700mV, the apparatus is put into BRUKER 500MHz nmr spectrometer, shimming and field locking are performed by using the spectrometer self-contained program, and the field locking line is recorded as shown in fig. 8, then electrolysis is performed for one hour, then the spectrometer self-contained Presat pressurized water sequence is used under the power-on condition, the pressurized water site is set, the spectrum width is set to be 10ppm, scanning is performed for 4 times, the experiment time is 48s (waiting time is 8s, sampling time is 4s), obtaining a one-dimensional H1 spectrum, recording the full width at half maximum of the one-dimensional hydrogen spectrum, and recording received electrochemical data; then taking out the device, using a traditional electrochemical workstation with the model of CHI660, connecting the workstation and a three-electrode 7 system by using electric wires, putting the three-electrode 7 system into an in-situ nuclear magnetic tube 26 filled with 550 mu L of 0.05M p-phenol sample, setting the workstation for constant potential electrolysis with the voltage of 700mV, then putting the nuclear magnetic tube 26 into a rotor of a nuclear magnetic resonance spectrometer, putting the nuclear magnetic resonance spectrometer into a self-contained program for full shimming and field locking, recording field locking lines as shown in figure 9, then carrying out electrolysis for one hour, scanning by using the same parameters as the set by a Presat pressurized water sequence to obtain a one-dimensional H1 spectrum, recording electrochemical data of the electrochemical workstation at a computer end, combining two one-dimensional hydrogen spectra into figures 10 and 11 by using MestReNavo software, wherein a gray outline is a spectrum electrolyzed by using the electrochemical workstation, and an internal black outline is a spectrum electrolyzed by using the device, in FIG. 10, 6.86ppm is the product peak, 6.79ppm is the reactant peak, and in FIG. 110 ppm is the peak of internal standard TMS; and the half-height widths of the three peak statistics are made into figure 12; the electrochemical data of the device and the data reading of the electrochemical workstation of the traditional method are made into figure 13.
In the field frequency interlocking system, the flatter the upper part line of a common lock field line, namely fig. 8 and 9, the better the lock field effect and the more stable the magnetic field, and as can be compared by fig. 8 and 9, the interference wave shown by a dotted line square frame in fig. 8 can be introduced by using the traditional wired method for connection, so that the internal magnetic field and the lock field effect of the nuclear magnetic resonance spectrometer are influenced; comparing fig. 10 and fig. 11, it can be easily seen that the line width obtained by wire connection using the conventional electrochemical workstation is larger than the line width obtained by using the apparatus, the resolution of the peak obtained by the experiment of the present invention is higher, and further comparing the data of the full width at half maximum as shown in fig. 12, it can be seen that the full width at half maximum of the peak obtained by using the present invention is only half of that obtained by the conventional method; meanwhile, electrochemical signals acquired by the device are compared, and as can be seen from fig. 13, the electrochemical data obtained by the method is basically consistent with that of the traditional electrochemical workstation, the electrochemical data cannot be influenced by wireless transmission, and the electrochemical performance is reliable.
The flowchart and block diagrams in the figures illustrate the architecture, functionality, and operation of possible implementations of apparatus, methods and computer program products according to various embodiments of the present application. In this regard, each block in the flowchart or block diagrams may represent a module, segment, or portion of code, which comprises one or more executable instructions for implementing the specified logical function(s). It should also be noted that, in some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based devices that perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.
The modules described in the embodiments of the present application may be implemented by software or hardware. The modules described may also be provided in a processor.
In the description of the present application, it is to be understood that the word "comprising" does not exclude the presence of elements or steps not listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims shall not be construed as limiting the scope. The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed.
It will be appreciated by those skilled in the art that the scope of the invention herein disclosed is not limited to the particular combination of features described above, but also encompasses other arrangements formed by any combination of the above features or their equivalents without departing from the spirit of the invention. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. The utility model provides an anti-interference nuclear magnetic resonance normal position electrochemistry allies oneself with device, its characterized in that, including connecting rod, energy supply control assembly and with the three-core shielded wire that energy supply control assembly connects, the inside cavity of connecting rod can hold the three-core shielded wire passes, three copper lines in the three-core shielded wire are connected with reference electrode, working electrode and auxiliary electrode respectively, the end of connecting rod be equipped with coaxial nuclear-magnetism pipe fixed column and the electrode fixed column of connecting rod, the nuclear-magnetism pipe fixed column is used for fixed nuclear-magnetism pipe, reference electrode, working electrode and auxiliary electrode are fixed on the electrode fixed column and in the electrode fixed column with the three-core shielded wire is connected, energy supply control assembly includes control module, data conversion module, current detection module, wireless communication module and power module, data conversion module, power module, The working electrode and the reference electrode are connected with the data conversion module sequentially through the three-core shielding wire and the operational amplifier, the control module is used for calculating a corrected voltage value according to the voltage of the reference electrode and outputting the corrected voltage value to the working electrode, a current path is formed between the working electrode and the auxiliary electrode, the auxiliary electrode is connected with the current detection module and the data conversion module through the three-core shielding wire, and the control module calculates current data according to voltage difference data acquired by the current detection module and sends the current data to a terminal through the wireless communication module.
2. The anti-interference NMR in-situ electrochemical combination apparatus of claim 1, wherein the data conversion module comprises an analog-to-digital converter and a digital-to-analog converter, the working electrode is connected to the digital-to-analog converter, the digital-to-analog converter is configured to convert the corrected voltage value into an analog signal and output the analog signal to the working electrode, the reference electrode is connected to the analog-to-digital converter, the current detection module is connected to the analog-to-digital converter, and the analog-to-digital converter is configured to convert the voltage signal transmitted by the reference electrode and the current signal output by the current detection module into digital signals and transmit the digital signals to the control module.
3. The anti-interference NMR in-situ electrochemical co-usage apparatus according to claim 1, wherein the three-core shielding wires comprise an upper three-core shielding wire and a lower three-core shielding wire, the connecting rod comprises an upper connecting rod and a lower connecting rod, the upper connecting rod and the lower connecting rod respectively accommodate the upper three-core shielding wire and the lower three-core shielding wire to pass through, and the upper connecting rod and the lower connecting rod are connected through threads.
4. The anti-interference NMR in-situ electrochemical combination device according to claim 3, wherein the bottom of the electrode fixing column is provided with a reserved hole for allowing the reference electrode, the working electrode and the auxiliary electrode to pass through.
5. The anti-interference nuclear magnetic resonance in-situ electrochemical combination device according to claim 1, wherein the working electrode is made of a conductive glass material, and the reference electrode and the auxiliary electrode are arranged around the insulating surfaces on the two sides of the working electrode.
6. The anti-interference nuclear magnetic resonance in-situ electrochemical combination device according to claim 3, wherein the nuclear magnetic tube fixing columns and the electrode fixing columns are integrally formed with the lower connecting rod, a gap is formed between the nuclear magnetic tube fixing columns and the electrode fixing columns, a step is formed between the nuclear magnetic tube fixing columns and the lower connecting rod, the nuclear magnetic tubes are formed by coaxially splicing round tubes with different diameters, and a tube wall above the nuclear magnetic tubes can be sleeved in the gap.
7. The anti-jamming nmr in situ electrochemical cell coupling device of claim 3, wherein the power supply control assembly is housed within a housing that is integrally formed with the upper connecting rod.
8. The anti-interference NMR in-situ electrochemical coupling device of claim 1, wherein the wireless communication module is a Bluetooth module, the power supply module comprises a battery module and a charging management module, the charging management module is connected with the battery module and used for controlling charging and discharging of the battery module, and the battery module is connected with the control module to supply power.
9. The anti-interference NMR in-situ electrochemical combination apparatus of claim 1, further comprising a display module connected to the control module for displaying electrochemical data.
10. A method for using the anti-interference nmr in-situ electrochemical apparatus of any one of claims 1-9, comprising the steps of:
1) manufacturing a working electrode, connecting the working electrode, the reference electrode and the auxiliary electrode with a lower three-core shielding wire, and respectively fixing the working electrode, the reference electrode and the auxiliary electrode on an electrode fixing column; the lower three-core shielding wire penetrates out of the lower connecting rod and is connected with the upper three-core shielding wire, the upper three-core shielding wire penetrates out of the upper connecting rod, the upper connecting rod and the lower connecting rod are fixedly connected, and the upper three-core shielding wire is connected with the energy supply control assembly to complete the assembly of the device;
2) placing an electrolyte to be tested in a nuclear magnetic tube, fixing the nuclear magnetic tube in a gap between a nuclear magnetic tube fixing column and an electrode fixing column, inserting the nuclear magnetic tube fixing column into a gauge matched with a nuclear magnetic resonance spectrometer, and adjusting the positions of an auxiliary electrode and a reference electrode to enable the auxiliary electrode and the reference electrode to just reach the upper boundary of a corresponding detection area on the gauge matched with the nuclear magnetic resonance spectrometer;
3) placing the upper connecting rod, the lower connecting rod, the nuclear magnetic tube fixing column, the electrode fixing column and the nuclear magnetic tube into a sample inlet of a nuclear magnetic resonance spectrometer, and fixing the device on the nuclear magnetic resonance spectrometer through a step between the lower connecting rod and the nuclear magnetic tube fixing column;
4) adopt the terminal with energy supply control module carries out wireless connection to transmit the electrochemistry parameter of setting for energy supply control module treats that nuclear magnetic resonance spectrometer's collection parameter sets up the completion back, begins the electrolysis by terminal control to control nuclear magnetic resonance spectrometer and gather the wave spectrum, pass through wireless communication with current data transmission for the terminal after the electrolysis is accomplished.
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