CN114199963A - On-site detection device capable of realizing multiple electrochemical detection methods - Google Patents
On-site detection device capable of realizing multiple electrochemical detection methods Download PDFInfo
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Abstract
The invention relates to a field detection device capable of realizing multiple electrochemical detection methods, which comprises a potentiostat, a screen printing electrode sensor and a mobile terminal, wherein the potentiostat comprises an MCU module, an ADC module, a DAC module, a TIA trans-impedance amplifier module, a voltage follower module, an electrode interface module and a communication module; the MCU module generates voltage excitation waveforms of different electrochemical detections through the DAC module, and then applies the voltage excitation waveforms to the substance to be detected through the sensor to generate response current, and the MCU module samples the response current through the ADC module, so that quantitative judgment of the concentration of the substance to be detected is realized. The device is beneficial to automatically carrying out on-site detection on the substance to be detected based on various electrochemical methods.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to an on-site detection device capable of realizing multiple electrochemical detection methods.
Background
Common electrochemical methods include chronoamperometry, cyclic voltammetry, differential pulse voltammetry, and the like. Chronoamperometry can be used for quantitative analysis of substances. The cyclic voltammetry can be used for judging the modification condition of the electrode surface and can also be used for detecting substances. The differential pulse voltammetry has the advantages of low background current, higher detection sensitivity and lower detection limit, and is very advantageous in the simultaneous detection of various substances. In practical applications, different electrochemical methods are required in different application contexts, and it is also possible that multiple electrochemical methods are required in the same experiment. In the prior art, when the electrochemical method is used for detection, the detection parameter setting is usually manually set, and some devices adopt fixed and unchangeable single detection parameter setting, so that a user cannot set the detection parameter in a personalized manner. The manual setting of electrochemical detection parameters can lead to electrochemical detection that is too cumbersome and inefficient, making detection not simple enough, and a single detection parameter that is fixed and not the same would bring about a lack of device versatility.
Disclosure of Invention
The invention aims to provide an on-site detection device capable of realizing multiple electrochemical detection methods, which is beneficial to automatically carrying out on-site detection on a substance to be detected based on multiple electrochemical methods.
In order to achieve the purpose, the invention adopts the technical scheme that: the constant potential instrument comprises a microcontroller module MCU, an analog-to-digital conversion module ADC, a digital-to-analog conversion module DAC, a TIA transimpedance amplifier module, a voltage follower module, an electrode interface module and a communication module, wherein the MCU module is respectively connected with the ADC module and the DAC module through an SPI bus, the ADC module is connected with the electrode interface module through the TIA transimpedance amplifier module, the DAC module is connected with the electrode interface module through the voltage follower module, the voltage follower module and the electrode interface module form the constant potential module, the electrode interface module is connected with the screen printing electrode sensor, and the MCU module is connected with the communication module and is in data communication with the mobile terminal through the communication module;
the voltage excitation waveform detection device comprises an MCU module, a DAC module, a constant potential module, a TIA transimpedance amplifier module, an ADC module and a power supply module, wherein the MCU module generates voltage excitation waveforms corresponding to different electrochemical detection methods, the DAC module converts voltage excitation waveform digital signals into analog signals and transmits the analog signals to the constant potential module, the constant potential module maintains the stability of voltage excitation waveforms required during electrochemical detection, applies the voltage excitation waveforms to a substance to be detected through a screen printing electrode sensor, the substance to be detected generates an oxidation reduction reaction of electrons on the surface of the sensor and generates a response current, the TIA transimpedance amplifier module converts and amplifies the current to the voltage of the response current, and the ADC module samples the response current so as to realize quantitative judgment of the concentration of the substance to be detected;
before electrochemical detection, the device automatically performs one or even a plurality of times of pre-detection processes with corresponding electrochemical detection methods: under the condition that other detection parameters are determined, the key detection parameters in each detection method are subjected to single-variable optimization automatic adjustment, so that the key detection parameters are subjected to continuous automatic parameter value adjustment in the pre-detection process, and the optimal detection parameter value capable of achieving the optimal detection precision is finally obtained; and when the pre-detection is finished, reserving the optimal detection parameter value for subsequent experimental detection.
Further, the electrochemical detection method includes cyclic voltammetry, differential pulse voltammetry, and time-current curve method.
Further, when cyclic voltammetry detection is carried out, the key detection parameter which is automatically adjusted is the voltage scanning rate; when the differential pulse voltammetry detection is carried out, the key detection parameter which is automatically adjusted is the detection voltage range; when the time-current curve method is used for detection, the key detection parameter which is automatically adjusted is the detection time.
Further, when the cyclic voltammetry detection is performed, the method for automatically adjusting the voltage scanning rate comprises the following steps: when the voltage scanning rate needs to be dynamically adjusted, the adjustment of the voltage scanning rate each time is delta% of the current circuit voltage scanning rate value, wherein the adjustment is a set voltage scanning rate adjustment value.
Further, when the differential pulse voltammetry is detected, the method for automatically adjusting the detection voltage range comprises the following steps: firstly judging whether the detected volt-ampere result belongs to a peak type or a trough type, after the waveform is judged, detecting the substance by using the differential pulse volt-ampere method of which the detected result is the peak type, wherein the detection voltage range is automatically set to be epsilon before and after the peak voltage1Between V, i.e. [ peak voltage-epsilon ]1V-peak voltage + epsilon1V](ii) a For the detection substance with trough-shaped detection result, the detection voltage range is automatically set to epsilon before and after the trough voltage2Between V, i.e. [ trough voltage-epsilon ]2V-trough voltage + epsilon2V](ii) a Wherein the peak voltage and the trough voltage are respectively obtained from the detection voltages corresponding to the peak current maximum and the trough current maximum, and epsilon1、ε2Respectively set peak and trough voltage adjusting values.
Further, when the time-current curve method is used for detection, the method for automatically adjusting the detection time comprises the following steps: and searching the position of a time node where a current stable value appears in the detection volt-ampere result, and automatically determining the range of the detection time according to the position.
Furthermore, the communication module is a Bluetooth module, the MCU module is in data communication with the mobile terminal through a serial port connected with the Bluetooth module, and receives a control command from the mobile terminal, wherein the control command comprises initial settings related to voltage and scanning period; the MCU module is also used for sending the sampled response current data to the mobile terminal through the Bluetooth module, and carrying out data processing through the mobile terminal, thereby realizing quantitative judgment on the concentration of the substance to be detected.
Furthermore, the mobile terminal is a data processing center of the device, and an electrochemical detection program module is arranged on the mobile terminal so as to select various electrochemical detection methods, set parameters, control detection and draw a voltammogram in real time.
Compared with the prior art, the invention has the following beneficial effects: the field detection device can realize the field detection of various electrochemical detection methods, and can cover the electrochemical detection requirements of a wider range of substances. Meanwhile, when the device carries out different electrochemical detection methods, one or even a plurality of times of pre-detection processes can be carried out before the detection is formally started, so that the detection parameters of the detection method are automatically set, the optimal electrochemical detection parameters are automatically matched for the electrochemical detection, and the accuracy, reliability and convenience of the electrochemical detection are improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus according to an embodiment of the present invention;
FIG. 2 is a circuit diagram of the implementation of the modules of the apparatus according to the embodiment of the present invention;
FIG. 3 is a flow chart of the detection of the field test by the mobile terminal according to the embodiment of the present invention;
FIG. 4 is a flow chart of apparatus detection in an embodiment of the present invention;
FIG. 5 is a schematic diagram of a main detection interface of the mobile terminal according to an embodiment of the present invention;
FIG. 6 is a voltage driving waveform diagram of three detection methods according to an embodiment of the present invention.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As shown in fig. 1 and 2, the present embodiment provides an in-situ test device capable of implementing multiple electrochemical test methods, including a potentiostat, a screen-printed electrode sensor and a mobile terminal, the potentiostat comprises a microcontroller module MCU, an analog-to-digital conversion module ADC, a digital-to-analog conversion module DAC, a TIA trans-impedance amplifier module, a voltage follower module, an electrode interface module and a communication module, the MCU module is respectively connected with the ADC module and the DAC module through an SPI bus, the ADC module is connected with the electrode interface module through a TIA trans-impedance amplifier module, the DAC module is connected with the electrode interface module through the voltage follower module, the voltage follower module and the electrode interface module form a constant potential module, the electrode interface module is connected with the screen printing electrode sensor, the MCU module is connected with the communication module, and data communication is carried out between the MCU module and the mobile terminal through the communication module.
The voltage excitation waveform detection device comprises an MCU module, a DAC module, a constant potential module, a screen printing electrode sensor, a TIA transimpedance amplifier module, an ADC module and a power supply module, wherein the MCU module generates voltage excitation waveforms corresponding to different electrochemical detection methods, the DAC module converts voltage excitation waveform digital signals into analog signals and transmits the analog signals to the constant potential module, the constant potential module maintains the stability of voltage excitation waveforms required during electrochemical detection, the voltage excitation waveforms are applied to a substance to be detected through the screen printing electrode sensor, the substance to be detected generates an oxidation reduction reaction of electrons on the surface of the sensor and generates a response current, the TIA transimpedance amplifier module converts and amplifies the current to the voltage of the response current, and the ADC module samples the response current so as to realize quantitative judgment of the concentration of the substance to be detected.
The mobile terminal is a data processing center of the device, and the mobile terminal is provided with an electrochemical detection APP so as to perform selection, parameter setting, detection control and real-time voltammogram drawing of various electrochemical detection methods.
In this embodiment, the communication module is a bluetooth module, the MCU module performs data communication with the mobile terminal through a serial port connected to the bluetooth module, and receives a control command from the mobile terminal, including initial settings related to voltage and scan period; the MCU module is also used for sending the sampled response current data to the mobile terminal through the Bluetooth module, and carrying out data processing through the mobile terminal, thereby realizing quantitative judgment on the concentration of the substance to be detected.
Before electrochemical detection, the device automatically performs one or even a plurality of times of pre-detection processes on the corresponding electrochemical detection method: the key of the pre-detection is that under the condition that other detection parameters are determined, the key detection parameters in each detection method are subjected to single-variable optimized automatic adjustment, so that the key detection parameters can continuously and automatically adjust parameter values in the pre-detection process, and finally the optimal detection parameter values which can achieve the optimal detection precision are obtained; and when the pre-detection is finished, reserving the optimal detection parameter value for subsequent experimental detection. Thereby automatically matching the optimal electrochemical detection parameters for electrochemical detection to improve the accuracy of electrochemical detection.
In this embodiment, the electrochemical detection method includes cyclic voltammetry, differential pulse voltammetry, and time-current curve method. The voltage excitation waveforms for the three detection methods are shown in fig. 6.
When the cyclic voltammetry detection is carried out, the key detection parameter which is automatically adjusted is the voltage scanning rate. The specific method for automatically adjusting the voltage scanning rate comprises the following steps: when the voltage scanning rate needs to be dynamically adjusted, the adjustment of the voltage scanning rate is 10% of the current circuit voltage scanning rate value each time, and the total range of the voltage scanning rate is 1 mV/s-400 mV/s.
When the differential pulse voltammetry detection is carried out, the key detection parameter which is automatically adjusted is the detection voltage range. The specific method for automatically adjusting the detection voltage range comprises the following steps: firstly, judging whether a detection volt-ampere result belongs to a peak type or a trough type, and after the waveform judgment is finished, automatically setting the detection voltage range of a differential pulse volt-ampere method detection substance with the detection result of the peak type to be between 0.4V before and after the peak voltage, namely [ the peak voltage is-0.4V-the peak voltage +0.4V ]; for a detection substance with a trough-shaped detection result, the detection voltage range is automatically set to be between 0.4V before and after the trough voltage, namely [ the trough voltage is-0.4V-the trough voltage +0.4V ]; the peak voltage and the trough voltage are correspondingly taken from the detection voltages corresponding to the peak current maximum and the trough current maximum.
When the time-current curve method is used for detection, the key detection parameter which is automatically adjusted is the detection time. The specific method for automatically adjusting the detection time comprises the following steps: and searching the position of a time node where a current stable value appears in the detection volt-ampere result, and automatically determining the range of the detection time according to the position.
The parameters are key parameters which greatly affect the reliability and the accuracy of the detection result in the corresponding electrochemical detection method, and the reliability and the accuracy of the electrochemical detection result can be improved by properly setting the parameters. The implementation of these parameter auto-adjustments is further described below.
1) Automatic setting of voltage sweep rate in cyclic voltammetry detection
When the device is used for cyclic voltammetry detection, for most electrochemical detection processes conforming to diffusion control, the peak current in the cyclic voltammetry detection process is increased along with the increase of the voltage scanning rate, and the peak current of the detection result is in positive correlation with the voltage scanning rate, so that the problem that the peak current is too large even exceeds the current detection range to generate overrange when the voltage scanning rate is too large is brought, and the peak clipping phenomenon appears in the detection voltammetry result graph; when the voltage scanning rate is too small, the peak current is too small, which is represented as a phenomenon of short and flat detection voltammetry result graph, and is not beneficial to observation of detection results. Therefore, only an appropriate voltage scanning rate can enable the detection result of the cyclic voltammetry to be more accurate and reliable.
The device will therefore invoke a voltage sweep rate auto-adjustment routine before the formal detection of cyclic voltammetry is initiated, which determines the optimal voltage sweep rate parameters by performing one, or even multiple, cyclic voltammetry pre-detection processes. When the voltage scanning rate is too high, the problem of over-range of current detection is easy to occur in electrochemical detection, which is represented as the phenomenon of peak clipping in a detected volt-ampere result graph. The detailed procedure for determining the excessive voltage scan rate and the automatic adjustment scheme are as follows: when the device was carrying out the electrochemistry and is detecting, the constant potential circuit will detect the real-time current data that obtains and send to APP through the bluetooth, and the current data is saved as the data list in APP. Designing an integer variable A in an APP voltage scanning rate automatic regulation program, wherein the integer variable A is used for accumulating the number of current data of which the absolute value of the current data is more than or equal to the upper limit value of a current detection range in a current data list in an electrochemical detection process, and once the number of the variable is more than or equal to a preset threshold B, judging that the voltage scanning rate is too high in the detection process of the cyclic voltammetry, automatically adjusting the voltage scanning rate downwards by a device and immediately and automatically restarting the detection, and also adjusting the peak current in the detection process of the cyclic voltammetry downwards by the reduction of the voltage scanning rate. The adjustment of the voltage scan rate is mainly based on the following program logic: when the voltage scanning rate needs to be dynamically adjusted, the adjustment of the voltage scanning rate is 10% of the current circuit voltage scanning rate value each time, and the total range of the voltage scanning rate is 1 mV/s-400 mV/s.
Meanwhile, when the voltage scanning rate is too low, an automatic regulating mechanism also exists, and when the voltage scanning rate is too low, the phenomenon that the detection voltammetry result graph is short and flat appears is shown, so that the observation of the detection result is not facilitated. The exhaustive voltage scan rate is crossed low and is judged flow and automatic adjustment scheme as follows, and the device is when carrying out the electrochemistry detection, and the constant potential circuit passes through the bluetooth with the real-time current data that obtain of detection and sends to APP, and the current data is saved as the data list in APP. And at the end of the single electrochemical detection, subtracting the current minimum value from the current maximum value in the current data list to obtain a maximum and minimum current difference value. Comparing the maximum and minimum current difference with the current detection range limit value, if the program detects that the maximum and minimum current difference is less than or equal to half of the current detection range limit value, judging that abnormal behavior of too low voltage scanning rate occurs in the detection process, automatically restarting the detection immediately, automatically adjusting the voltage scanning rate by the device while restarting the detection, and adjusting the peak current in the cyclic voltammetry detection process by the increase of the voltage scanning rate. The adjustment of the voltage scan rate is mainly based on the following program logic: when the voltage scanning rate needs to be dynamically adjusted, the adjustment of the voltage scanning rate is 10% of the current circuit voltage scanning rate value each time, and the total range of the voltage scanning rate is 1 mV/s-400 mV/s.
2) Automatic setting of detection voltage range during detection of differential pulse voltammetry
When the device carries out differential pulse voltammetry detection, the detected voltammetry result waveform is usually presented as a peak-shaped detected waveform or a valley-shaped detected waveform, and the voltage position of the peak/trough is relatively fixed, therefore, the proper differential pulse voltammetry detection voltage range is found, the peak/trough position in the detection result can be in the detection voltage setting range, and the proper voltage detection range is set to enable the detection result of the differential pulse voltammetry to be more accurate and reliable.
Therefore, the device calls a voltage detection range automatic regulating program before formal detection of the differential pulse voltammetry is started, and the program determines the optimal voltage detection range parameters through the differential pulse voltammetry pre-detection (wide voltage detection range: 2.047 to + 2.047V) process which is executed once or even for many times. When the voltage detection range parameter is automatically determined, whether the detection result belongs to a wave crest type or a wave trough type is automatically judged through a program, and the voltage detection range is further automatically set after the judgment of the detection waveform type result is finished. The detailed automatic setting flow of the voltage detection range is as follows:
when the device is used for electrochemical detection of the differential pulse voltammetry, a detected voltammetry result graph is usually represented as a detected result curve with an obvious peak or a peak.
When the program is used for carrying out differential pulse voltammetry pre-detection (wide voltage detection range of-2.047 to + 2.047V) for one time or more, the constant potential circuit sends real-time current data obtained by detection to the APP through Bluetooth in the detection process, and the current data is stored in the APP as a data list. After the current data detection result is obtained, the voltage detection range automatic adjustment program firstly judges whether the waveform is of a wave crest type or a wave trough type. Firstly, the peak value and the trough value in a detected volt-ampere result graph must be found out, a sliding window with the length of L (L = 11) is set, the sliding window starts to slide along the waveform, whether the midpoint of the window is larger than the first half data in the window and larger than the second half data in the window is judged each time, if so, the midpoint is recorded, a recorded point set is processed by using a non-maximum suppression algorithm to obtain the final peak current maximum value, and similar processing is used for searching the trough current minimum value. And then averaging the current data, and respectively subtracting the average value of the current data from the peak current maximum value and the trough current minimum value and taking the absolute value. And if the absolute difference value of the current average value and the peak current maximum value is larger, judging that the detected volt-ampere result graph is in a peak type, otherwise, judging that the detected volt-ampere result graph is in a trough type. After the waveform judgment is finished, the detection voltage range of the material is automatically set to be between 0.4V before and after the peak voltage, namely [ the peak voltage is-0.4V to the peak voltage +0.4V ] for the differential pulse voltammetry detection material with the detection result of the peak type. For the detection material with the trough-shaped detection result, the detection voltage range is automatically set to be between 0.4V before and after the trough voltage, namely [ trough voltage minus 0.4V to trough voltage plus 0.4V ]. The peak voltage and the trough voltage are correspondingly taken from the detection voltages corresponding to the peak current maximum and the trough current maximum.
3) Automatic setting of detection time in time-current curve method detection
When the device is used for detecting by a time-current curve method, the detection process of the device usually shows a detection trend that the current is from high to low, then the change of the current value is gradually reduced along with the increase of the detection time, the current value tends to be stable, and the detection waveform is reflected to be similar to a horizontal straight line. When the time current curve method is used for detecting the concentrations of different substances, the current stability values of the detection results are different, and the concentration curve fitting of the substances to be detected is carried out by using the current stability values, so that the method can be used for electrochemical quantitative detection of the substances. Therefore, finding a suitable detection time range of the time-current curve method enables the detection current value in the detection result to reach a stable value, but the detection speed is not influenced by too long time. The detection result of the time-current curve detection method can be more accurate, reliable and rapid only by setting a proper detection time range.
Therefore, the device calls a detection time range automatic adjusting program before formal detection of the time-current curve detection method is started, and the program determines the optimal detection time range parameter through the process of executing one-time or even multiple times of time-current curve detection method pre-detection (pre-detecting the minimum detection time length for 1 minute, then automatically increasing the detection time length according to the intensity of the current change condition and the indefinite time length). When the detection time range parameter is automatically determined, whether the current detection result tends to be stable or not is automatically determined by a program. The detailed automatic detection time range setting process is as follows:
when the device is used for electrochemical detection of a time current curve detection method, a detected volt-ampere result graph of the device is usually represented as a detection result curve with a current value obviously reduced, then, the current value tends to be stable along with the increase of detection time, the detected volt-ampere result graph is represented as a horizontal detection curve with the detection curve tending to be stable on a detection waveform, and the obtained current detection value is a stable value and can be used for calculating the concentration of a substance. The automatic adjustment of the detection time range of the time-current curve detection method mainly comprises the steps of finding the position of a time node where a current stable value appears in a detection volt-ampere result, and automatically determining the detection time range according to the position.
When the program is executed once or even for multiple times, the time-current curve detection method is used for pre-detecting (the minimum detection time is pre-detected for 1 minute, then the detection time is automatically increased according to the intensity of the current change condition and the indefinite time), the constant potential circuit sends real-time current data obtained by detection to the APP through Bluetooth in the detection process, and the current data are stored in the APP as a data list. After the current data detection result exists, the detection time range automatic regulating program firstly carries out standard deviation (RSD) solution on 20 bits of data at the tail end of the detected current data, and accumulates the detection time length according to a formula (RSD multiplied by 300+30 s) according to the standard deviation evaluation result, namely the larger the standard deviation is, the larger the time length required to be increased is until the calculated value of the standard deviation of the detected current data which is not 20 bits is less than 1%. At the moment, the automatic detection time range adjusting program automatically sets the current detection time length as the detection time length of the time-current curve detection method.
The specific detection process for carrying out field detection by utilizing the device comprises the following steps:
first, the potentiostat of the device is powered up. Opening an electrochemical detection APP in the mobile terminal, selecting an electrochemical detection method of a target on a home page of the APP, and entering an electrochemical detection interface after clicking confirmation. The upper half part of the detection interface is a voltammogram curve display window, and after detection is finished, detection data can be displayed below the window; the lower half part of the detection interface is a parameter setting part, different electrochemical methods are adopted, and parameters needing to be set in the detection interface are different. After entering the detection interface, firstly clicking a Bluetooth connection button, and connecting the mobile terminal with the potentiostat through Bluetooth. And then setting parameters of the detection method, such as initial potential, terminal potential, potential increment and the like, sending working parameters to the potentiostat by the APP after clicking confirmation and starting detection, receiving voltage and current data returned by the potentiostat circuit by the APP, and drawing a voltammogram graph in real time. After the detection, the detection data are displayed below the voltammogram. Meanwhile, a 'view data' button can be clicked to view historical detection data. And finally, disconnecting the Bluetooth connection and quitting the APP. Fig. 3 is a detection flow chart of electrochemical detection APP on a mobile terminal. Fig. 4 is a corresponding apparatus detection flow chart.
Fig. 5 is a schematic diagram of a main detection interface of electrochemical detection APP on a mobile terminal, where: (a) a method selection interface; (b) cyclic voltammetry; (c) differential pulse voltammetry; (d) a chronoamperometry; (e) and (6) linearly fitting a curve. Voltammograms plotted on the detection interface are all detection results in a 5mM potassium ferricyanide/potassium ferrocyanide aqueous solution.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. An on-site detection device capable of realizing multiple electrochemical detection methods is characterized by comprising a potentiostat, a screen printing electrode sensor and a mobile terminal, the potentiostat comprises a microcontroller module MCU, an analog-to-digital conversion module ADC, a digital-to-analog conversion module DAC, a TIA trans-impedance amplifier module, a voltage follower module, an electrode interface module and a communication module, the MCU module is respectively connected with the ADC module and the DAC module through an SPI bus, the ADC module is connected with the electrode interface module through a TIA trans-impedance amplifier module, the DAC module is connected with the electrode interface module through the voltage follower module, the voltage follower module and the electrode interface module form a constant potential module, the electrode interface module is connected with the screen printing electrode sensor, the MCU module is connected with the communication module and is in data communication with the mobile terminal through the communication module;
the voltage excitation waveform detection device comprises an MCU module, a DAC module, a constant potential module, a TIA transimpedance amplifier module, an ADC module and a power supply module, wherein the MCU module generates voltage excitation waveforms corresponding to different electrochemical detection methods, the DAC module converts voltage excitation waveform digital signals into analog signals and transmits the analog signals to the constant potential module, the constant potential module maintains the stability of voltage excitation waveforms required during electrochemical detection, applies the voltage excitation waveforms to a substance to be detected through a screen printing electrode sensor, the substance to be detected generates an oxidation reduction reaction of electrons on the surface of the sensor and generates a response current, the TIA transimpedance amplifier module converts and amplifies the current to the voltage of the response current, and the ADC module samples the response current so as to realize quantitative judgment of the concentration of the substance to be detected;
before electrochemical detection, the device automatically performs one or even a plurality of times of pre-detection processes with corresponding electrochemical detection methods: under the condition that other detection parameters are determined, the key detection parameters in each detection method are subjected to single-variable optimization automatic adjustment, so that the key detection parameters are subjected to continuous automatic parameter value adjustment in the pre-detection process, and the optimal detection parameter value capable of achieving the optimal detection precision is finally obtained; and when the pre-detection is finished, reserving the optimal detection parameter value for subsequent experimental detection.
2. The in-situ test device of claim 1, wherein the electrochemical test method comprises cyclic voltammetry, differential pulsed voltammetry, and time-current curve method.
3. The in-situ test device capable of implementing multiple electrochemical test methods as claimed in claim 2, wherein the key test parameter for automatic adjustment is voltage scan rate when performing cyclic voltammetry test; when the differential pulse voltammetry detection is carried out, the key detection parameter which is automatically adjusted is the detection voltage range; when the time-current curve method is used for detection, the key detection parameter which is automatically adjusted is the detection time.
4. The in-situ testing device capable of implementing multiple electrochemical testing methods according to claim 3, wherein the voltage sweep rate is automatically adjusted by performing cyclic voltammetry testing by: when the voltage scanning rate needs to be dynamically adjusted, the adjustment of the voltage scanning rate each time is delta% of the current circuit voltage scanning rate value, wherein the adjustment is a set voltage scanning rate adjustment value.
5. The on-site detection device capable of realizing multiple electrochemical detection methods according to claim 3, wherein when performing differential pulse voltammetry detection, the method for automatically adjusting the detection voltage range comprises: firstly judging whether the detected volt-ampere result belongs to a peak type or a trough type, after the waveform is judged, detecting the substance by using the differential pulse volt-ampere method of which the detected result is the peak type, wherein the detection voltage range is automatically set to be epsilon before and after the peak voltage1Between V, i.e. [ peak voltage-epsilon ]1V-peak voltage + epsilon1V](ii) a For the detection substance with trough-shaped detection result, the detection voltage range is automatically set to epsilon before and after the trough voltage2Between V, i.e. [ trough voltage-epsilon ]2V-trough voltage + epsilon2V](ii) a Wherein the peak voltage and the trough voltage are respectively obtained from the detection voltages corresponding to the peak current maximum and the trough current maximum, and epsilon1、ε2Respectively set peak and trough voltage adjusting values.
6. The on-site detection device capable of realizing multiple electrochemical detection methods according to claim 3, wherein when the time-current curve method is used for detection, the method for automatically adjusting the detection time comprises the following steps: and searching the position of a time node where a current stable value appears in the detection volt-ampere result, and automatically determining the range of the detection time according to the position.
7. The in-situ testing device capable of implementing multiple electrochemical testing methods as claimed in claim 1, wherein said communication module is a bluetooth module, said MCU module performs data communication with the mobile terminal through a serial port connected to the bluetooth module, and receives control commands from the mobile terminal, including initial settings related to voltage and scan period; the MCU module is also used for sending the sampled response current data to the mobile terminal through the Bluetooth module, and carrying out data processing through the mobile terminal, thereby realizing quantitative judgment on the concentration of the substance to be detected.
8. The on-site detection device capable of realizing multiple electrochemical detection methods according to claim 1, wherein the mobile terminal is a data processing center of the device, and the mobile terminal is provided with an electrochemical detection program module for selection, parameter setting, detection control and real-time voltammogram drawing of multiple electrochemical detection methods.
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