Detection system and method based on photoelectrochemistry

Abstract

The invention provides a detection system and method based on photoelectrochemistry, and the method comprises the steps: carrying out the self-correlation detection of an initial photocurrent signal, obtaining a photocurrent self-detection correlation coefficient, carrying out the differential correlation detection of a low-frequency oscillation photocurrent signal segment set, and obtaining a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-inspection correlation coefficient, performing photocurrent increment feature extraction on the low-frequency oscillation photocurrent signal segment set by the oscillation frequency period to obtain a photocurrent increment feature; performing signal correction on the initial light current signal according to the light current increment characteristics to obtain a light current detection signal; the photocurrent detection signal is subjected to signal analysis to obtain a photoelectrochemical detection result, and the detection photocurrent can be subjected to signal correction according to the photocurrent increment characteristics in the low-frequency oscillation period, so that the random environment interference on the photocurrent signal is reduced, and the accuracy of the photoelectrochemical detection result is improved.

Description

Technical Field

[0001] The present application relates to the field of photoelectrochemical detection technology, and more specifically, to a detection system and method based on photoelectrochemistry. Background Art

[0002] The photoelectrochemical detection system is a device system that combines optical and electrochemical technologies to detect and analyze specific substances. This system uses the principle that the photogenerated charge of the photoelectric response material can trigger the redox chemical reaction of the substance to be detected under light excitation, and the redox chemical reaction will cause the corresponding photocurrent signal on the photoelectrochemical electrode to change. The photocurrent signal generated in the electrochemical reaction is measured by electrodes in electrolyte chemical solutions to analyze the properties or concentration of the target substance. It has the characteristics of high detection sensitivity and strong detection selectivity. Therefore, the photoelectrochemical detection system is widely used in environmental monitoring, biosensing, materials science and new energy fields.

[0003] In the process of photoelectrochemical detection, it is necessary to remove the interference factors in the detection process. The existing photoelectrochemical detection method mainly detects the dark current of the photoelectrochemical electrode and eliminates the dark current in the final photocurrent signal to reduce background interference. However, this method is difficult to eliminate the interference caused by factors such as electromagnetic radiation and temperature changes in the detection environment, which greatly affects the accuracy of photoelectrochemical detection. Therefore, how to reduce the interference of environmental factors on the photocurrent signal during photoelectrochemical detection has become an urgent problem to be solved. Summary of the invention

[0004] The present application provides a detection system and method based on photoelectrochemistry, which can perform signal correction on the detected photocurrent according to the photocurrent increment characteristics under the low-frequency oscillation period, thereby reducing the random environmental interference of the photocurrent signal and improving the accuracy of the photoelectrochemical detection results.

[0005] In a first aspect, the present application provides a method for processing photoelectrochemical detection signals, which may be executed by a network device, or may be executed by a chip configured in the network device, and the present application does not limit this.

[0006] Specifically, the method includes:

[0007] Collecting photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal;

[0008] Re-collecting and segmenting the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments;

[0009] Performing an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and performing a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient;

[0010] When the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment feature extraction is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period to obtain the photocurrent increment feature;

[0011] The initial photocurrent signal is corrected according to the photocurrent increment characteristic to obtain a photocurrent detection signal; and the photocurrent detection signal is analyzed to obtain a photoelectrochemical detection result.

[0012] In combination with the first aspect, in certain implementations of the first aspect, collecting photocurrent from a photoelectrochemical electrode in an electrolyte chemical solution to obtain an initial photocurrent signal specifically includes:

[0013] Combining a photosensitive material with a conductive material to form a photoelectrochemical electrode;

[0014] After the target to be detected is introduced into the detection area, the photoelectrochemical electrode is irradiated with a light source of a preset wavelength;

[0015] The photocurrent generated by the photoelectrochemical electrode under light is recorded by an electrochemical workstation to obtain an initial photocurrent signal.

[0016] In combination with the first aspect, in certain implementations of the first aspect, a 0.1 mol sodium sulfate solution is used as the electrolyte chemical solution.

[0017] In combination with the first aspect, in certain implementations of the first aspect, re-collecting and segmenting the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in the low-frequency oscillation mode to obtain the low-frequency oscillation photocurrent signal segment set specifically includes:

[0018] Obtaining a preset oscillation frequency period;

[0019] Collecting a photocurrent signal in a low-frequency oscillation mode, and performing time-series segmentation on the photocurrent signal in the low-frequency oscillation mode according to the oscillation frequency period to obtain a plurality of low-frequency oscillation photocurrent signal segments;

[0020] The low-frequency oscillation photocurrent signal segment set is composed of a plurality of low-frequency oscillation photocurrent signal segments.

[0021] In combination with the first aspect, in certain implementations of the first aspect, performing an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient specifically includes:

[0022] Obtaining a preset oscillation frequency period;

[0023] Performing time-series segmentation on the initial photocurrent signal based on a preset oscillation frequency period to obtain a plurality of initial photocurrent related signals;

[0024] A cross-correlation test is performed on multiple initial photocurrent related signals to obtain the photocurrent self-test correlation coefficient.

[0025] In combination with the first aspect, in certain implementations of the first aspect, when the photocurrent oscillation correlation coefficient is lower than the photocurrent self-detection correlation coefficient, an initial photocurrent signal is acquired, and a signal analysis is performed based on the initial photocurrent signal to obtain a photoelectrochemical detection result.

[0026] In combination with the first aspect, in certain implementations of the first aspect, extracting photocurrent increment features from a set of low-frequency oscillation photocurrent signal segments using the oscillation frequency period to obtain the photocurrent increment features specifically includes:

[0027] Combining the low-frequency oscillation photocurrent signal segments in the low-frequency oscillation photocurrent signal segment set based on the time sequence to obtain a low-frequency oscillation photocurrent signal;

[0028] Acquiring an oscillation frequency period and an oscillation frequency gain of the low-frequency oscillation mode, and performing a hysteresis analysis on the low-frequency oscillation photocurrent signal according to the oscillation frequency period and the oscillation frequency gain to obtain a photocurrent increment signal;

[0029] A photocurrent increment feature is extracted from the photocurrent increment signal to obtain a photocurrent increment feature.

[0030] In a second aspect, the present application provides a detection system based on photoelectrochemistry, which includes a photoelectrochemical detection signal processing unit, and the photoelectrochemical detection signal processing unit includes:

[0031] A collection module, used for collecting photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal;

[0032] The acquisition module is further used to re-acquire and segment the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments;

[0033] A processing module, configured to perform an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and perform a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to an oscillation frequency period and an oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient;

[0034] The processing module is further configured to extract photocurrent increment features from a set of low-frequency oscillation photocurrent signal segments according to the oscillation frequency period to obtain photocurrent increment features when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient;

[0035] The execution module is used to perform signal correction on the initial photocurrent signal according to the photocurrent increment characteristic to obtain a photocurrent detection signal; and perform signal analysis on the photocurrent detection signal to obtain a photoelectrochemical detection result.

[0036] In a third aspect, the present application provides a computer terminal device, comprising a memory and a processor, wherein the memory stores a code, and the processor is configured to obtain the code and execute the above-mentioned photoelectrochemical detection signal processing method.

[0037] In a fourth aspect, the present application provides a computer-readable storage medium, wherein the computer-readable storage medium stores at least one computer program, and the computer program is loaded and executed by a processor to implement the operations performed by the above-mentioned photoelectrochemical detection signal processing method.

[0038] The technical solution provided by the embodiments disclosed in this application has the following beneficial effects:

[0039] In a detection system and method based on photoelectrochemistry provided by the present application, first, photocurrent is collected from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal; the photocurrent is collected and segmented from the photoelectrochemical electrode in the electrolyte chemical solution again in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments; an autocorrelation test is performed on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and a differential correlation test is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment feature extraction is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period to obtain a photocurrent increment feature; signal correction is performed on the initial photocurrent signal according to the photocurrent increment feature to obtain a photocurrent detection signal; and signal analysis is performed on the photocurrent detection signal to obtain a photoelectrochemical detection result.

[0040] It can be seen that in this application, by analyzing the photocurrent signal within the oscillation frequency period, the signal extraction using the low-frequency oscillation period can effectively distinguish the real periodic signal caused by the photoelectrochemical reaction from the environmental random noise, which helps to remove the noise component from the photocurrent signal and retain the effective signal. The autocorrelation test of the initial photocurrent signal can identify its internal correlation and obtain the photocurrent self-test correlation coefficient. This coefficient is used as a benchmark to reflect the stability of the signal in the absence of external oscillation. The photocurrent signal in the low-frequency oscillation mode is subjected to differential processing and correlation test, and the obtained oscillation correlation coefficient reflects the change characteristics of the signal under periodic disturbance. If the photocurrent oscillation correlation coefficient is higher than the self-test correlation coefficient, it indicates that the signal change in the oscillation mode is more due to the reaction change caused by the oscillation rather than the random fluctuation caused by environmental noise. Then, the effective change characteristics are extracted through the photocurrent increment signal within the oscillation period, and the initial photocurrent signal is corrected using the photocurrent increment characteristics. This can effectively reduce the interference of random environmental factors on the signal, thereby improving the accuracy of the detection signal. In summary, the present application can perform signal correction on the detected photocurrent according to the photocurrent increment characteristics under the low-frequency oscillation period, thereby reducing the random environmental interference on the photocurrent signal and improving the accuracy of the photoelectrochemical detection results. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is an exemplary flow chart of a photoelectrochemical detection signal processing method according to some embodiments of the present application;

[0042] Figure 2 is an exemplary flow chart for obtaining a photocurrent self-test correlation coefficient in some embodiments of the present application;

[0043] Figure 3 is a schematic diagram of exemplary hardware and / or software of a photoelectrochemical detection signal processing unit according to some embodiments of the present application;

[0044] Figure 4 It is a structural schematic diagram of a computer terminal device for implementing a photoelectrochemical detection signal processing method according to some embodiments of the present application. DETAILED DESCRIPTION

[0045] The present application first collects photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal; re-collects and segments the photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments; performs an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and performs a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, extracts photocurrent increment features from the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period to obtain a photocurrent increment feature; performs signal correction on the initial photocurrent signal according to the photocurrent increment feature to obtain a photocurrent detection signal; performs signal analysis on the photocurrent detection signal to obtain a photoelectrochemical detection result, and can perform signal correction on the detected photocurrent according to the photocurrent increment feature under the low-frequency oscillation period, thereby reducing random environmental interference on the photocurrent signal and improving the accuracy of the photoelectrochemical detection result.

[0046] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods. Figure 1 , which is an exemplary flow chart of a photoelectrochemical detection signal processing method according to some embodiments of the present application. The photoelectrochemical detection signal processing method 100 mainly includes the following steps:

[0047] In step S101, photocurrent is collected from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal.

[0048] It should be noted that the initial photocurrent signal is a photocurrent signal collected on a photoelectrochemical electrode when performing photoelectrochemical detection on a target to be detected. Optionally, in some embodiments, collecting the initial photocurrent signal may be achieved by the following steps:

[0049] Combine photosensitive materials (such as semiconductor materials TiO2, ZnO, etc.) with conductive materials to form photoelectrochemical electrodes;

[0050] During the detection process, an appropriate electrolyte chemical solution is selected as the detection medium. In specific implementation, a 0.1 mol sodium sulfate solution can be used as the electrolyte chemical solution. Alternatively, the pH value, ionic strength and other parameters of the electrolyte chemical solution can be selected according to the material characteristics of the detection target for detection medium selection, which will not be elaborated here.

[0051] Introducing the target to be detected into the detection system, the target to be detected in this application can be any liquid, gas or solid to be detected;

[0052] irradiating the photoelectrochemical electrode with a light source of a preset wavelength;

[0053] The photocurrent generated by the photoelectrochemical electrode under light is recorded by an electrochemical workstation to obtain the initial photocurrent signal.

[0054] Optionally, in some embodiments, after collecting photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution and obtaining the initial photocurrent signal, the method further includes: amplifying the initial photocurrent signal; in specific implementation, a transimpedance amplifier may be used to amplify the initial photocurrent signal. In some other embodiments, other devices or equipment capable of signal amplification may also be used, which is not limited here.

[0055] Optionally, in some embodiments, a 0.1 mol sodium sulfate solution is used as the electrolyte chemical solution.

[0056] In step S102, the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is collected and segmented again in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments.

[0057] It should be noted that the low-frequency oscillation mode is a working mode of the photoelectrochemical-based detection system. In this working mode, low-frequency oscillation is applied to the electrolyte chemical solution to generate regular mechanical movement inside the solution. In specific implementation, the electrolyte chemical solution can be oscillated by a vibrating rod or other vibration device to increase the contact area between the high-concentration electrolyte chemical solution and the photoelectrochemical electrode, thereby increasing the photoelectrochemical reaction rate to a certain extent. In addition, the shear stress and friction of the electrolyte chemical solution in the oscillation mode will also cause the local temperature of the electrode surface to increase. The temperature increase will increase the thermal energy of electrons and holes, and increase the probability of electrons jumping from the valence band to the conduction band, thereby increasing the generation rate of electron-hole pairs (i.e., the photoelectrochemical reaction rate increases), thereby increasing the amplitude of the photocurrent signal. In addition, in some embodiments, titanium dioxide (TiO2) can be used as the photosensitive material of the photoelectrochemical electrode. The increase in surface temperature will increase the conductivity of titanium dioxide, and help activate the catalytic sites on its surface, enhance the photocatalytic activity, and increase the amplitude of the photocurrent signal.

[0058] Optionally, in some embodiments, the photoelectrochemical-based detection system controls the vibration device according to a frequency control signal loaded in the vibration device control chip, and the fixed parameters of the frequency control signal include: initial oscillation frequency, oscillation frequency gain and oscillation frequency period; wherein, the initial oscillation frequency is the starting frequency of the vibration device, that is, the initial vibration frequency set when the vibration device starts working; the oscillation frequency gain is the frequency value increased each time the vibration device performs periodic frequency increase, that is, the increment each time the vibration device periodically increases the vibration frequency; the oscillation frequency period is the cycle time each time the periodic frequency increase is performed, that is, the time interval of each frequency increase; in specific implementation, the initial oscillation frequency, oscillation frequency gain and oscillation frequency period can be calibrated through multiple experiments, and the initial oscillation frequency, oscillation frequency gain and oscillation frequency period when the amplitude of the photocurrent signal changes greatly are selected, thereby improving the signal differential characteristics when the photocurrent signal changes.

[0059] Optionally, in some embodiments, the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is collected and segmented again in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments, which can be achieved by the following steps:

[0060] Obtaining a preset oscillation frequency period;

[0061] Collecting a photocurrent signal in a low-frequency oscillation mode, and performing time-series segmentation on the photocurrent signal in the low-frequency oscillation mode according to the oscillation frequency period to obtain a plurality of low-frequency oscillation photocurrent signal segments;

[0062] The low-frequency oscillation photocurrent signal segment set is composed of a plurality of low-frequency oscillation photocurrent signal segments.

[0063] In specific implementation, the time segmentation of the photocurrent signal in the low-frequency oscillation mode according to the oscillation frequency period can be achieved by the following steps: using the oscillation frequency period as the segmentation period, segmenting the photocurrent signal in the low-frequency oscillation mode, and obtaining multiple low-frequency oscillation photocurrent signal segments.

[0064] In step S103, an autocorrelation test is performed on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and a differential correlation test is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient.

[0065] It should be noted that the photocurrent self-test correlation coefficient in the present application represents the degree of autocorrelation of the initial photocurrent signal. The larger the photocurrent self-test correlation coefficient, the more stable the initial photocurrent signal, the less interference the signal has, and the higher the credibility of the signal. The photocurrent self-test correlation coefficient is determined by the autocorrelation of the initial photocurrent signal. Optionally, in some embodiments, reference Figure 2 As shown, this figure is an exemplary flow chart of obtaining the photocurrent self-test correlation coefficient in some embodiments of the present application. The initial photocurrent signal is subjected to an autocorrelation test to obtain the photocurrent self-test correlation coefficient, which can be achieved by using the following steps:

[0066] In step S1031, a preset oscillation frequency period is obtained;

[0067] In step S1032, the initial photocurrent signal is time-sequence segmented based on a preset oscillation frequency period to obtain a plurality of initial photocurrent related signals;

[0068] In step S1033, a cross-correlation test is performed on a plurality of initial photocurrent related signals to obtain a photocurrent self-test correlation coefficient.

[0069] In a specific implementation, during the process of performing cross-correlation test on multiple initial photocurrent related signals to obtain the photocurrent self-test correlation coefficient, the average value of the Pearson correlation coefficients between the multiple initial photocurrent related signals can be used as the photocurrent self-test correlation coefficient.

[0070] It should be noted that the photocurrent oscillation correlation coefficient described in the present application represents the correlation degree of the photocurrent signal change increment in the low-frequency oscillation mode. The larger the photocurrent oscillation correlation coefficient, the more stable the photocurrent signal change increment, the less the signal is interfered, and the higher the credibility of the signal. The photocurrent oscillation correlation coefficient is determined based on the correlation degree of the photocurrent signal change increment in different oscillation frequency periods. Optionally, in some embodiments, according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode, a differential correlation test is performed on the low-frequency oscillation photocurrent signal segment set, and the photocurrent oscillation correlation coefficient can be obtained by the following steps:

[0071] Performing differential processing on each low-frequency oscillation photocurrent signal segment in the low-frequency oscillation photocurrent signal segment set to obtain a plurality of oscillation differential signal segments;

[0072] Acquire the oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode, and determine the oscillation mode calibration coefficient according to the oscillation frequency period and the oscillation frequency gain;

[0073] Based on the oscillation mode calibration coefficient, a differential correlation test is performed on all oscillation differential signal segments to obtain a photocurrent oscillation correlation coefficient.

[0074] In a specific implementation, in the process of determining the oscillation mode calibration coefficient according to the oscillation frequency period and the oscillation frequency gain, the oscillation mode calibration coefficient can be mapped from the interval range corresponding to the oscillation frequency period and the oscillation frequency gain according to a preset mapping table. Generally speaking, the smaller the oscillation frequency period and the larger the oscillation frequency gain, the larger the oscillation mode calibration coefficient.

[0075] Optionally, in some embodiments, the oscillation mode calibration coefficient = a calibrated proportional coefficient × the oscillation frequency gain / the oscillation frequency period, wherein the calibrated proportional coefficient is used to normalize the oscillation mode calibration coefficient, and the proportional coefficient can be calibrated through multiple tests.

[0076] Optionally, in some embodiments, performing a differential correlation test on all oscillation differential signal segments based on the oscillation mode calibration coefficient to obtain the photocurrent oscillation correlation coefficient may be implemented by the following steps:

[0077] Obtaining the signal mean values ​​corresponding to each oscillation differential signal segment;

[0078] For each oscillation differential signal segment, scaling the signal based on the corresponding signal mean according to the oscillation mode calibration coefficient to obtain the corresponding oscillation related signal segment;

[0079] Based on the cross-correlation test of all oscillation-related signal segments, the photocurrent oscillation correlation coefficient is obtained.

[0080] Among them, the oscillation-related signal segment can be determined according to the following formula:

[0081]

[0082] in, is the i-th oscillation-related signal segment, S i is the i-th oscillation differential signal segment, μ i is the signal mean corresponding to the i-th oscillation differential signal segment, and K is the oscillation mode calibration coefficient.

[0083] Optionally, in some embodiments, in the process of performing cross-correlation test based on all oscillation-related signal segments to obtain the photocurrent oscillation correlation coefficient, the average of the Pearson correlation coefficients between multiple oscillation differential signal segments can be used as the photocurrent oscillation correlation coefficient.

[0084] Optionally, in some embodiments, in the process of performing differential processing on each low-frequency oscillation photocurrent signal segment in the low-frequency oscillation photocurrent signal segment set to obtain multiple oscillation differential signal segments, the low-frequency oscillation photocurrent signal segment set can be regarded as a two-dimensional array, each row of the array is a separate low-frequency oscillation photocurrent signal segment, and each low-frequency oscillation photocurrent signal segment can be subtracted from the array same-bit data in the adjacent previous low-frequency oscillation photocurrent signal segment to obtain multiple oscillation differential signal segments. For example, when the oscillation frequency period is 1 second and the number of signal points collected in each oscillation frequency period is 1000, each low-frequency oscillation photocurrent signal segment is an array with a length of 1000, and the oscillation differential signal segment corresponding to the low-frequency oscillation photocurrent signal segment can be obtained by subtracting the array same-bit data in the adjacent previous low-frequency oscillation photocurrent signal segment.

[0085] In step S104, when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment feature extraction is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period to obtain photocurrent increment feature.

[0086] It should be noted that the autocorrelation test of the initial photocurrent signal can identify its internal similarity or consistency and obtain the photocurrent self-test correlation coefficient; this coefficient, as a benchmark, reflects the stability of the signal in the absence of external oscillation; and the photocurrent signal in the low-frequency oscillation mode is subjected to differential processing and correlation test, and the oscillation correlation coefficient obtained reflects the changing characteristics of the signal under periodic disturbance; if the photocurrent oscillation correlation coefficient is higher than the self-test correlation coefficient, it indicates that the signal change in the oscillation mode is more due to the reaction change caused by the oscillation, rather than the random fluctuation caused by environmental noise. At this time, the signal stability of the initial photocurrent signal is affected by external interference, and its signal credibility is lower than the signal increment of the photocurrent signal in the low-frequency oscillation mode. It is difficult to obtain accurate detection results by performing signal analysis on the initial photocurrent signal, and there is a partial signal increment in the photocurrent signal in the low-frequency oscillation mode. This partial signal increment is obtained by periodically increasing the photoelectrochemical reaction rate, and is therefore less affected by environmental factors. It is necessary to perform photocurrent increment feature extraction based on the photocurrent signal in the low-frequency oscillation mode for photoelectrochemical signal correction, thereby increasing the accuracy of the photoelectrochemical detection results.

[0087] Optionally, in some embodiments, when the photocurrent oscillation correlation coefficient is lower than the photocurrent self-detection correlation coefficient, an initial photocurrent signal is acquired, and a signal analysis is performed based on the initial photocurrent signal to obtain a photoelectrochemical detection result.

[0088] It should be noted that the photocurrent increment feature described in the present application is an incremental feature signal obtained after feature extraction based on the photocurrent signal increment in the low-frequency oscillation mode. Signal correction of the initial photocurrent signal based on the photocurrent increment feature can reduce environmental interference in the initial photocurrent signal and improve the accuracy of the photoelectrochemical detection results. Optionally, in some embodiments, the photocurrent increment feature is extracted from the low-frequency oscillation photocurrent signal segment set based on the oscillation frequency period, and the photocurrent increment feature can be obtained by the following steps:

[0089] Combining the low-frequency oscillation photocurrent signal segments in the low-frequency oscillation photocurrent signal segment set based on the time sequence to obtain a low-frequency oscillation photocurrent signal;

[0090] Acquiring an oscillation frequency period and an oscillation frequency gain of the low-frequency oscillation mode, and performing a hysteresis analysis on the low-frequency oscillation photocurrent signal according to the oscillation frequency period and the oscillation frequency gain to obtain a photocurrent increment signal;

[0091] A photocurrent increment feature is extracted from the photocurrent increment signal to obtain a photocurrent increment feature.

[0092] Optionally, in some embodiments, when the low-frequency oscillation photocurrent signal segment set is divided, each low-frequency oscillation photocurrent signal segment has a unique timing identifier, and signals can be combined according to the unique identifiers corresponding to the low-frequency oscillation photocurrent signal segments to obtain the low-frequency oscillation photocurrent signal.

[0093] Preferably, in some embodiments, the hysteresis analysis of the low-frequency oscillation photocurrent signal is performed according to the oscillation frequency period and the oscillation frequency gain to obtain the photocurrent increment signal, which can be achieved by the following steps:

[0094] The low-frequency oscillation photocurrent signal is subjected to signal differential hysteresis according to the oscillation frequency period to obtain a transition signal, and then the transition signal is subjected to signal scaling according to the oscillation frequency gain to obtain the photocurrent increment signal.

[0095] In specific implementation, a time delay equal to the oscillation frequency cycle time can be introduced into the low-frequency oscillation photocurrent signal to obtain a delayed signal, and the differential signal between the low-frequency oscillation photocurrent signal and the delayed signal is used as a transition signal. Then, the transition signal can be linearly scaled according to the ratio of the oscillation frequency gain to the preset standard gain as a proportional coefficient to obtain a final photocurrent increment signal, which is the photocurrent signal increment caused by the low-frequency oscillation mode.

[0096] Preferably, in some embodiments, photocurrent increment feature extraction is performed on the photocurrent increment signal, and obtaining the photocurrent increment feature can be achieved by the following steps: performing empirical mode decomposition on the photocurrent increment signal to obtain the intrinsic mode function of the photocurrent increment signal as the photocurrent increment feature. It should be noted that by performing photocurrent increment feature extraction on the photocurrent increment signal, the smoothness of the photocurrent signal can be increased and the accuracy of the photoelectrochemical detection results can be improved.

[0097] In step S104, the initial photocurrent signal is corrected according to the photocurrent increment characteristic to obtain a photocurrent detection signal; and the photocurrent detection signal is analyzed to obtain a photoelectrochemical detection result.

[0098] When the photocurrent oscillation correlation coefficient is higher than the self-test correlation coefficient, it means that the signal fluctuation is mainly related to the oscillation. The effective change part can be extracted through the photocurrent increment signal within the oscillation period. This part of the incremental signal represents the real reaction dynamics of the photoelectrochemical reaction within the oscillation period, and can reflect more accurate photoelectrochemical reaction characteristics. Using these incremental signals to correct the initial photocurrent signal can effectively reduce the interference of random environmental factors on the signal, thereby improving the accuracy of the detection signal.

[0099] Optionally, in some embodiments, the initial photocurrent signal is corrected according to the photocurrent increment characteristic to obtain a photocurrent detection signal, which can be achieved by using the following steps:

[0100] Extracting cross-correlation features of the initial photocurrent signal according to the photocurrent increment feature to obtain a cross-correlation feature signal segment of the photocurrent increment feature and the initial photocurrent signal;

[0101] The signal mean of the cross-correlation characteristic signal segment is extracted, and the initial photocurrent signal is corrected according to the signal mean of the cross-correlation characteristic signal segment to obtain a photocurrent detection signal.

[0102] In a specific implementation, the initial photocurrent signal is cross-correlated with the photocurrent increment feature according to the photocurrent increment feature. In the process of obtaining the cross-correlation feature signal segment of the photocurrent increment feature and the initial photocurrent signal, the photocurrent increment feature can be segmented, and the obtained signal segments are cross-correlated with the initial photocurrent signal respectively, and the signal segment with the largest cross-correlation feature is used as the cross-correlation feature signal segment of the photocurrent increment feature and the initial photocurrent signal.

[0103] Among them, the signal mean of the mutual correlation characteristic signal segment is extracted, and the initial photocurrent signal is corrected according to the signal mean of the mutual correlation characteristic signal segment to obtain the photocurrent detection signal. In specific implementation, the ratio of the signal mean of the mutual correlation characteristic signal segment to the signal mean of the initial photocurrent signal can be used as a correction coefficient to perform signal correction on the initial photocurrent signal to obtain the photocurrent detection signal. In some embodiments, the signal variance of the mutual correlation characteristic signal segment can also be obtained, and the ratio of the signal variance to the preset variance is used as a scaling factor. According to the scaling factor, the initial photocurrent signal is center-scaled based on its signal mean. It should be noted that the signal correction of the initial photocurrent signal through the photocurrent increment feature can improve the signal similarity between the initial photocurrent signal and the photocurrent increment feature, thereby reducing the signal interference of the environment on the initial photocurrent signal and increasing the accuracy of the photoelectrochemical detection results.

[0104] Preferably, in some embodiments, the signal analysis of the photocurrent detection signal to obtain the photoelectrochemical detection result can be achieved by the following steps: extracting the signal characteristics of the photocurrent detection signal and comparing them with the standard concentration characteristics of the analyte to obtain the photoelectrochemical detection result.

[0105] In addition, in another aspect of the present application, in some embodiments, the present application provides a detection system based on photoelectrochemistry, the device includes a photoelectrochemical detection signal processing unit, reference Figure 3 , which is a schematic diagram of exemplary hardware and / or software of a photoelectrochemical detection signal processing unit according to some embodiments of the present application, the photoelectrochemical detection signal processing unit 200 includes: an acquisition module 201, a processing module 202 and an execution module 203, which are described as follows:

[0106] The acquisition module 201 is used to collect the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal;

[0107] The acquisition module 201 is further used to re-acquire and segment the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments;

[0108] The processing module 202 is used to perform an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and perform a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient;

[0109] The processing module 202 is further configured to extract photocurrent increment features from a set of low-frequency oscillation photocurrent signal segments according to the oscillation frequency period to obtain photocurrent increment features when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient;

[0110] The execution module 203 is used to perform signal correction on the initial photocurrent signal according to the photocurrent increment characteristic to obtain a photocurrent detection signal; and perform signal analysis on the photocurrent detection signal to obtain a photoelectrochemical detection result.

[0111] The above describes in detail an example of a photoelectrochemical-based detection system and method provided in an embodiment of the present application. It can be understood that in order to achieve the above functions, the corresponding device includes a hardware structure and / or software module corresponding to executing each function.

[0112] Those skilled in the art should easily realize that, in combination with the units and algorithm steps of each example described in the embodiments disclosed in this document, the present application can be implemented in the form of hardware or a combination of hardware and computer software. Whether a certain function in the application is executed in hardware or in a computer software-driven hardware manner depends on the specific application and design constraints of the technical solution. Therefore, professional and technical personnel can use different methods to implement the described functions for each specific application, but such implementation should not be considered to be beyond the scope of this application.

[0113] In addition, the present application also provides a computer terminal device, which includes a memory and a processor, wherein the memory stores a code, and the processor is configured to obtain the code and execute the above-mentioned photoelectrochemical detection signal processing method.

[0114] In some embodiments, reference Figure 4 , which is a schematic diagram of the structure of a computer terminal device for implementing a photoelectrochemical detection signal processing method according to some embodiments of the present application. The photoelectrochemical detection signal processing method in the above embodiment can be Figure 3 The computer terminal device 300 shown in the figure is implemented, and the computer terminal device 300 includes at least one communication bus 301, a communication interface 302, a processor 303 and a memory 304.

[0115] The processor 303 can be a general-purpose central processing unit (CPU), an application-specific integrated circuit (ASIC), or one or more processors for controlling the execution of the photoelectrochemical detection signal processing method in the present application.

[0116] The communication bus 301 may include a path for transmitting information between the above-mentioned components.

[0117] The memory 304 may be a read-only memory (ROM) or other types of static storage devices that can store static information and instructions, a random access memory (RAM) or other types of dynamic storage devices that can store information and instructions, or an electrically erasable programmable read-only memory (EEPROM), a compact disc read-only memory (CD-ROM) or other optical disc storage, an optical disc storage (including a compressed optical disc, a laser disc, an optical disc, a digital versatile disc, a Blu-ray disc, etc.), a disk or other magnetic storage device, or any other medium that can be used to carry or store the desired program code in the form of an instruction or data structure and can be accessed by a computer, but is not limited thereto. The memory 304 may exist independently and be connected to the processor 303 via the communication bus 301. The memory 304 may also be integrated with the processor 303.

[0118] The memory 304 is used to store the program code for executing the solution of the present application, and the execution is controlled by the processor 303. The processor 303 is used to execute the program code stored in the memory 304. The program code may include one or more software modules. The determination of the photocurrent increment feature in the above embodiment can be implemented by the processor 303 and one or more software modules in the program code in the memory 304.

[0119] The communication interface 302 uses any transceiver or other device for communicating with other devices or communication networks, such as Ethernet, radio access network (RAN), wireless local area networks (WLAN), etc.

[0120] Optionally, the computer terminal device 300 may further include a power supply 305 for providing power to various devices or circuits in the real-time computer terminal device.

[0121] In a specific implementation, as an embodiment, a computer terminal device may include multiple processors, each of which may be a single-CPU processor or a multi-CPU processor. The processor here may refer to one or more devices, circuits, and / or processing cores for processing data (e.g., computer program instructions).

[0122] The computer terminal device may be a general-purpose computer terminal device or a dedicated computer terminal device. In a specific implementation, the computer terminal device may be a desktop computer, a portable computer, a network server, a personal digital assistant (PDA), a mobile phone, a tablet computer, a wireless terminal device, a communication device or an embedded device. The embodiment of the present application does not limit the type of computer terminal device.

[0123] In addition, in other aspects of the present application, a computer-readable storage medium is provided, wherein the computer-readable storage medium stores at least one computer program, and the computer program is loaded and executed by a processor to implement the operations performed by the above-mentioned photoelectrochemical detection signal processing method.

[0124] In summary, in a detection system and method based on photoelectrochemistry disclosed in an embodiment of the present application, first, photocurrent is collected from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal; the photocurrent is collected and segmented from the photoelectrochemical electrode in the electrolyte chemical solution in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments; an autocorrelation test is performed on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and a differential correlation test is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, the photocurrent increment feature of the low-frequency oscillation photocurrent signal segment set is extracted according to the oscillation frequency period to obtain a photocurrent increment feature; the initial photocurrent signal is signal corrected according to the photocurrent increment feature to obtain a photocurrent detection signal; the photocurrent detection signal is signal analyzed to obtain a photoelectrochemical detection result, and the detected photocurrent can be signal corrected according to the photocurrent increment feature under the low-frequency oscillation period, thereby reducing the random environmental interference of the photocurrent signal and improving the accuracy of the photoelectrochemical detection result.

[0125] The above is only an embodiment of the present application, and the common knowledge such as the specific technical scheme or characteristics in the scheme is not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical scheme of the present application, several modifications and improvements can be made, which should also be regarded as the scope of protection of the present application, and these will not affect the effect of the implementation of the present application and the practicality of the patent.

[0126] The scope of protection claimed by this application shall be based on the content of its claims. The specific implementation methods and other records in the specification can be used to interpret the content of the claims. Obviously, those skilled in the art can make various changes and modifications to this application without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of this application fall within the scope of the claims of this application and their equivalents, this application is also intended to include these modifications and variations.

Claims

1. A photoelectrochemical detection signal processing method, used for detecting signal processing in a detection system based on photoelectrochemistry, characterized in that: The method comprises the following steps: Starting the photoelectrochemical detection, collecting the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution, and obtaining an initial photocurrent signal; Re-collecting and segmenting the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments; Performing an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and performing a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient; When the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment feature extraction is performed on the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period to obtain the photocurrent increment feature; The initial photocurrent signal is corrected according to the photocurrent increment characteristic to obtain a photocurrent detection signal, and the photocurrent detection signal is analyzed to obtain a photoelectrochemical detection result.

2. The method according to claim 1, characterized in that The photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is collected to obtain the initial photocurrent signal, which specifically includes: combining a photosensitive material with a conductive material to form a photoelectrochemical electrode and placing it in an electrolyte chemical solution; After the target to be detected is introduced into the detection area, the photoelectrochemical electrode is irradiated with a light source of a preset wavelength; The photocurrent generated by the photoelectrochemical electrode under light is recorded by an electrochemical workstation to obtain an initial photocurrent signal.

3. The method according to claim 1, characterized in that A 0.1 mol sodium sulfate solution was used as the electrolyte chemical solution.

4. The method according to claim 1, characterized in that The photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is collected and segmented again in the low-frequency oscillation mode to obtain a low-frequency oscillation photocurrent signal segment set, which specifically includes: Obtaining a preset oscillation frequency period; Collecting a photocurrent signal on the photoelectrochemical electrode in the electrolyte chemical solution in a low-frequency oscillation mode, and performing time-series segmentation on the photocurrent signal in the low-frequency oscillation mode according to the oscillation frequency period to obtain a plurality of low-frequency oscillation photocurrent signal segments; The low-frequency oscillation photocurrent signal segment set is composed of a plurality of low-frequency oscillation photocurrent signal segments.

5. The method according to claim 1, characterized in that Performing an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient specifically includes: Obtaining a preset oscillation frequency period; Performing time-series segmentation on the initial photocurrent signal based on a preset oscillation frequency period to obtain a plurality of initial photocurrent related signals; A cross-correlation test is performed on multiple initial photocurrent related signals to obtain the photocurrent self-test correlation coefficient.

6. The method according to claim 1, characterized in that When the photocurrent oscillation correlation coefficient is lower than the photocurrent self-detection correlation coefficient, an initial photocurrent signal is acquired, and a signal analysis is performed based on the initial photocurrent signal to obtain a photoelectrochemical detection result.

7. The method according to claim 1, characterized in that The photocurrent increment feature is extracted from the low-frequency oscillation photocurrent signal segment set according to the oscillation frequency period, and the photocurrent increment feature obtained specifically includes: Combining the low-frequency oscillation photocurrent signal segments in the low-frequency oscillation photocurrent signal segment set based on the time sequence to obtain a low-frequency oscillation photocurrent signal; Acquiring an oscillation frequency period and an oscillation frequency gain of the low-frequency oscillation mode, and performing a hysteresis analysis on the low-frequency oscillation photocurrent signal according to the oscillation frequency period and the oscillation frequency gain to obtain a photocurrent increment signal; A photocurrent increment feature is extracted from the photocurrent increment signal to obtain a photocurrent increment feature.

8. A detection system based on photoelectrochemistry, comprising a photoelectrochemical detection signal processing unit, characterized in that: The photoelectrochemical detection signal processing unit comprises: A collection module, used for collecting photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal; The acquisition module is further used to re-acquire and segment the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments; A processing module, configured to perform an autocorrelation test on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient, and perform a differential correlation test on the low-frequency oscillation photocurrent signal segment set according to an oscillation frequency period and an oscillation frequency gain of the low-frequency oscillation mode to obtain a photocurrent oscillation correlation coefficient; The processing module is further used to extract photocurrent increment features from a set of low-frequency oscillation photocurrent signal segments according to the oscillation frequency period to obtain photocurrent increment features when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient; The execution module is used to perform signal correction on the initial photocurrent signal according to the photocurrent increment characteristic to obtain a photocurrent detection signal; and perform signal analysis on the photocurrent detection signal to obtain a photoelectrochemical detection result.

9. A computer terminal device, characterized in that: The computer terminal device includes a memory and a processor, the memory stores codes, and the processor is configured to obtain the codes and execute a photoelectrochemical detection signal processing method as described in any one of claims 1 to 7.

10. A computer-readable storage medium storing at least one computer program, characterized in that: The computer program is loaded and executed by a processor to implement the operations performed by the photoelectrochemical detection signal processing method as described in any one of claims 1 to 7.

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