A photoelectrochemical-based detection system and method

Abstract

The application provides a photoelectrochemical detection system and method, which obtains a photocurrent autocorrelation coefficient by autocorrelation testing of an initial photocurrent signal, obtains a photocurrent oscillation correlation coefficient by differential correlation testing of a low-frequency oscillation photocurrent signal segment set, extracts a photocurrent increment feature from the low-frequency oscillation photocurrent signal segment set by an oscillation frequency period when the photocurrent oscillation correlation coefficient is higher than the photocurrent autocorrelation coefficient, corrects the initial photocurrent signal according to the photocurrent increment feature to obtain a photocurrent detection signal, and analyzes the photocurrent detection signal to obtain a photoelectrochemical detection result, which can correct the detection photocurrent according to the photocurrent increment feature under a low-frequency oscillation period, thereby reducing random environmental interference on the photocurrent signal and improving the accuracy of the photoelectrochemical detection result.

Description

Technical Field

[0001] This application relates to the field of photoelectrochemical detection technology, and more specifically, to a photoelectrochemical-based detection system and method. Background Technology

[0002] A photoelectrochemical detection system is a device system that combines optical and electrochemical technologies to detect and analyze specific substances. This system works by utilizing the principle that the photogenerated charge of a photoelectrochemically responsive material, under light excitation, triggers a redox chemical reaction in the substance to be detected. This redox reaction causes a change in the photocurrent signal on the corresponding photoelectrochemical electrode. By measuring the photocurrent signal generated during the electrochemical reaction using electrodes in an electrolyte chemical solution, the system analyzes the properties or concentration of the target substance. It features high detection sensitivity and strong selectivity, making it widely used in environmental monitoring, biosensing, materials science, and new energy fields.

[0003] In the process of photoelectrochemical detection, it is necessary to remove interference factors. Existing photoelectrochemical detection methods mainly reduce background interference by detecting the dark current of the photoelectrochemical electrode and eliminating the dark current in the final photocurrent signal. However, this method is difficult to eliminate 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] This application provides a photoelectrochemical-based detection system and method, which can perform signal correction on the detected photocurrent based on the photocurrent increment characteristics under low-frequency oscillation period, thereby reducing random environmental interference on the photocurrent signal and improving the accuracy of photoelectrochemical detection results.

[0005] In a first aspect, this application provides a photoelectrochemical detection signal processing method, which can be executed by a network device or by a chip configured in the network device, and this application does not limit the execution of such method.

[0006] Specifically, the method includes:

[0007] The photocurrent was collected by the photoelectrochemical electrode in the electrolyte chemical solution to obtain the initial photocurrent signal;

[0008] The photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is re-acquired and segmented in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments.

[0009] The initial photocurrent signal is subjected to autocorrelation test to obtain the photocurrent autocorrelation coefficient. Based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode, the set of low-frequency oscillation photocurrent signal segments is subjected to differential correlation test to obtain the photocurrent oscillation correlation coefficient.

[0010] When the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, the photocurrent increment feature is extracted from the low-frequency oscillation photocurrent signal segment set by the oscillation frequency period to obtain the photocurrent increment feature.

[0011] The initial photocurrent signal is corrected based on the photocurrent increment characteristics to obtain a photocurrent detection signal; the photocurrent detection signal is then analyzed to obtain a photoelectrochemical detection result.

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

[0013] By combining photosensitive materials with conductive materials, a photoelectrochemical electrode can be formed.

[0014] After the target to be tested 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 illumination was recorded using an electrochemical workstation to obtain the initial photocurrent signal.

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

[0017] In conjunction with the first aspect, in certain implementations of the first aspect, the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution is re-acquired and segmented in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments, specifically including:

[0018] Obtain the preset oscillation frequency period;

[0019] The photocurrent signal under low-frequency oscillation mode is acquired, and the photocurrent signal under low-frequency oscillation mode is time-sequence segmented according to the oscillation frequency period to obtain multiple low-frequency oscillation photocurrent signal segments.

[0020] The low-frequency oscillating photocurrent signal segment set is composed of multiple low-frequency oscillating photocurrent signal segments.

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

[0022] Obtain the preset oscillation frequency period;

[0023] The initial photocurrent signal is time-sequentially segmented based on a preset oscillation frequency period to obtain multiple initial photocurrent related signals;

[0024] Cross-correlation tests were performed on multiple initial photocurrent correlation signals to obtain the photocurrent self-test correlation coefficient.

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

[0026] In conjunction with the first aspect, in certain implementations of the first aspect, the extraction of photocurrent increment features from the set of low-frequency oscillating photocurrent signal segments based on the oscillation frequency period to obtain photocurrent increment features specifically includes:

[0027] Based on the timing sequence, the low-frequency oscillating photocurrent signal segments in the set of low-frequency oscillating photocurrent signal segments are combined to obtain the low-frequency oscillating photocurrent signal.

[0028] The oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode are obtained, and the low-frequency oscillation photocurrent signal is subjected to hysteresis analysis based on the oscillation frequency period and the oscillation frequency gain to obtain the photocurrent increment signal.

[0029] The photocurrent increment signal is subjected to photocurrent increment feature extraction to obtain the photocurrent increment feature.

[0030] Secondly, this application provides a photoelectrochemical-based detection system, which includes a photoelectrochemical detection signal processing unit, the photoelectrochemical detection signal processing unit comprising:

[0031] The acquisition module is used to acquire the photocurrent of the photoelectrochemical electrode in the electrolyte chemical solution to obtain the initial photocurrent signal.

[0032] The acquisition module is also 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] The processing module is used to perform autocorrelation test on the initial photocurrent signal to obtain the photocurrent autocorrelation coefficient, and to perform differential correlation test on the set of low-frequency oscillating photocurrent signal segments based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain the photocurrent oscillation correlation coefficient.

[0034] The processing module is further configured to extract photocurrent increment features from the set of low-frequency oscillating photocurrent signal segments by means of the oscillation frequency period when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, thereby obtaining photocurrent increment features.

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

[0036] Thirdly, this application provides a computer terminal device, which includes a memory and a processor. The memory stores code, and the processor is configured to acquire the code and execute the above-described photoelectrochemical detection signal processing method.

[0037] Fourthly, this application provides a computer-readable storage medium storing at least one computer program, which is loaded and executed by a processor to perform the operations performed by the above-described photoelectrochemical detection signal processing method.

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

[0039] This application provides a photoelectrochemical-based detection system and method, which first acquires photocurrent from a photoelectrochemical electrode in an electrolyte chemical solution to obtain an initial photocurrent signal; then, the photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution is acquired again in a low-frequency oscillation mode and segmented to obtain a set of low-frequency oscillating photocurrent signal segments; an autocorrelation test is performed on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient; based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode, a differential correlation test is performed on the set of low-frequency oscillating photocurrent signal segments to obtain a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment features are extracted from the set of low-frequency oscillation photocurrent signal segments based on the oscillation frequency period to obtain photocurrent increment features; the initial photocurrent signal is corrected based on the photocurrent increment features to obtain a photocurrent detection signal; and signal analysis is performed on the photocurrent detection signal to obtain the photoelectrochemical detection result.

[0040] Therefore, this application analyzes the photocurrent signal within the oscillation frequency period. Thus, using the low-frequency oscillation period for signal extraction effectively distinguishes between the true periodic signal caused by the photoelectrochemical reaction and environmental random noise. This helps remove noise components from the photocurrent signal and retain the effective signal. The autocorrelation test of the initial photocurrent signal can identify its internal correlation, obtaining the photocurrent self-test correlation coefficient. This coefficient serves as a benchmark, reflecting the signal stability without external oscillation. The photocurrent signal under the low-frequency oscillation mode, after differential processing and correlation testing, yields an oscillation correlation coefficient that reflects the signal variation characteristics under periodic perturbations. If the correlation coefficient of photocurrent oscillation 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 oscillation than random fluctuations caused by environmental noise. Therefore, effective change features can be extracted by the photocurrent increment signal within the oscillation period. The initial photocurrent signal can be corrected using the photocurrent increment features, which can effectively reduce the interference of random environmental factors on the signal and thus improve the accuracy of the detection signal. In summary, this application can correct the detection photocurrent signal based on the photocurrent increment features under the low-frequency oscillation period, thereby reducing the random environmental interference on the photocurrent signal and improving the accuracy of photoelectrochemical detection results. Attached Figure Description

[0041] Figure 1 This is an exemplary flowchart of a photoelectrochemical detection signal processing method according to some embodiments of this application;

[0042] Figure 2 This is an exemplary flowchart of obtaining the photocurrent self-test correlation coefficient in some embodiments of this application;

[0043] Figure 3 These are schematic diagrams of exemplary hardware and / or software of a photoelectrochemical detection signal processing unit according to some embodiments of this application;

[0044] Figure 4 This is a schematic diagram of the structure of a computer terminal device that implements a photoelectrochemical detection signal processing method according to some embodiments of this application. Detailed Implementation

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

[0046] To better understand the above technical solutions, a detailed description of the solutions will be provided below in conjunction with the accompanying drawings and specific implementation methods. (Reference) Figure 1 The figure is an exemplary flowchart of a photoelectrochemical detection signal processing method according to some embodiments of this 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 the photocurrent signal collected on the photochemical electrode during photoelectrochemical detection of the target. Optionally, in some embodiments, the initial photocurrent signal can be collected by the following steps:

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

[0050] During the detection process, an appropriate electrolyte chemical solution is selected as the detection medium. Specifically, a sodium sulfate solution of 0.1 mol / L 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 characteristics of the target substance. This will not be elaborated here.

[0051] The target to be tested is introduced into the detection system. In this application, the target to be tested can be any liquid, gas or solid to be tested.

[0052] The photoelectrochemical electrode is irradiated with a light source of a preset wavelength;

[0053] The initial photocurrent signal was obtained by recording the photocurrent generated by the photoelectrochemical electrode under illumination using an electrochemical workstation.

[0054] Optionally, in some embodiments, after collecting the 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. Specifically, a transimpedance amplifier can be used to amplify the initial photocurrent signal. In some other embodiments, other devices or equipment capable of signal amplification can also be used, which are not limited here.

[0055] Optionally, in some embodiments, a sodium sulfate solution of 0.1 mol / L 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 one 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. Specifically, 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 improving 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 increase the local temperature of the electrode surface. The increase in temperature will increase the thermal energy of electrons and holes, increasing the probability of electrons transitioning from the valence band to the conduction band, thereby increasing the generation rate of electron-hole pairs (i.e., increasing the photoelectrochemical reaction rate), thus increasing the amplitude of the photocurrent signal. Furthermore, in some embodiments, titanium dioxide (TiO2) can be used as the photosensitive material of the photoelectrochemical electrode. The increase in surface temperature will improve the conductivity of titanium dioxide and help activate the catalytic sites on its surface, enhancing photocatalytic activity and increasing 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. The fixed parameters of the frequency control signal include: initial oscillation frequency, oscillation frequency gain, and oscillation frequency period. The initial oscillation frequency is the starting frequency of the vibration device, i.e., the initial vibration frequency set when the vibration device starts working. The oscillation frequency gain is the frequency increase value each time the vibration device periodically increases its frequency, i.e., the increment when the vibration device periodically increases its vibration frequency. The oscillation frequency period is the periodic time of each periodic frequency increase, i.e., the time interval between each frequency increase. Specifically, the initial oscillation frequency, oscillation frequency gain, and oscillation frequency period can be calibrated through multiple experiments, selecting an initial oscillation frequency, oscillation frequency gain, and oscillation frequency period when the photocurrent signal amplitude changes significantly, 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 re-acquired and segmented in a low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments. This can be achieved by the following steps:

[0060] Obtain the preset oscillation frequency period;

[0061] The photocurrent signal under low-frequency oscillation mode is acquired, and the photocurrent signal under low-frequency oscillation mode is time-sequentially segmented according to the oscillation frequency period to obtain multiple low-frequency oscillation photocurrent signal segments.

[0062] The low-frequency oscillating photocurrent signal segment set is composed of multiple low-frequency oscillating photocurrent signal segments.

[0063] In specific implementation, the time-series 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, the photocurrent signal in the low-frequency oscillation mode is segmented to obtain multiple low-frequency oscillation photocurrent signal segments.

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

[0065] It should be noted that the photocurrent self-test correlation coefficient mentioned in this application represents the degree of autocorrelation of the initial photocurrent signal. A larger photocurrent self-test correlation coefficient indicates a more stable initial photocurrent signal, less interference, and higher signal reliability. The photocurrent self-test correlation coefficient is determined by the autocorrelation of the initial photocurrent signal. Optionally, in some embodiments, reference is made to... Figure 2 As shown, this figure is an exemplary flowchart for obtaining the photocurrent self-test correlation coefficient in some embodiments of this application. The process of performing an autocorrelation test on the initial photocurrent signal to obtain the photocurrent self-test correlation coefficient can be achieved through the following steps:

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

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

[0068] In step S1033, cross-correlation tests are performed on multiple initial photocurrent correlation signals to obtain the photocurrent self-test correlation coefficient.

[0069] In practice, during the process of performing cross-correlation tests on multiple initial photocurrent correlation signals to obtain the photocurrent self-test correlation coefficient, the mean of the Pearson correlation coefficients among multiple initial photocurrent correlation signals can be used as the photocurrent self-test correlation coefficient.

[0070] It should be noted that the photocurrent oscillation correlation coefficient mentioned in this application represents the correlation degree of the photocurrent signal change increment under the low-frequency oscillation mode. The larger the photocurrent oscillation correlation coefficient, the more stable the photocurrent signal change increment, the less interference the signal is subject to, and the higher the reliability of the signal. The photocurrent oscillation correlation coefficient is determined based on the correlation degree of the photocurrent signal change increment within different oscillation frequency periods. Optionally, in some embodiments, the photocurrent oscillation correlation coefficient can be obtained by performing a differential correlation test on the set of low-frequency oscillation photocurrent signal segments based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode. This can be achieved by the following steps:

[0071] Differential processing is performed on each low-frequency oscillating photocurrent signal segment in the set of low-frequency oscillating photocurrent signal segments to obtain multiple oscillating differential signal segments;

[0072] Obtain the oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode, and determine the oscillation mode calibration coefficient based on the oscillation frequency period and the oscillation frequency gain;

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

[0074] In practice, during the process of determining the oscillation mode calibration coefficient based on the oscillation frequency period and the oscillation frequency gain, the oscillation mode calibration coefficient can be obtained by mapping 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 = calibrated proportional coefficient × oscillation frequency gain / 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 experiments.

[0076] Optionally, in some embodiments, the differential correlation test is performed on all oscillation differential signal segments based on the oscillation mode calibration coefficient to obtain the photocurrent oscillation correlation coefficient, which can be achieved by the following steps:

[0077] Obtain the signal mean value corresponding to each oscillation differential signal segment;

[0078] For each oscillation differential signal segment, the signal scale is scaled based on the corresponding signal mean according to the oscillation mode calibration coefficient to obtain the corresponding oscillation related signal segment.

[0079] Cross-correlation tests were performed on all oscillation-related signal segments to obtain the photocurrent oscillation correlation coefficient.

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

[0081]

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

[0083] Optionally, in some embodiments, during the process of obtaining the photocurrent oscillation correlation coefficient by performing cross-correlation tests based on all oscillation-related signal segments, the average of the Pearson correlation coefficients among multiple oscillation-differential signal segments can be used as the photocurrent oscillation correlation coefficient.

[0084] Optionally, in some embodiments, during the differential processing of each low-frequency oscillating photocurrent signal segment in the set of low-frequency oscillating photocurrent signal segments to obtain multiple oscillating differential signal segments, the set of low-frequency oscillating photocurrent signal segments can be regarded as a two-dimensional array, where each row of the array is a separate low-frequency oscillating photocurrent signal segment. Multiple oscillating differential signal segments can be obtained by subtracting the corresponding data in the array of each low-frequency oscillating photocurrent signal segment from the corresponding data in the adjacent previous low-frequency oscillating photocurrent signal segment. 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 oscillating photocurrent signal segment is an array of length 1000. By subtracting the corresponding data in the array of the adjacent previous low-frequency oscillating photocurrent signal segment, the oscillating differential signal segment corresponding to the low-frequency oscillating photocurrent signal segment can be obtained.

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

[0086] It should be noted that the autocorrelation test of the initial photocurrent signal can identify its internal similarity or consistency, obtaining the photocurrent self-test correlation coefficient. This coefficient serves as a benchmark, reflecting the signal stability without external oscillation. The photocurrent signal in the low-frequency oscillation mode, after differential processing and correlation testing, yields an oscillation correlation coefficient that reflects the signal variation characteristics under periodic perturbations. If the photocurrent oscillation correlation coefficient is higher than the self-test correlation coefficient, it indicates that the signal variation in the oscillation mode is more due to oscillation-induced reaction changes than random fluctuations caused by environmental noise. In this case, the signal stability of the initial photocurrent signal is affected by external interference, and its signal reliability is lower than that of the photocurrent signal increment in the low-frequency oscillation mode. Signal analysis of the initial photocurrent signal is difficult to obtain accurate detection results. However, the photocurrent signal in the low-frequency oscillation mode has a partial signal increment. This partial signal increment is obtained by periodically increasing the photoelectrochemical reaction rate, and therefore is less affected by environmental factors. It is necessary to extract the photocurrent increment feature 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-test correlation coefficient, an initial photocurrent signal is acquired, and signal analysis is performed based on the initial photocurrent signal to obtain the photoelectrochemical detection result.

[0088] It should be noted that the photocurrent increment feature described in this application is an increment feature signal obtained after feature extraction based on the photocurrent signal increment under 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 photoelectrochemical detection results. Optionally, in some embodiments, the photocurrent increment feature is extracted from the set of low-frequency oscillation photocurrent signal segments based on the oscillation frequency period. This can be achieved using the following steps:

[0089] Based on the timing sequence, the low-frequency oscillating photocurrent signal segments in the set of low-frequency oscillating photocurrent signal segments are combined to obtain the low-frequency oscillating photocurrent signal.

[0090] The oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode are obtained, and the low-frequency oscillation photocurrent signal is subjected to hysteresis analysis based on the oscillation frequency period and the oscillation frequency gain to obtain the photocurrent increment signal.

[0091] The photocurrent increment signal is subjected to photocurrent increment feature extraction to obtain the photocurrent increment feature.

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

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

[0094] The low-frequency oscillating photocurrent signal is differentially hystereticized according to the oscillation frequency period to obtain a transition signal. Then, the transition signal is scaled according to the oscillation frequency gain to obtain the photocurrent increment signal.

[0095] In a specific implementation, a time delay of the same duration as the oscillation frequency period can be introduced into the low-frequency oscillating photocurrent signal to obtain a delayed signal. The difference between the low-frequency oscillating photocurrent signal and the delayed signal is used as a transition signal. Then, the transition signal is linearly scaled according to the ratio of the oscillation frequency gain to a preset standard gain as a scaling factor to obtain the final photocurrent increment signal. The photocurrent increment signal is the photocurrent signal increment caused by the low-frequency oscillation mode.

[0096] Preferably, in some embodiments, the extraction of photocurrent increment features from the photocurrent increment signal 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 extracting photocurrent increment features from the photocurrent increment signal, the stability of the photocurrent signal can be increased, and the accuracy of photoelectrochemical detection results can be improved.

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

[0098] When the correlation coefficient of photocurrent oscillation is higher than the self-test correlation coefficient, it indicates that the fluctuation of the signal is mainly related to the oscillation. The effective change part can be extracted by the incremental photocurrent signal within the oscillation period. This incremental signal represents the real dynamic reaction of photoelectrochemical reaction within the oscillation period, which 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 based on the photocurrent increment characteristics to obtain the photocurrent detection signal, which can be achieved by the following steps:

[0100] Based on the photocurrent increment characteristics, cross-correlation features are extracted from the initial photocurrent signal to obtain the photocurrent increment characteristics and the cross-correlation feature signal segment of the initial photocurrent signal;

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

[0102] In specific implementation, during the process of extracting cross-correlation features from the initial photocurrent signal based on the photocurrent increment features to obtain the cross-correlation feature signal segments of the photocurrent increment features and the initial photocurrent signal, the photocurrent increment features can be segmented, and the obtained signal segments can be cross-correlation features extracted from the initial photocurrent signal respectively. The signal segment with the largest cross-correlation feature is taken as the cross-correlation feature signal segment of the photocurrent increment features and the initial photocurrent signal.

[0103] In this process, the mean signal of the cross-correlation feature signal segment is extracted, and the initial photocurrent signal is corrected based on the mean signal of the cross-correlation feature signal segment to obtain the photocurrent detection signal. In specific implementations, the ratio of the mean signal of the cross-correlation feature signal segment to the mean signal of the initial photocurrent signal can be used as a correction coefficient to correct the initial photocurrent signal and obtain the photocurrent detection signal. In some embodiments, the signal variance of the cross-correlation feature signal segment can also be obtained, and the ratio of the signal variance to a preset variance can be used as a scaling factor. The initial photocurrent signal is then centered and scaled based on its mean signal value according to the scaling factor. It should be noted that correcting the initial photocurrent signal using the photocurrent increment feature can improve the signal similarity between the initial photocurrent signal and the photocurrent increment feature, thereby reducing environmental interference on the initial photocurrent signal and increasing the accuracy of the photoelectrochemical detection results.

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

[0105] Furthermore, in another aspect of this application, in some embodiments, this application provides a photoelectrochemical-based detection system, the device including a photoelectrochemical detection signal processing unit, referenced... Figure 3 The figure is a schematic diagram of exemplary hardware and / or software of a photoelectrochemical detection signal processing unit according to some embodiments of this 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 below:

[0106] Acquisition module 201 is used to acquire photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution to obtain the initial photocurrent signal;

[0107] The acquisition module 201 is also 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] Processing module 202 is used to perform autocorrelation test on the initial photocurrent signal to obtain the photocurrent autocorrelation coefficient, and to perform differential correlation test on the set of low-frequency oscillating photocurrent signal segments according to the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain the photocurrent oscillation correlation coefficient.

[0109] The processing module 202 is further configured to extract photocurrent increment features from the low-frequency oscillation photocurrent signal segment set by the oscillation frequency period when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, thereby obtaining photocurrent increment features.

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

[0111] The foregoing has provided a detailed example of a photoelectrochemical-based detection system and method provided in the embodiments of this application. It is understood that the corresponding device includes hardware structures and / or software modules for performing each function in order to achieve the above functions.

[0112] Those skilled in the art should readily recognize that, based on the units and algorithm steps of the various examples described in conjunction with the embodiments disclosed herein, this application can be implemented in hardware or a combination of hardware and computer software. Whether a certain function in the application is executed in a manner that drives hardware or computer software depends on the specific application and design constraints of the technical solution. Therefore, those skilled in the art can use different methods to implement the described function for each specific application, but such implementation should not be considered to be beyond the scope of this application.

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

[0114] In some embodiments, reference Figure 4 The figure 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 this application. The photoelectrochemical detection signal processing method in the above embodiments can... Figure 3 The computer terminal device 300 shown is used to implement this, and the computer terminal device 300 includes at least one communication bus 301, communication interface 302, processor 303 and memory 304.

[0115] The processor 303 may be a general-purpose central processing unit (CPU), an application-specific integrated circuit (ASIC), or one or more devices used to control the execution of the photoelectrochemical detection signal processing method in this application.

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

[0117] Memory 304 may be a read-only memory (ROM) or other type of static storage device capable of storing static information and instructions, random access memory (RAM) or other type of dynamic storage device capable of storing information and instructions, or electrically erasable programmable read-only memory (EEPROM), compact disc read-only memory (CD-ROM) or other optical disc storage, optical disc storage (including compressed optical discs, laser discs, optical discs, digital versatile optical discs, Blu-ray discs, etc.), magnetic disks or other magnetic storage devices, or any other medium capable of carrying or storing desired program code in the form of instructions or data structures and accessible by a computer, but not limited thereto. Memory 304 may exist independently and be connected to processor 303 via communication bus 301. Memory 304 may also be integrated with processor 303.

[0118] The memory 304 stores program code for executing the scheme of this application, and its execution is controlled by the processor 303. The processor 303 executes the program code stored in the memory 304. The program code may include one or more software modules. In the above embodiments, the determination of the photocurrent increment characteristics can be achieved by the processor 303 and one or more software modules in the program code in the memory 304.

[0119] Communication interface 302 uses any transceiver-like 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 also 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 one example, a computer terminal device may include multiple processors, each of which may be a single-core (single-CPU) processor or a multi-core (multi-CPU) processor. Here, a processor may refer to one or more devices, circuits, and / or processing cores for processing data (e.g., computer program instructions).

[0122] The aforementioned computer terminal device can be a general-purpose computer terminal device or a dedicated computer terminal device. In specific implementations, the computer terminal device can be a desktop computer, a portable computer, a network server, a handheld computer (PDA), a mobile phone, a tablet computer, a wireless terminal device, a communication device, or an embedded device. This application does not limit the type of computer terminal device.

[0123] In addition, other aspects of this application provide a computer-readable storage medium storing at least one computer program, which is loaded and executed by a processor to perform the operations performed by the above-described photoelectrochemical detection signal processing method.

[0124] In summary, the photoelectrochemical-based detection system and method disclosed in this application firstly acquires photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution to obtain an initial photocurrent signal; then, the photocurrent from the photoelectrochemical electrode in the electrolyte chemical solution is reacquired and segmented in a low-frequency oscillation mode to obtain a set of low-frequency oscillating photocurrent signal segments; an autocorrelation test is performed on the initial photocurrent signal to obtain a photocurrent self-test correlation coefficient; based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode, a differential correlation test is performed on the set of low-frequency oscillating photocurrent signal segments to obtain a photocurrent oscillation correlation coefficient; when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, photocurrent increment features are extracted from the set of low-frequency oscillation photocurrent signal segments based on the oscillation frequency period to obtain photocurrent increment features; the initial photocurrent signal is corrected based on the photocurrent increment features to obtain a photocurrent detection signal; and signal analysis is performed on the photocurrent detection signal to obtain the photoelectrochemical detection result. This method can correct the detected photocurrent signal based on the photocurrent increment features under the low-frequency oscillation period, thereby reducing random environmental interference to the photocurrent signal and improving the accuracy of the photoelectrochemical detection result.

[0125] The above descriptions are merely embodiments of this application, and common knowledge such as specific technical solutions or characteristics in the solutions are not described in detail here. It should be noted that those skilled in the art can make several modifications and improvements without departing from the technical solutions of this application, and these should also be considered within the scope of protection of this application, without affecting the effectiveness of the implementation of this application or the practicality of the patent.

[0126] The scope of protection claimed in this application shall be determined by the content of its claims. The specific embodiments described in the specification can be used to interpret the content of the claims. Obviously, those skilled in the art can make various modifications and variations to this application without departing from the spirit and scope of the invention. Therefore, if these modifications and variations of this application fall within the scope of the claims of this application and their equivalents, this application also intends to include these modifications and variations.

Claims

1. A photoelectrochemical detection signal processing method, used for detection signal processing in a photoelectrochemical-based detection system, characterized in that, The method includes the following steps: Acquire the initial photocurrent signal during photoelectrochemical detection; The photocurrent signal under low-frequency oscillation mode is acquired and segmented to obtain a set of low-frequency oscillation photocurrent signal segments; The initial photocurrent signal is subjected to autocorrelation test to obtain the photocurrent autocorrelation coefficient. Based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode, the set of low-frequency oscillation photocurrent signal segments is subjected to differential correlation test to obtain the photocurrent oscillation correlation coefficient. When the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, the photocurrent increment feature is extracted from the low-frequency oscillation photocurrent signal segment set by the oscillation frequency period to obtain the photocurrent increment feature. The photocurrent increment feature is the increment feature signal obtained after feature extraction based on the photocurrent signal increment under the low-frequency oscillation mode. The initial photocurrent signal is corrected based on the photocurrent increment characteristics to obtain a photocurrent detection signal, and the photocurrent detection signal is analyzed to obtain the photoelectrochemical detection result.

2. The method as described in claim 1, characterized in that, The initial photocurrent signal acquired during photoelectrochemical detection specifically includes: By combining photosensitive materials with conductive materials, a photoelectrochemical electrode can be formed. After the target to be tested 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 illumination was recorded using an electrochemical workstation to obtain the initial photocurrent signal.

3. The method as described in claim 1, characterized in that, After acquiring the initial photocurrent signal during photoelectrochemical detection, the method further includes amplifying the initial photocurrent signal using a transimpedance amplifier.

4. The method as described in claim 1, characterized in that, The photocurrent signal under low-frequency oscillation mode is acquired and segmented to obtain a set of low-frequency oscillation photocurrent signal segments, specifically including: Obtain the preset oscillation frequency period; The photocurrent signal under low-frequency oscillation mode is acquired, and the photocurrent signal under low-frequency oscillation mode is time-sequence segmented according to the oscillation frequency period to obtain multiple low-frequency oscillation photocurrent signal segments. The low-frequency oscillating photocurrent signal segment set is composed of multiple low-frequency oscillating photocurrent signal segments.

5. The method as described in claim 1, characterized in that, The initial photocurrent signal is subjected to an autocorrelation test to obtain the photocurrent autocorrelation coefficient, which specifically includes: Obtain the preset oscillation frequency period; The initial photocurrent signal is time-sequentially segmented based on a preset oscillation frequency period to obtain multiple initial photocurrent related signals; Cross-correlation tests were performed on multiple initial photocurrent correlation signals to obtain the photocurrent self-test correlation coefficient.

6. The method as described in claim 1, characterized in that, When the photocurrent oscillation correlation coefficient is lower than the photocurrent self-test correlation coefficient, the initial photocurrent signal is acquired, and the photoelectrochemical detection result is obtained by signal analysis based on the initial photocurrent signal.

7. The method as described in claim 1, characterized in that, The photocurrent increment features are extracted from the set of low-frequency oscillating photocurrent signal segments based on the oscillation frequency period. The specific photocurrent increment features include: Based on the timing sequence, the low-frequency oscillating photocurrent signal segments in the set of low-frequency oscillating photocurrent signal segments are combined to obtain the low-frequency oscillating photocurrent signal. The oscillation frequency period and the oscillation frequency gain of the low-frequency oscillation mode are obtained, and the low-frequency oscillation photocurrent signal is subjected to hysteresis analysis based on the oscillation frequency period and the oscillation frequency gain to obtain the photocurrent increment signal. The photocurrent increment signal is subjected to photocurrent increment feature extraction to obtain the photocurrent increment feature.

8. A photoelectrochemical-based detection system, comprising a photoelectrochemical detection signal processing unit, wherein the photoelectrochemical detection signal processing unit performs photoelectrochemical detection signal processing using the method described in any one of claims 1 to 7, characterized in that, The photoelectrochemical detection signal processing unit includes: The acquisition module is used to acquire the initial photocurrent signal during photoelectrochemical detection; The acquisition module is also used to acquire and segment the photocurrent signal in the low-frequency oscillation mode to obtain a set of low-frequency oscillation photocurrent signal segments. The processing module is used to perform autocorrelation test on the initial photocurrent signal to obtain the photocurrent autocorrelation coefficient, and to perform differential correlation test on the set of low-frequency oscillating photocurrent signal segments based on the oscillation frequency period and oscillation frequency gain of the low-frequency oscillation mode to obtain the photocurrent oscillation correlation coefficient. The processing module is further configured to extract photocurrent increment features from the set of low-frequency oscillating photocurrent signal segments by means of the oscillation frequency period when the photocurrent oscillation correlation coefficient is higher than the photocurrent self-test correlation coefficient, thereby obtaining photocurrent increment features. The execution module is used to perform signal correction on the initial photocurrent signal according to the photocurrent increment characteristics to obtain a photocurrent detection signal; and to 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 code, and the processor is configured to acquire the code 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 perform the operations of the photoelectrochemical detection signal processing method as described in any one of claims 1 to 7.

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