An ultrahigh-throughput photocatalytic material automatic screening system

Abstract

The present application relates to the technical field of automation screening, and particularly relates to an ultrahigh-throughput photocatalytic material automatic screening system, which comprises a photocatalytic detection module for sequentially performing full-spectrum and visible light detection on a calcined sample array to obtain fluorescence image data and visible light image data; a data processing module for determining fluorescence brightness time series and dye color time series and converting them into dye degradation rate constant time series; a total amount change determination module for determining whether the total amount of photo-generated carriers changes; a spectral response ratio determination module for determining active spectral response ratio and fluorescence spectral response ratio based on double-spectral data; a sorting instruction generation module for determining screening classification types and generating sorting instructions; and a mechanical conveying mechanism for executing sorting and transferring. The present application can determine the physical source of the difference between sample stability and activity in a single round of detection and execute differentiated sorting, thereby improving screening throughput and sorting accuracy.

Description

Technical Field

[0001] This invention relates to the field of automated screening technology, and in particular to an automated screening system for ultra-high throughput photocatalytic materials. Background Technology

[0002] Photocatalytic materials have broad application prospects in energy conversion and environmental governance. The core of developing efficient photocatalysts lies in rapidly screening material systems with excellent performance from a large number of candidate formulations. However, photocatalytic reactions involve multiple sequential physical processes, such as photon absorption, carrier excitation, carrier separation and transport, and surface reactions, with the final activity controlled by the slowest step. Traditional screening methods construct a single photocatalytic reaction platform and sequentially test the degradation or hydrogen production of each candidate sample. This method can only evaluate a single sample at a time, has a long detection cycle, and can only obtain the final apparent degradation performance or hydrogen production rate, failing to distinguish the physical reasons behind performance differences. As a result, many candidate materials whose potential can be realized through optimization of a single step are mistakenly discarded.

[0003] Chinese Patent Application Publication No. CN102621062A discloses a method for high-throughput screening of photocatalysts based on photoelectric performance and its dedicated chip. Existing methods prepare arrays of semiconductor materials with different compositions on a substrate using techniques such as screen printing, inkjet printing, or microdroplet deposition. Under multiple external field coupling conditions, including illumination, electric field, and optionally magnetic field, thermal field, or atmosphere, the photocurrent signal of each sample is collected. From this signal, multi-level physical parameters such as photoconductivity, carrier concentration, carrier mobility, electron-hole recombination rate, photoelectric conversion efficiency, carrier lifetime, grain boundary barrier, surface defect concentration, and depletion layer width are extracted. These photoelectric performance parameters are used as evaluation indicators to indirectly infer the photocatalytic performance of the material, thereby enabling parallel evaluation of multiple samples.

[0004] However, the above-mentioned solutions still have the following problems: the relevant technical solutions require comprehensive testing of multiple external fields such as light, electric field and optional magnetic field, thermal field, atmosphere, etc., the detection conditions are complex, and the collected photocurrent signal needs to be fitted with multiple parameters to indirectly infer the photocatalytic performance. The single-round detection process is time-consuming and it is difficult to achieve rapid parallel evaluation of a large number of samples in ultra-high throughput screening scenarios. Summary of the Invention

[0005] To address this issue, the present invention provides an automated screening system for ultra-high throughput photocatalytic materials. This system overcomes the problem in the prior art where, during single-round parallel detection, the time-varying interference factor of the total number of photogenerated carriers is coupled with the intrinsic activity of the material and cannot be independently determined. This leads to the sorting criteria misjudging the activity decay caused by photocorrosion or depletion of sacrificial agents as insufficient intrinsic performance of the material, thus causing screening errors.

[0006] To achieve the above objectives, the present invention provides an automated screening system for ultra-high throughput photocatalytic materials, comprising: The photocatalytic detection module includes a sample stage for supporting the calcined sample array, a light source, a fluorescence camera for acquiring several fluorescence image data, and a color camera for acquiring several visible light image data, for sequentially performing first spectral detection and second spectral detection on the calcined sample array. A data processing module is used to determine a fluorescence brightness time series based on several fluorescence image data, and to determine a dye color time series based on several visible light image data; A spectral response ratio determination module is used to determine the activity spectral response ratio based on the dye color time series and the fluorescence spectral response ratio based on the fluorescence brightness time series; The total change determination module is used to determine whether there is a change in the total amount of photogenerated carriers based on the fluorescence brightness time series and the dye color time series. The sorting instruction generation module is used to determine the corresponding screening classification type based on the judgment result of the change in the total amount of photogenerated carriers, the active spectral response ratio and the fluorescence spectral response ratio, and generate the corresponding sorting instruction. The screening classification types include unstable type, photoactivated type, qualified type, bulk phase recombination failure type, surface reaction hindered type, type to be re-inspected type and insufficient light absorption type. The sorting instructions include rejection instruction, transfer to characterization module instruction, retention instruction and send to narrow bandgap optimization queue instruction. A mechanical conveying mechanism is used to receive the sorting instruction and transfer the corresponding roasted sample from the sample stage based on the sorting instruction to complete the sorting of the roasted sample.

[0007] Furthermore, the data processing module is also used to extract the corresponding grayscale mean values ​​of several fluorescence image data, and arrange the grayscale mean values ​​in chronological order to obtain the fluorescence brightness time series.

[0008] Furthermore, the data processing module is also used to extract specific color channel values ​​corresponding to several of the visible light image data, and arrange the specific color channel values ​​in chronological order to obtain the dye color time series; The specific color channel value is the pixel value of the color channel corresponding to the characteristic absorption wavelength of the dye.

[0009] Furthermore, the data processing module also performs standard curve conversion based on the dye color time series to obtain the dye degradation rate constant time series.

[0010] Furthermore, the spectral response ratio determination module is also used to determine the activity spectral response ratio based on the dye degradation rate constant time series corresponding to the first spectral detection and the dye degradation rate constant time series corresponding to the second spectral detection, and to determine the fluorescence spectral response ratio based on the fluorescence brightness time series corresponding to the first spectral detection and the fluorescence brightness time series corresponding to the second spectral detection.

[0011] Furthermore, the total change determination module is also used to determine the direction of fluorescence change based on the change in the average gray value of adjacent sampling times in the fluorescence brightness time series, and to determine the direction of dye degradation based on the change in the specific color channel value of adjacent sampling times in the dye color time series. The total change determination module also determines whether there is a change in the total amount of photogenerated carriers based on the direction of fluorescence change and the direction of dye degradation.

[0012] Furthermore, the total change determination module also determines that the direction of fluorescence change is the same as the direction of dye degradation based on the decrease in fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the decrease in the specific color channel value at adjacent sampling times in the dye color time series, and confirms that there is a decrease in the total amount of photogenerated carriers. The total change determination module also determines that the direction of fluorescence brightness change is the same as the direction of dye degradation based on the increase in fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the increase in the specific color channel value at the same adjacent sampling times in the dye color time series, and determines that there is an increase in the total amount of photogenerated carriers.

[0013] Furthermore, the total change determination module also determines that the direction of fluorescence brightness change is opposite to the direction of dye degradation based on the increase of fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the decrease of a specific color channel value at the same adjacent sampling times in the dye color time series, or the decrease of fluorescence brightness and the increase of a specific color channel value, and thus determines that there is no change in the total amount of photogenerated carriers.

[0014] Furthermore, the sorting instruction generation module is also used to determine the type as the unstable type based on the determination result that there is a decrease in the total number of photogenerated carriers, and to determine the sorting instruction as the rejection instruction; The sorting instruction generation module further determines the type as the photoactivated type based on the determination result that there is an increase in the total amount of photogenerated carriers, and determines the sorting instruction as the instruction to transfer to the characterization module.

[0015] Furthermore, the sorting instruction generation module also determines the screening classification type based on the judgment result that there is no change in the total amount of photogenerated carriers, based on the activity spectral response ratio, the fluorescence spectral response ratio, and the final value of the dye degradation rate constant time series corresponding to the first spectral detection; If the final value of the dye degradation rate constant time series corresponding to the first spectral detection is greater than or equal to the reference degradation rate, and the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, and the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio, the type is determined to be the qualified type, and the retention instruction is generated. If the final value of the dye degradation rate constant time series corresponding to the first spectral detection is less than the reference degradation rate, and the comparison result of the activity spectrum response ratio being greater than or equal to the reference activity spectrum response ratio and the fluorescence spectrum response ratio being greater than or equal to the reference fluorescence spectrum response ratio, the type is determined to be the bulk composite failure type, and the instruction to transfer to the characterization module is generated. If the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio, and the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, the screening classification type is determined to be the type to be reviewed, and a transfer instruction to the characterization module is generated. If the comparison result shows that the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio and the activity spectral response ratio is less than the reference activity spectral response ratio, the type is determined to be the surface reaction-hindered type, and the instruction to transport to the characterization module is generated. If the comparison result shows that the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio and the activity spectral response ratio is less than the reference activity spectral response ratio, the type is determined to be the insufficient light absorption type, and the instruction to send to the narrow bandgap optimization queue is generated.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: the photocatalytic detection module performs first and second spectral detections on the calcined sample array sequentially using a light source; fluorescence image data and visible light image data are acquired simultaneously by a fluorescence camera and a color camera; the data processing module determines the fluorescence brightness time series based on the fluorescence image data and the dye color time series based on the visible light image data; the spectral response ratio determination module determines the activity spectral response ratio based on the dye color time series and the fluorescence spectral response ratio based on the fluorescence brightness time series; the total change determination module determines whether there is a change in the total amount of photogenerated carriers based on the fluorescence brightness time series and the dye color time series; and the sorting instruction generation module determines the corresponding screening and classification type and generates sorting instructions based on the determination result of the total change in the total amount of photogenerated carriers, the activity spectral response ratio, and the fluorescence spectral response ratio. This invention employs two detection methods under different spectral conditions to determine the change in the total amount of photogenerated carriers, thereby independently extracting the stability characteristics of the sample during the detection process. This avoids misjudging the activity decay caused by photocorrosion or depletion of sacrificial agents as insufficient intrinsic material properties. Finally, by combining the determination results of three independent physical dimensions—change in the total amount of photogenerated carriers, activity spectral response ratio, and fluorescence spectral response ratio—stability anomalies and activity differences can be simultaneously identified and accurately classified. This enables multi-dimensional parallel screening of a large number of samples in a single round of detection, reducing the false rejection and false retention rates caused by a single sorting criterion, and improving screening throughput and sorting accuracy.

[0017] Furthermore, this invention determines the fluorescence brightness time series by extracting the grayscale mean of the corresponding region of each sample in the fluorescence image data and arranging it in chronological order, and extracting the specific color channel values ​​of the corresponding region of each sample in the visible light image data and arranging them in chronological order to determine the dye color time series. This allows the fluorescence response and dye concentration change of each sample in each spectral detection to be quantified into time series data with clear physical meaning, thereby providing standardized input parameters for determining the total change and calculating the spectral response ratio.

[0018] Furthermore, this invention converts the dye color time series into a dye degradation rate constant time series using a standard curve, and then uses a spectral response ratio determination module to determine the active spectral response ratio based on the dye degradation rate constant time series corresponding to the first spectral detection and the dye degradation rate constant time series corresponding to the second spectral detection, and to determine the fluorescence spectral response ratio based on the fluorescence brightness time series corresponding to the first spectral detection and the fluorescence brightness time series corresponding to the second spectral detection. This avoids the nonlinear error introduced by directly calculating the ratio using color channel values, and improves the physical interpretability and accuracy of the active spectral response ratio.

[0019] Furthermore, this invention determines the direction of fluorescence change based on the change in the average gray value of adjacent sampling times in the fluorescence brightness time series using a total change determination module, and determines the direction of dye degradation based on the change in the value of a specific color channel at the same adjacent sampling times in the dye color time series. When the value of a specific color channel decreases, it is determined that there is a decrease in the total amount of photogenerated carriers. This allows the fluorescence and degradation processes to be independently verified as being driven by the same carrier source, thereby decoupling the stability index of the change in the total amount of photogenerated carriers from the absolute value of activity, reducing the probability of misjudging the activity fluctuations caused by the change in the total amount of carriers as intrinsic properties of the material.

[0020] Furthermore, this invention, through a sorting instruction generation module, determines the screening classification type as unstable and generates a rejection instruction when it is determined that there is a decrease in the total amount of photogenerated carriers. When it is determined that there is no change in the total amount of photogenerated carriers, the corresponding screening classification type is determined based on the combination of the activity spectrum response ratio and the fluorescence spectrum response ratio. This allows stability problems to be identified and isolated first, and the physical sources of performance differences are further subdivided after stability verification. This achieves a hierarchical screening strategy of first determining stability and then diagnosing the cause of failure, avoiding the waste of resources caused by unstable samples entering the subsequent characterization stage. Attached Figure Description

[0021] Figure 1 This is a block diagram of the automated screening system for ultra-high throughput photocatalytic materials according to an embodiment of the present invention. Figure 2 This is a schematic diagram of the structure of the automated screening system for ultra-high throughput photocatalytic materials according to an embodiment of the present invention; Figure 3 A logic diagram for determining whether there is a change in the total number of photogenerated carriers in an embodiment of the present invention; Figure 4 A logic decision diagram for generating corresponding sorting instructions for embodiments of the present invention.

[0022] In the diagram, 1 is a color camera; 2 is a light source; 3 is a fluorescence camera; 4 is a multi-axis robotic arm; 5 is a conveyor belt; and 6 is a sample stage. Detailed Implementation

[0023] To make the objectives and advantages of the present invention clearer, the present invention will be further described below with reference to embodiments; it should be understood that the specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention.

[0024] Preferred embodiments of the present invention will now be described with reference to the accompanying drawings. Those skilled in the art should understand that these embodiments are merely illustrative of the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0025] It should be noted that in the description of this invention, the terms "upper", "lower", "left", "right", "inner", "outer", etc., which indicate directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings. This is only for the convenience of description and is not intended to indicate or imply that the device or element must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation of this invention.

[0026] Furthermore, it should be noted that, in the description of this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0027] Please see Figure 1 and Figure 2 As shown, Figure 1 This is a block diagram of the automated screening system for ultra-high throughput photocatalytic materials according to an embodiment of the present invention. Figure 2 This is a schematic diagram of the structure of the automated screening system for ultra-high throughput photocatalytic materials according to an embodiment of the present invention. The automated screening system in this embodiment includes a multi-channel liquid preparation module, an ultrasonic mixing module, a muffle furnace calcination module, a photocatalytic detection module, a data processing module, a total change determination module, a spectral response ratio determination module, a sorting instruction generation module, a mechanical conveying mechanism, and a characterization module.

[0028] In this embodiment, the multi-channel solution preparation module prepares the sample array to be screened based on the initial component ratio; The ultrasonic mixing module performs synchronous ultrasonic mixing on the prepared sample array to obtain a homogenized sample array. The muffle furnace roasting module roasts the mixed sample array to obtain a roasted sample array. The photocatalytic detection module performs first and second spectral detections on the calcined sample array in sequence, and the fluorescence camera 3 and the color camera 1 simultaneously acquire fluorescence image data and visible light image data, respectively. The data processing module determines the fluorescence intensity time series based on fluorescence image data, and determines the dye color time series based on visible light image data and converts it into a dye degradation rate constant time series. The total change determination module determines whether there is a change in the total amount of photogenerated carriers based on the direction of change of the same adjacent sampling time in the fluorescence brightness time series and dye color time series. The spectral response ratio determination module determines the activity spectral response ratio and the fluorescence spectral response ratio based on the dye degradation rate constant time series and the fluorescence brightness time series corresponding to the two spectral detection methods, respectively. The sorting instruction generation module determines the corresponding screening and classification type and generates sorting instructions based on the judgment result of the change in the total amount of photogenerated carriers, the activity spectrum response ratio, and the fluorescence spectrum response ratio. The mechanical conveying mechanism transfers the corresponding roasted sample from the sample stage 6 based on the sorting instruction to complete the sorting of the roasted sample; the characterization module is used to perform supplementary characterization on the transferred sample.

[0029] Specifically, the multi-channel solution preparation module is used to prepare the array of samples to be screened based on the initial component ratio.

[0030] The multi-channel solution preparation module includes a multi-channel syringe pump, raw material storage bottles, and a solution preparation robotic arm. Each channel of the multi-channel syringe pump is independently controlled, and each channel corresponds to a sample position. The solution preparation robotic arm extracts the corresponding volume of precursor solution from each raw material storage bottle according to the preset component ratio, injects it into the mixing chamber of the corresponding channel of the multi-channel syringe pump, and then distributes it to the corresponding position on the sample stage 6 after mixing.

[0031] In this embodiment, the ultrasonic mixing module is used to perform synchronous ultrasonic mixing on the prepared sample array to obtain a mixed sample array.

[0032] Specifically, the ultrasonic mixing module includes an ultrasonic cleaning tank and a sample holder. The sample holder immerses the prepared sample array in the ultrasonic cleaning tank, where the sample array is simultaneously ultrasonically mixed to ensure that the precursor solution at each sample site is thoroughly and uniformly mixed.

[0033] In this embodiment, the muffle furnace roasting module is used to roast the mixed sample array to obtain a roasted sample array.

[0034] Specifically, the muffle furnace roasting module includes a heating chamber, a temperature controller, and an atmosphere control system. The temperature controller controls the temperature inside the heating chamber, while the atmosphere control system introduces inert or oxidizing gases into the heating chamber to control the roasting atmosphere. The mixed sample array is placed into the heating chamber of the muffle furnace roasting module for roasting to obtain a roasted sample array.

[0035] It is understandable that photocatalytic reactions involve multiple sequential physical processes, including photon absorption, carrier excitation, carrier separation and transport, and surface reactions, with the final activity controlled by the slowest step. When a sample's activity is lower than expected, there are three possible physical reasons: an excessively wide band gap leading to insufficient light absorption, excessive bulk defects causing rapid nonradiative recombination of carriers, and blockage of surface active sites preventing carriers from effectively participating in the reaction. However, under single-spectral conditions, only a comprehensive activity value can be obtained, which is the combined output of the three sequential steps mentioned above. This value cannot decouple the contribution of each step and cannot accurately distinguish the specific physical reasons behind the performance differences. Therefore, it is necessary to combine dual-spectral detection with time-series change direction determination to determine the physical sources of stability and activity differences in parallel within a single round of detection.

[0036] In this embodiment, the photocatalytic detection module is used to sequentially perform first and second spectral detections on the calcined sample array. It includes a sample stage 6, a light source 2, a fluorescence camera 3, and a color camera 1. The sample stage 6 supports the calcined sample array; the light source 2 generates the full-spectrum conditions corresponding to the first spectral detection and the visible-only conditions corresponding to the second spectral detection; the fluorescence camera 3 synchronously acquires several fluorescence image data at preset sampling intervals during the first and second spectral detections; and the color camera 1 synchronously acquires several visible-light image data at preset sampling intervals during the first and second spectral detections.

[0037] The preset sampling interval is determined based on industry standards for photocatalytic degradation testing. Specifically, methylene blue concentration is measured at fixed time points after the start of illumination. In this embodiment, it is necessary to determine whether the total charge carrier quantity has changed by observing the direction of change in the dye color channel value between adjacent sampling times. The concentration change between adjacent sampling times must be recognizable by the color camera, and the number of sampling points throughout the detection cycle must be sufficient to reflect the temporal trend. Therefore, the preset sampling interval can be set to 10 minutes as an example.

[0038] Specifically, the light source 2 includes a xenon lamp source, a filter wheel, and a beam splitter. The xenon lamp source is mounted above the sample stage 6 to generate a broadband output encompassing both ultraviolet and visible light bands. The filter wheel is installed in the optical path between the xenon lamp source and the sample stage 6 and is driven to rotate by a stepper motor. The filter wheel is equipped with an ultraviolet cut-off filter and a neutral density filter. Specifically, during the first spectral detection, the stepper motor drives the filter wheel to move the ultraviolet cut-off filter out of the optical path, allowing the full-spectrum output of the xenon lamp source to be homogenized by the beam splitter before illuminating the sample stage 6. During the second spectral detection, the stepper motor drives the filter wheel to insert the ultraviolet cut-off filter into the optical path, filtering out the ultraviolet band, allowing only the visible light band to be homogenized by the beam splitter before illuminating the sample stage 6. Before the detection, the total photon flux reaching the surface of the sample stage 6 is calibrated using an optical power meter under full-spectrum and visible-only conditions. The driving current of the light source 2 is adjusted or a neutral density filter with a corresponding attenuation ratio is selected to keep the total number of incident photons equal under the two spectral conditions.

[0039] Specifically, the fluorescence camera 3 is mounted above the sample stage 6, with its lens optical axis perpendicular to the surface of the sample stage 6. A fluorescence filter is mounted in front of the lens of the fluorescence camera 3. The passband of the fluorescence filter is selected to be within the wavelength range of the dye fluorescence emission, and the stopband covers the excitation wavelength range of the light source 2. This ensures that the fluorescence camera 3 only receives the fluorescence emitted by the dye molecules after excitation and is not affected by the excitation light from the light source 2.

[0040] A color camera 1 is mounted diagonally above the sample stage 6 to acquire visible light image data. The color channel value of each pixel in the visible light image determines the degree of absorption of characteristic wavelength light by the dye at that location. Higher dye concentration results in stronger absorption of the characteristic absorption wavelength light and weaker transmission or reflection of light, leading to a lower color channel value for that wavelength; conversely, lower dye concentration results in weaker absorption and stronger transmission or reflection of light, leading to a higher color channel value for that wavelength.

[0041] Understandably, the key to distinguishing insufficient light absorption from bulk recombination or surface obstruction lies in obtaining the material's response differences to different spectral components. The band gap width of a photocatalytic material determines the lower limit of photon energy it can absorb; wide band gap materials can only absorb ultraviolet light, while narrow band gap materials can absorb both ultraviolet and visible light simultaneously. When the incident spectrum switches from the full spectrum to visible light only, wide band gap materials with insufficient light absorption lose their main excitation source due to the filtering out of the ultraviolet band, and their activity and fluorescence will decrease significantly. In contrast, materials with suitable band gaps can maintain relatively stable activity and fluorescence output before and after the spectral switch. Therefore, by obtaining the activity spectral response ratio and fluorescence spectral response ratio through dual-spectral detection, the failure mode of insufficient light absorption can be independently distinguished from other failure modes. If only a single spectral detection is performed, this information on spectral response differences cannot be obtained.

[0042] In this embodiment, the data processing module is used to determine the fluorescence brightness time series based on several fluorescence image data and to determine the dye color time series based on several visible light image data, and to convert the dye color time series into a dye degradation rate constant time series.

[0043] Specifically, the data processing module includes a fluorescence brightness extraction unit, a dye color extraction unit, and a standard curve conversion unit.

[0044] The fluorescence brightness extraction unit is used to extract the mean gray value of the corresponding region of each sample to be screened in several fluorescence image data, and arrange the mean gray values ​​at each sampling time in chronological order to obtain the fluorescence brightness time series. The region corresponding to each sample to be screened is a rectangular sub-region in the fluorescence image where the sample is located, and the mean gray value is determined based on the arithmetic mean of the gray values ​​of all pixels within the sample region.

[0045] The dye color extraction unit extracts specific color channel values ​​from the corresponding regions of each sample to be screened in several visible light image data sets, and arranges the specific color channel values ​​at each sampling time in chronological order to obtain a dye color time series. The specific color channel values ​​are determined based on the arithmetic mean of the pixel values ​​of the corresponding color channel for all pixels within the sample region.

[0046] The standard curve conversion unit converts the specific color channel values ​​at each sampling time in the dye color time series into dye degradation rate constants using a standard curve, and arranges them in chronological order to obtain a dye degradation rate constant time series. The relationship between absorbance and concentration is obtained by fitting according to the Lambert-Beer law; the concentration-degradation rate constant relationship is obtained by performing photocatalytic degradation experiments on standard solutions of known concentrations, recording the concentration decay over time, and fitting with first-order kinetics. Specifically, the absorbance-concentration standard curve is established based on spectrophotometry. The absorbance of several standard solutions of known concentrations is measured at the characteristic absorption wavelength of methylene blue, and specific color channel values ​​of each standard solution are acquired using a color camera 1 under the same conditions as spectrophotometry. Each specific color channel value is mapped one-to-one with an independently determined dye degradation rate constant, establishing a mapping in the form of a lookup table. During detection, for any measured specific color channel value, the two nearest calibration data points are retrieved through the lookup table, and the corresponding dye degradation rate constant is obtained through linear interpolation.

[0047] Among them, using the color channel values ​​of a color camera to replace the absorbance readings of a spectrophotometer for quantitative analysis is an existing application of image colorimetry. Lookup table retrieval and linear interpolation are conventional techniques in the field of numerical computation, which will not be elaborated here.

[0048] Please see Figure 3As shown, it is a logic determination diagram for determining whether there is a change in the total amount of photogenerated carriers in an embodiment of the present invention. The total amount change determination module is used to determine whether there is a change in the total amount of photogenerated carriers based on the fluorescence brightness time series and the dye color time series.

[0049] Understandably, in photocatalytic reactions, the generation of photogenerated carriers originates from photon absorption, and their consumption pathways include surface chemical reactions and radiative recombination luminescence. Fluorescence intensity determines the carrier consumption rate of the radiative recombination channel, while the dye degradation rate determines the carrier utilization rate of the surface reaction channel; both originate from the same photogenerated carrier source. When the total number of carriers remains constant, the two channels compete for the same batch of carriers. An increase in activity is necessarily accompanied by a decrease in fluorescence, and a decrease in activity is necessarily accompanied by an increase in fluorescence; their directions of change are necessarily opposite. If their directions of change are the same, it necessarily means that the total number of carriers has changed. If only the final activity value is relied upon for judgment, it is impossible to distinguish whether the low activity is due to insufficient intrinsic material properties or a decrease in the total number of carriers during the detection process.

[0050] In this embodiment, the total change determination module includes a change direction determination unit and a total change determination unit.

[0051] Specifically, the change direction determination unit is used to determine the direction of fluorescence change based on the change in the average gray value of adjacent sampling times in the fluorescence brightness time series, and to determine the direction of dye degradation based on the change in the specific color channel value of adjacent sampling times in the dye color time series. Specifically, an increase in the average gray value is determined to be an increase in fluorescence brightness, and a decrease in the average gray value is determined to be a decrease in fluorescence brightness; an increase in the specific color channel value is determined to be dye degradation, i.e., a decrease in dye concentration and an increase in the degree of degradation; a decrease in the specific color channel value is determined to be an increase in dye concentration and a decrease in the degree of degradation.

[0052] Specifically, the total change determination unit determines whether there is a change in the total amount of photogenerated carriers based on the direction of fluorescence change and the direction of dye degradation.

[0053] If the fluorescence brightness decreases and the value of a specific color channel decreases, it indicates that the decrease in fluorescence brightness and the decrease in degradation occur simultaneously, the reduction in radiative recombination and the decrease in activity are in the same direction, and the total number of charge carriers is decreasing. Determining that the direction of fluorescence brightness change is the same as the direction of dye degradation confirms the existence of a decrease in the total number of photogenerated charge carriers.

[0054] If fluorescence intensity increases and the value of a specific color channel also increases, it indicates that the increase in fluorescence intensity and the increase in degradation occur simultaneously, the increase in radiative recombination and the increase in activity are in the same direction, and the total number of charge carriers is increasing. Determining that the direction of fluorescence intensity change is the same as the direction of dye degradation confirms the existence of an increase in the total number of photogenerated charge carriers.

[0055] If fluorescence intensity increases while the value of a specific color channel decreases, or fluorescence intensity decreases while the value of a specific color channel increases, it indicates that the change in fluorescence intensity is inversely related to the change in the degree of degradation, which conforms to the conservation of charge carriers, and the total number of charge carriers remains unchanged. Determining that the direction of fluorescence intensity change is opposite to the direction of dye degradation confirms that there is no change in the total number of photogenerated charge carriers.

[0056] In this embodiment, the spectral response ratio determination module is used to determine the active spectral response ratio based on the dye degradation rate constant time series corresponding to the first spectral detection and the dye degradation rate constant time series corresponding to the second spectral detection, and to determine the fluorescence spectral response ratio based on the fluorescence brightness time series corresponding to the first spectral detection and the fluorescence brightness time series corresponding to the second spectral detection.

[0057] It is understandable that, under the premise that the total amount of charge carriers remains unchanged, the response mode of the activity parameters and fluorescence brightness to spectral changes is determined by the main loss path of the charge carriers.

[0058] In this embodiment, the spectral response ratio determination module includes an activity response ratio calculation unit and a fluorescence response ratio calculation unit.

[0059] Specifically, the activity response ratio calculation unit is used to calculate the activity spectral response ratio by comparing the final value of the dye degradation rate constant time series corresponding to the first spectral detection with the final value of the dye degradation rate constant time series corresponding to the second spectral detection. This ratio is used to determine the sensitivity of the sample activity to changes in spectral composition and to indicate the change in the carrier utilization capacity of the sample surface reaction channels after removal in the ultraviolet band. Specifically, the fluorescence response ratio calculation unit is used to calculate the fluorescence spectral response ratio by comparing the final value of the fluorescence brightness time series corresponding to the first spectral detection with the final value of the fluorescence brightness time series corresponding to the second spectral detection. This ratio is used to determine the sensitivity of the sample's radiative recombination channel to changes in spectral composition, indicating the change in the carrier consumption capacity of the radiative recombination channel after removal of the ultraviolet band.

[0060] The final value is taken as the arithmetic mean of the last preset number of sampling points in the dye degradation rate constant time series or fluorescence brightness time series. The preset number is determined based on the ratio of the preset sampling interval to the detection duration of the photocatalytic detection module, so that the time window corresponding to the sampling point used to calculate the final value is located in the latter part of the detection process. The detection duration is determined based on the industry standard for photocatalytic degradation testing. For dye photocatalytic degradation testing, a 60-minute test cycle is used to ensure that the final value is taken from the stage where the reaction has reached a steady state.

[0061] Please see Figure 4As shown, this is a logic decision diagram for generating corresponding sorting instructions in an embodiment of the present invention. The sorting instruction generation module is used to determine the corresponding screening classification type based on the judgment result of the change in the total amount of photogenerated carriers, the activity spectrum response ratio, and the fluorescence spectrum response ratio, and to generate the corresponding sorting instructions. The screening classification types include unstable type, photoactivated type, qualified type, bulk phase recombination failure type, surface reaction hindered type, type to be re-inspected type, and light absorption insufficient type. The sorting instructions include rejection instructions, transfer to characterization module instructions, retention instructions, and sending to narrow bandgap optimization queue instructions.

[0062] Understandably, the key to screening photocatalytic materials lies in simultaneously determining the physical source of both the material's stability and activity differences. If activity differences are determined first, followed by stability, unstable materials caused by photocorrosion might be misclassified as a certain type of failure, triggering unnecessary subsequent characterization. Conversely, if stability is determined first, followed by activity differences, the causes of failure can be further subdivided after stability verification. Therefore, the sorting instruction generation module adopts a hierarchical screening strategy that first determines stability and then diagnoses the causes of failure.

[0063] In this embodiment, the sorting instruction generation module includes a first determination unit, a second determination unit, and an instruction generation unit.

[0064] Specifically, the first determination unit is used to perform the first-level determination based on the determination result of the total change determination module; If a decrease in the total number of photogenerated charge carriers is detected, it indicates that fluorescence and degradation activity are decreasing in the same direction, and the total number of charge carriers is decreasing. The material is undergoing irreversible degradation under the detection conditions and is not suitable to remain in the screening queue. The screening classification type is determined to be unstable, and the instruction generation unit generates a rejection instruction.

[0065] If an increase in the total number of photogenerated charge carriers is detected, and the screening classification type is determined to be photoactivated, it indicates that fluorescence and degradation activity are increasing in the same direction, and the total number of charge carriers is increasing. This material may have potentially superior properties and needs to be transferred to the characterization module for confirmation of the activation mechanism. The instruction generation unit generates an instruction to transfer to the characterization module.

[0066] If it is determined that there is no change in the total amount of photogenerated carriers, the second determination unit is used to perform further determination based on the activity spectrum response ratio and the fluorescence spectrum response ratio. If the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, and the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio, and the final value of the dye degradation rate constant time series corresponding to the first spectral detection is greater than or equal to the reference degradation rate, it indicates that the activity and fluorescence responses to spectral changes are normal, the absolute activity under full-spectrum conditions meets the standard, and the material has no obvious abnormalities in the absorption or transport domains. In this case, the sample is retained in the screening queue to continue participating in subsequent screenings. The screening classification type is determined to be qualified, and the instruction generation unit generates a retention instruction.

[0067] If the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, and the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio, and the final value of the dye degradation rate constant time series corresponding to the first spectral detection is less than the reference degradation rate, it indicates that the activity and fluorescence responses to spectral changes are normal, but the absolute activity under full-spectrum conditions is low. The spectral response characteristics are normal, but the activity is low. The only attributable loss path for charge carriers is bulk nonradiative recombination. The screening classification type is determined to be bulk recombination failure type, and the instruction generation unit generates a transfer instruction to the characterization module.

[0068] Even without a photocatalyst, dyes will undergo photolysis under illumination due to photon absorption, resulting in a slow decrease in dye concentration. Therefore, before the formal photocatalytic degradation test, a blank test without a catalyst needs to be conducted under the same reaction conditions. Specifically, after the illumination begins, samples are taken at fixed time intervals to measure the concentration of methylene blue. The natural logarithm of the methylene blue concentration measured at the sampling time is taken and linearly regressed against time. The absolute value of the slope of the regression line is the degradation rate constant of the blank test. The degradation rate constant is set as the reference degradation rate for example.

[0069] If the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio, and the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, it indicates that the activity is not sensitive to spectral changes while the fluorescence is sensitive to spectral changes. A separation occurs between the activity and fluorescence responses to spectral changes. However, this separation does not indicate an excessively wide band gap, nor does it indicate hindered surface reactions or bulk recombination. The screening classification type is determined to be "to be reviewed." The instruction generation unit generates an instruction to transfer the data to the characterization module, which then performs supplementary characterization to confirm the physical source of this separation characteristic.

[0070] If the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio, and the activity spectral response ratio is less than the reference activity spectral response ratio, it indicates that the activity is sensitive to spectral changes but not to fluorescence, and the responses of activity and fluorescence to spectral changes are separated, indicating that charge carriers are blocked in the surface reaction process. The screening classification type is determined to be surface reaction-impeded, and the instruction generation unit generates instructions for transfer to the characterization module.

[0071] If the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio, and the activity spectral response ratio is less than the reference activity spectral response ratio, it indicates that the response of activity and fluorescence to spectral changes decreases synchronously. The removal of the ultraviolet band leads to a proportional reduction in the total number of charge carriers, and the reaction channels and radiative recombination channels shrink synchronously. This response characteristic exclusively points to insufficient light absorption caused by an excessively wide bandgap. The screening classification type is determined to be insufficient light absorption, and the instruction generation unit generates instructions to be sent to the narrow bandgap optimization queue.

[0072] The reference active spectral response ratio is determined based on the theoretical value of the active spectral response ratio. Specifically, assuming the total number of incident photons remains equal, the difference between the full spectrum and visible light only lies in the spectral composition. For a standard photocatalyst with a sufficiently narrow band gap that can adequately absorb visible light, its full-spectrum activity and visible light only activity should be nearly equal, and the theoretical value of the active spectral response ratio is 1. For example, the reference active spectral response ratio is set to 1.

[0073] Similarly, the reference fluorescence spectral response ratio is determined based on the theoretical value of the fluorescence spectral response ratio. Specifically, the total number of excitable charge carriers in the radiative recombination channel is equal under both spectral conditions. For example, the reference fluorescence spectral response ratio is set to 1.

[0074] In this embodiment, the mechanical conveying mechanism is used to receive sorting instructions and transfer the corresponding roasted sample from the sample stage 6 based on the sorting instructions to complete the sorting of the roasted sample.

[0075] Specifically, the mechanical transfer mechanism includes a multi-axis robotic arm 4 and a conveyor belt 5. The range of motion of the multi-axis robotic arm 4 covers the sample stage 6, the characterization module inlet, the narrow bandgap optimization queue preparation area, and the sample rejection area.

[0076] When the mechanical conveying mechanism receives a rejection instruction, the multi-axis robotic arm 4 transfers the corresponding sample from the sample stage 6 to the sample rejection area, and the sample is removed from the screening queue in this round.

[0077] When the mechanical transfer mechanism receives the instruction to transfer to the characterization module, the multi-axis robotic arm 4 transfers the corresponding sample from the sample stage 6 to the sample inlet of the characterization module, where the characterization module performs supplementary characterization on the sample.

[0078] When the mechanical conveying mechanism receives a retention instruction, the corresponding sample is retained on the sample stage 6 and enters the next round of screening.

[0079] When the mechanical conveying mechanism receives the instruction to send to the narrow bandgap optimization queue, the formula data of the corresponding sample is sent to the narrow bandgap optimization queue, and the multi-channel liquid preparation module will re-prepare the formula corresponding to the sample according to the optimized component ratio in the next round of liquid preparation.

[0080] In this embodiment, the characterization module is used to perform supplementary characterization on the samples transported by the mechanical conveyor. The characterization module performs corresponding characterization operations on the samples according to the screening and classification type carried in the sorting instruction.

[0081] For photoactivated samples, the characterization module performs surface photovoltage spectroscopy or transient fluorescence spectroscopy to confirm whether the light irradiation has activated new catalytic sites or induced surface reconstruction.

[0082] For bulk composite failure samples, the characterization module performs deep-level defect density characterization or impedance spectroscopy detection to confirm the type and concentration of bulk defects.

[0083] For samples with inhibited surface reactions, the characterization module performs surface elemental analysis to confirm whether there are product residues or enrichment of poisoning elements on the surface.

[0084] Understandably, the mechanical transport mechanism performs differentiated transport of samples from different screening categories. Unstable samples, due to photocorrosion or depletion of sacrificial agents, have already irreversibly deteriorated, and continuing to occupy detection or characterization resources is meaningless; therefore, they must be directly discarded. Photoactivated samples may contain photoinduced activation mechanisms, bulk composite failure samples require confirmation of bulk defect types, and surface reaction-impaired samples require confirmation of surface products or poisoning elements. These three types of samples have different failure physical mechanisms and require different characterization methods. If all abnormal samples are sent to the same characterization process without distinction, characterization resources will be evenly distributed, making it impossible to obtain the physical evidence needed for targeted diagnosis. Therefore, the mechanical transport mechanism transports samples to different subsequent processing paths based on sorting instructions, enabling characterization resources to be allocated in a targeted manner according to the failure physical mechanism.

[0085] Any techniques not mentioned in the above embodiments are applicable to existing technologies. It is understood that those skilled in the art can adjust the thresholds accordingly based on actual needs, historical data analysis, or equipment usage.

[0086] The technical solution of the present invention has been described above with reference to the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will all fall within the scope of protection of the present invention.

Claims

1. An automated screening system for ultra-high throughput photocatalytic materials, characterized in that, include: The photocatalytic detection module includes a sample stage for supporting the calcined sample array, a light source, a fluorescence camera for acquiring several fluorescence image data, and a color camera for acquiring several visible light image data, for sequentially performing first spectral detection and second spectral detection on the calcined sample array. A data processing module is used to determine a fluorescence brightness time series based on several fluorescence image data, and to determine a dye color time series based on several visible light image data; A spectral response ratio determination module is used to determine the activity spectral response ratio based on the dye color time series and the fluorescence spectral response ratio based on the fluorescence brightness time series; The total change determination module is used to determine whether there is a change in the total amount of photogenerated carriers based on the fluorescence brightness time series and the dye color time series. The sorting instruction generation module is used to determine the corresponding screening classification type based on the judgment result of the change in the total amount of photogenerated carriers, the active spectral response ratio and the fluorescence spectral response ratio, and generate the corresponding sorting instruction. The screening classification types include unstable type, photoactivated type, qualified type, bulk phase recombination failure type, surface reaction hindered type, type to be re-inspected type and insufficient light absorption type. The sorting instructions include rejection instruction, transfer to characterization module instruction, retention instruction and send to narrow bandgap optimization queue instruction. A mechanical conveying mechanism is used to receive the sorting instruction and transfer the corresponding roasted sample from the sample stage based on the sorting instruction to complete the sorting of the roasted sample.

2. The automated screening system for ultra-high throughput photocatalytic materials according to claim 1, characterized in that, The data processing module is also used to extract the corresponding grayscale mean values ​​of several fluorescence image data, and arrange the grayscale mean values ​​in chronological order to obtain the fluorescence brightness time series.

3. The automated screening system for ultra-high throughput photocatalytic materials according to claim 2, characterized in that, The data processing module is also used to extract specific color channel values ​​corresponding to several of the visible light image data, and to arrange the specific color channel values ​​in chronological order to obtain the dye color time series; The specific color channel value is the pixel value of the color channel corresponding to the characteristic absorption wavelength of the dye.

4. The automated screening system for ultra-high throughput photocatalytic materials according to claim 3, characterized in that, The data processing module also performs standard curve conversion based on the dye color time series to obtain the dye degradation rate constant time series.

5. The automated screening system for ultra-high throughput photocatalytic materials according to claim 4, characterized in that, The spectral response ratio determination module is further configured to determine the activity spectral response ratio based on the dye degradation rate constant time series corresponding to the first spectral detection and the dye degradation rate constant time series corresponding to the second spectral detection, and to determine the fluorescence spectral response ratio based on the fluorescence brightness time series corresponding to the first spectral detection and the fluorescence brightness time series corresponding to the second spectral detection.

6. The automated screening system for ultra-high throughput photocatalytic materials according to claim 5, characterized in that, The total change determination module is also used to determine the direction of fluorescence change based on the change in the average gray value of adjacent sampling times in the fluorescence brightness time series, and to determine the direction of dye degradation based on the change in the specific color channel value of adjacent sampling times in the dye color time series. The total change determination module also determines whether there is a change in the total amount of photogenerated carriers based on the direction of fluorescence change and the direction of dye degradation.

7. The automated screening system for ultra-high throughput photocatalytic materials according to claim 6, characterized in that, The total change determination module also determines that the direction of fluorescence change is the same as the direction of dye degradation based on the decrease in fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the decrease in the specific color channel value at adjacent sampling times in the dye color time series, and determines that there is a decrease in the total amount of photogenerated carriers. The total change determination module also determines that the direction of fluorescence brightness change is the same as the direction of dye degradation based on the increase in fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the increase in the specific color channel value at the same adjacent sampling times in the dye color time series, and determines that there is an increase in the total amount of photogenerated carriers.

8. The automated screening system for ultra-high throughput photocatalytic materials according to claim 7, characterized in that, The total change determination module further determines that the direction of fluorescence brightness change is opposite to the direction of dye degradation based on the increase in fluorescence brightness at adjacent sampling times in the fluorescence brightness time series and the decrease in the specific color channel value at the same adjacent sampling times in the dye color time series, or the decrease in fluorescence brightness and the increase in the specific color channel value. This ensures that there is no change in the total amount of photogenerated carriers.

9. The automated screening system for ultra-high throughput photocatalytic materials according to claim 8, characterized in that, The sorting instruction generation module is also used to determine the type as the unstable type and the sorting instruction as the rejection instruction based on the determination result that there is a decrease in the total amount of photogenerated carriers; The sorting instruction generation module further determines the type as the photoactivated type based on the determination result that there is an increase in the total amount of photogenerated carriers, and determines the sorting instruction as the instruction to transfer to the characterization module.

10. The automated screening system for ultra-high throughput photocatalytic materials according to claim 9, characterized in that, The sorting instruction generation module further determines the screening classification type based on the judgment result that there is no change in the total amount of photogenerated carriers, and the final value of the time series of the dye degradation rate constant corresponding to the first spectral detection, based on the activity spectral response ratio, the fluorescence spectral response ratio, and the first spectral detection. If the final value of the dye degradation rate constant time series corresponding to the first spectral detection is greater than or equal to the reference degradation rate, and the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, and the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio, the type is determined to be the qualified type, and the retention instruction is generated. If the final value of the dye degradation rate constant time series corresponding to the first spectral detection is less than the reference degradation rate, and the comparison result of the activity spectrum response ratio being greater than or equal to the reference activity spectrum response ratio and the fluorescence spectrum response ratio being greater than or equal to the reference fluorescence spectrum response ratio, the type is determined to be the bulk composite failure type, and the instruction to transfer to the characterization module is generated. If the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio, and the activity spectral response ratio is greater than or equal to the reference activity spectral response ratio, the screening classification type is determined to be the type to be reviewed, and a transfer instruction to the characterization module is generated. If the comparison result shows that the fluorescence spectral response ratio is greater than or equal to the reference fluorescence spectral response ratio and the activity spectral response ratio is less than the reference activity spectral response ratio, the type is determined to be the surface reaction-hindered type, and the instruction to transport to the characterization module is generated. If the comparison result shows that the fluorescence spectral response ratio is less than the reference fluorescence spectral response ratio and the activity spectral response ratio is less than the reference activity spectral response ratio, the type is determined to be the insufficient light absorption type, and the instruction to send to the narrow bandgap optimization queue is generated.

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