Rapid in-situ field coated and uncoated environmental sample photo- piezoelectric performance testing apparatus and method

Abstract

A kind of quick test equipment and method of in-situ environmental sample photo-piezoelectric performance without coating, the equipment includes electrolytic cell, electrochemical test electrode system, light source, stirrer and electrochemical workstation.Electrolytic cell is provided with sample injection hole, and natural environment sample can be directly injected, so that the sample is directly contacted with internal electrochemical test electrode system.Light source provides controllable light, and photoelectric test is carried out in cooperation with electrode system;Stirrer applies controllable mechanical shear force to sample, and completes piezoelectric test in cooperation.Electrochemical workstation is responsible for applying preset electrical signal, controlling light source opening and closing and stirrer speed, and collecting photoelectric and piezoelectric I-T curve data.The equipment is free of coating treatment sample, reduces pre-treatment time consumption, can complete test quickly on site, provides effective tool for environmental pollutant degradation mechanism research and environmental capacity assessment.

Description

TECHNICAL FIELD

[0001] The present application relates to electrochemical testing technology, in particular to a rapid test device and method for photo-piezoelectric performance of a coating-free in-situ environmental sample. BACKGROUND

[0002] In the field of environmental monitoring and pollutant degradation research and analysis, performing photo-piezoelectric performance testing on natural samples such as sediments and suspended solids is a requirement for evaluating the self-purification capacity of the environment and analyzing the degradation mechanism of pollutants under the action of the natural environment. Traditional laboratory analysis requires multiple processes such as transportation and pretreatment, which leads to sample oxidation inactivation, structural changes, and the inability to capture the carrier migration mechanism and energy conversion characteristics of the material in the original environmental state.

[0003] The traditional testing method has many technical bottlenecks: sample pretreatment is complex and time-consuming: existing technology requires uniformly mixing the powder sample with a conductive binder (such as Nafion solution) and coating it on an ITO slide, and then fixing it by evaporating ethanol to form a film. This process requires precise control of film uniformity, takes 2-3 hours, and easily causes agglomeration of nanomaterials and covering of active sites, resulting in distortion of the intrinsic photo-generated carrier separation efficiency and piezoelectric polarization response of the material. At the same time, the dynamic testing anti-interference ability of the traditional detection method is insufficient, and the traditional electrolytic cell under high speed working condition (>1000 rpm), the vortex flow field of the electrolyte causes high frequency vibration of the titanium wire connection assembly, generates current noise, seriously interferes with the signal-to-noise ratio of the piezoelectric I-T curve, and cannot accurately capture the dynamic response characteristics of the material in a high shear environment. In addition, in the traditional device, the electrolytic cell and the stirrer are simply stacked, and under high speed, resonance vibration is caused by flexible contact, resulting in a micron-level gap at the contact interface between the working electrode and the sample, thereby increasing the uncertainty of the detection result.

[0004] It should be noted that the information disclosed in the above background section is only for understanding the background of the present application, and therefore can include information that does not constitute the prior art known to those of ordinary skill in the art. SUMMARY

[0005] The main purpose of the present application is to overcome the defects in the background art, provide a rapid test device and method for photo-piezoelectric performance of a coating-free in-situ environmental sample, and rapidly test the photo-piezoelectric performance of a natural environmental sample in-situ.

[0006] To achieve the above purpose, the present application adopts the following technical solutions:

[0007] A kind of quick test equipment of in-situ environmental sample photo piezoelectric performance of free coating, including electrolytic cell, electrochemical test electrode system, light source, agitator and electrochemical workstation;The electrochemical test electrode system is arranged in the electrolytic cell, the electrolytic cell is opened sample injection hole, for directly injecting natural environment sample and making sample and the electrochemical test electrode system directly contact;The light source is used to provide controllable light on the sample in the electrolytic cell to cooperate with the electrochemical test electrode system and carry out photoelectric test;The agitator is used to apply controllable mechanical shear force to the sample in the electrolytic cell to cooperate with the electrochemical test electrode system and carry out piezoelectric test;The electrochemical workstation is used to apply preset electrical signal to the electrochemical test electrode system, control the light source and the agitator speed adjustment, and collect photoelectric I-T curve and piezoelectric I-T curve data.

[0008] Further, the electrochemical test electrode system is a three-electrode system, including a horizontally arranged working electrode, and a counter electrode and a reference electrode.

[0009] Further, the speed regulation range of the magnetic agitator is 200-1000rpm, and the electrochemical workstation controls its speed regulation in a stepwise increasing manner.

[0010] Further, it further comprises:

[0011] Liquid circulation module, including pure water pool, sewage pool and double-pass small self-priming pump, the first pass of the small self-priming pump is connected with pure water pool and electrolytic cell inlet, the second pass is connected with electrolytic cell outlet and sewage pool, to form a closed loop cleaning circuit.

[0012] Further, the device is configured with at least two independent electrolytic cells, when the first electrolytic cell performs cleaning, the second electrolytic cell synchronously performs sample injection and test.

[0013] Further, the agitator is a magnetic agitator, and the electrolytic cell shell is rigidly fixed therewith to suppress mechanical vibration under high speed working condition, form a dynamic anti-interference module, and guarantee the signal-to-noise ratio of piezoelectric test;Preferably, the electrolytic cell shell and the magnetic agitator are rigidly fixed by embedded locking mechanism, to form an anti-resonance connection architecture.

[0014] Further, the electrochemical workstation is provided with current stability detection unit, and after detecting that the current is stable in the photoelectric property test stage, the light source is controlled to be turned on.

[0015] A kind of quick test method of in-situ environmental sample photo piezoelectric performance of free coating, using the device, comprising the following steps:

[0016] (a) directly inject natural environment sample through the sample injection hole of electrolytic cell, so that the sample is directly contacted with the electrochemical test electrode system;

[0017] (b) Turn on the electrochemical workstation to apply an electrical signal, and after the current is stable, turn on the light source to collect the photoelectric I-T curve, and the stirrer remains stationary during this stage;

[0018] (c) Turn off the light source, adjust the stirrer to the target high speed and collect the piezoelectric I-T curve.

[0019] Further, the target high speed in step (c) is 200-1000 rpm, and the speed is adjusted in a stepwise increasing manner.

[0020] Further, the method further comprises the following steps:

[0021] (d) Start the small self-priming pump, and through the first passage, extract ultrapure water in the pure water pool to clean the electrolytic cell, and through the second passage, transport the waste liquid to the sewage pool for recovery;

[0022] Preferably, when the first electrolytic cell performs step (d), steps (a) to (c) are performed in the second electrolytic cell in parallel, realizing continuous in-situ testing of multiple samples;

[0023] Preferably, the stirrer operates at a low speed to assist in flushing the inner wall of the electrolytic cell and the surface of the electrode during the cleaning of step (d).

[0024] The present application has the following beneficial effects:

[0025] The present application provides a rapid testing device and method for the photo-piezoelectric performance of a coating-free in-situ environmental sample, which can measure the I-T curve of the photo-piezoelectric material of a natural sample in-situ. By directly measuring the photo-induced current response (photoelectric I-T curve) and the mechanical stress-induced current response (piezoelectric I-T curve) in-situ, the key parameters such as the degradation kinetics of pollutants can be analyzed in real time. By rapidly obtaining the intrinsic photo-piezoelectric characteristics of natural environmental samples in-situ, the time efficiency of environmental monitoring is improved, the self-purification ability of the environment under changing conditions is accurately evaluated, and the development of ecological functional materials is promoted, which has high application value.

[0026] The photo-piezoelectric performance test device and method of the embodiment of the present application have the advantages of free coating, anti-interference and supporting on-site in-situ rapid operation. The natural environment sample is directly injected through the sample injection hole at the top of the electrolytic cell, and the sample is directly contacted by using the electrochemical test electrode system, so that the problem caused by sample coating is solved; through the three-level connection structure of rigidly fixed electrolytic cell, stirrer, embedded locking working electrode and sealed pipeline, mechanical vibration under high rotation speed is effectively inhibited, and the signal-to-noise ratio of piezoelectric test is guaranteed; the automatic cleaning closed loop composed of a small self-priming pump, a pure water tank and a sewage tank is integrated, the in-situ cleaning efficiency is significantly improved, and the parallel operation of multiple electrolytic cells is supported, so that the in-situ rapid continuous test is realized. The present application reduces the time-consuming of sample pretreatment and mechanical vibration interference problem, and can complete the intrinsic photo-piezoelectric performance measurement of water and sediment samples in 5 minutes on site, provides an on-site detection tool for the degradation mechanism research of environmental pollutants and the accurate evaluation of environmental capacity, and has important value for realizing the in-situ analysis of environmental materials “sampling-test” integration and promoting the application of ecological monitoring equipment.

[0027] Other beneficial effects in the embodiment of the present application will be further described below. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 It is a whole schematic diagram of the free-coating on-site environmental sample photo-piezoelectric rapid test device of the embodiment of the present application.

[0029] Figure 2 It is a whole schematic diagram of the electrolytic cell of the embodiment of the present application.

[0030] Figure 3 It is a flow chart of the test method of the embodiment of the present application.

[0031] The drawings show that: 1, battery; 2, small self-priming pump; 3, pure water tank; 4, sewage tank; 5, electrochemical workstation; 6, working electrode; 7, electrolytic cell; 8, sample injection hole; 9, stirrer; 10, light source; 11, counter electrode; 12, reference electrode; 13, level gauge; 23, electrolytic cell shell; 24, stirring rod. DETAILED DESCRIPTION

[0032] The following will be described in detail. It should be emphasized that the following description is only exemplary and is not intended to limit the scope of the present application and its application.

[0033] It should be noted that when an element is referred to as being “fixed to” or “disposed on” another element, it can be directly on the other element or indirectly on the other element. When an element is referred to as being “connected to” another element, it can be directly connected to the other element or indirectly connected to the other element. In addition, the connection can be for fixing or for coupling or communicating.

[0034] It should be understood that the terms "length", "width", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate directions or positions based on the directions or positions shown in the drawings and are used for purposes of convenience and brevity and do not imply or suggest that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be construed as limiting the application.

[0035] In addition, the terms "first", "second", "third", etc. are used only for descriptive purposes and should not be construed as indicating or implying relative importance or an indicated number of technical features. Therefore, the features defined as "first", "second", etc. can include one or more of the features explicitly or implicitly. In the description of the embodiments of the application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0036] Referring to Figure 1 and Figure 2 , the embodiments of the application provide a rapid test device for photo piezoelectric properties of coating-free in-situ environmental samples, which comprises an electrolytic cell 7, an electrochemical test electrode system, a light source 10, a stirrer 9 and an electrochemical workstation 5. The electrochemical test electrode system is arranged in the electrolytic cell 7, the electrolytic cell 7 is provided with a sample injection hole 8 for directly injecting a natural environment sample and making the sample directly contact with the electrochemical test electrode system. The light source 10 is used to provide controllable light on the sample in the electrolytic cell 7 to cooperate with the electrochemical test electrode system to perform photoelectric test, wherein the sample generates a photo-induced current under the action of light, and the current is collected by the electrochemical test electrode system to form a photoelectric I-T curve. The stirrer 9 is used to apply controllable mechanical shear force to the sample in the electrolytic cell 7 to cooperate with the electrochemical test electrode system to perform piezoelectric test, wherein the sample generates a stress-induced current under the action of mechanical stress, and the current is collected by the electrochemical test electrode system to form a piezoelectric I-T curve. The electrochemical workstation 5 is used to apply a preset electrical signal to the electrochemical test electrode system, control the opening and closing of the light source 10 and the rotation speed adjustment of the stirrer 9, and collect photoelectric I-T curve and piezoelectric I-T curve data.

[0037] In some embodiments, the electrochemical test electrode system is a three-electrode system, which comprises a horizontally arranged working electrode 6, a counter electrode 11 and a reference electrode 12. Preferably, the horizontal distance between the counter electrode 11 and the working electrode 6 is 5-15 mm. The working electrode surface can be microstructured with grooves or roughened, and low-speed stirring can be used in the initial stage to promote uniform contact of the sample with the electrode.

[0038] In some embodiments, the magnetic stirrer has a rotation speed adjustment range of 200-1000 rpm, and the electrochemical workstation 5 controls it to adjust the rotation speed in a stepwise increasing manner to simulate a high shear environment and ensure test stability.

[0039] In some embodiments, a liquid circulation module is further included, containing a pure water tank 3, a wastewater tank 4, and a double-channel small self-priming pump 2, the first channel of which is connected to the pure water tank 3 and the inlet of the electrolytic cell 7, and the second channel is connected to the outlet of the electrolytic cell 7 and the wastewater tank 4, forming a closed-loop cleaning circuit. In the liquid circulation module, the pure water tank 3 and the wastewater tank 4 constitute a waste liquid directional recovery system driven by the small self-priming pump 2.

[0040] In some embodiments, the device is configured with at least two independent electrolytic cells 7, and when the first electrolytic cell performs cleaning, the second electrolytic cell simultaneously performs sample injection and testing. In this way, the closed-loop cleaning circuit supports parallel testing of multiple electrolytic cells.

[0041] Referring to Figure 2 In some embodiments, the stirrer 9 is a magnetic stirrer, and the electrolytic cell shell 23 is rigidly fixed thereto to suppress mechanical vibration under high rotation speed conditions, form a dynamic anti-interference module, and guarantee the signal-to-noise ratio of the piezoelectric test; the electrochemical workstation can be built-in with an adaptive filtering algorithm to deduct periodic noise related to the stirring frequency, guarantee the accuracy of the piezoelectric signal; preferably, the electrolytic cell shell 23 and the magnetic stirrer are rigidly fixed through an embedded locking mechanism to form an anti-resonance connection architecture.

[0042] In some embodiments, the electrochemical workstation 5 is provided with a current stabilization detection unit, which controls the opening of the light source 10 after detecting current stabilization during the photoelectric property test stage.

[0043] Referring to Figures 1 to 3 The present application also provides a rapid test method for the photo-piezoelectric properties of a coating-free in-situ environmental sample, which uses the device of the aforementioned embodiments, comprising:

[0044] Step a, directly injecting a natural environmental sample through the sample injection hole 8 of the electrolytic cell 7 to make the sample directly contact with the electrochemical test electrode system;

[0045] Step b, turning on the electrochemical workstation 5 to apply an electric signal, and starting the light source 10 to collect the photoelectric I-T curve after the current is stabilized, and the stirrer 9 remains stationary during this stage;

[0046] Step c, turning off the light source 10, adjusting the stirrer 9 to the target high rotation speed, and collecting the piezoelectric I-T curve. After the light source is turned off, a short period of time can be allowed for the recombination of photo-generated carriers before starting the piezoelectric test to avoid signal superposition.

[0047] The order of steps b and c is not limited.

[0048] In some embodiments, the target high rotation speed in step c is 200-1000 rpm, and the rotation speed is adjusted in a stepwise increasing manner.

[0049] In some embodiments, the method further comprises step d: starting the small self-priming pump 2 to extract ultrapure water in the pure water tank 3 to clean the electrolytic cell 7 through the first passage, and to transport waste liquid to the sewage tank 4 for recovery through the second passage. After cleaning, the background current can be detected by applying a step voltage, and if the fluctuation is greater than a set threshold, a secondary cleaning is triggered until the current is stable. Preferably, when the first electrolytic cell performs step d, steps a to c are performed in the second electrolytic cell in parallel to realize continuous in-situ testing of multiple samples;

[0050] Preferably, the agitator 9 keeps running at a low rotation speed to assist in flushing the inner wall of the electrolytic cell 7 and the surface of the electrode during step d.

[0051] The in-situ rapid testing device and method for the photo piezoelectric performance of a non-coated environmental sample according to the embodiments of the present application are performed in a natural environment, including but not limited to a test environment of soil suspension, river / lake sediments, industrial wastewater suspended particles, algae or microbial aggregates in natural water bodies.

[0052] Specifically, the device comprises a power supply and power module (battery 1 drives small self-priming pump 2), a liquid storage and circulation module (pure water tank 3 and sewage tank 4 constitute a closed-loop cleaning system), and a testing and reaction module. The core improvement is: non-coated sample processing: the sample is directly injected into the natural environment through the sample injection hole 8 at the top of the electrolytic cell 7, and the ITO glass working electrode 6 is horizontally arranged to directly contact the sample, avoiding the distortion of active sites caused by coating with traditional conductive adhesive; anti-interference dynamic testing: the electrolytic cell shell 23 is rigidly fixed with the magnetic agitator, which suppresses mechanical vibration under high rotation speed (0-1000 rpm) and ensures the signal-to-noise ratio of the piezoelectric I-T curve; efficient in-situ operation: the integrated three-electrode system (working / counter / reference electrode) and light source 10 support continuous collection of photoelectric / piezoelectric I-T curves; the small self-priming pump 2 constructs an automatic cleaning loop of "pure water tank→ electrolytic cell→ sewage tank", realizing parallel testing of multiple samples. The present application reduces the time-consuming of sample pretreatment and mechanical vibration interference, and can complete the intrinsic photo piezoelectric performance measurement of water and sediment samples in 5 minutes on site, providing an in-situ detection tool for the degradation mechanism research of environmental pollutants and the accurate assessment of environmental capacity.

[0053] The operation steps of the device include: a. placing the device horizontally on the ground or platform before testing, and observing whether the level 13 is horizontal; b. directly injecting the natural environment sample into the electrolytic cell 7 through the sample injection hole 8; c. turning on the electrochemical workstation 5 to apply an electrical signal, and starting the light source 10 after the current is stable, and collecting the photoelectric I-T curve; d. turning off the light source 10, adjusting the magnetic stirrer to the target speed, and collecting the piezoelectric I-T curve; e. starting the small self-priming pump 2 to pump the ultrapure water in the pure water pool 3 to clean the electrolytic cell, and the waste liquid is recycled to the sewage pool 4.

[0054] The test method specifically includes the following steps:

[0055] (a) Direct injection of sample: through the sample injection hole 8 at the top of the electrolytic cell 7, the natural environment sample collected in situ is directly injected into the electrolytic cell 7, so that the sample is in direct contact with the horizontally arranged ITO glass working electrode 6;

[0056] (b) Photoelectric property test: turn on the electrochemical workstation 5 to apply a preset electrical signal to the three-electrode system integrated in the electrolytic cell 7; after the response current of the working electrode 6 stabilizes, start the light source 10 to provide controllable light, and simultaneously collect and record the photo-induced current-time (photoelectric I-T) curve of the working electrode 6 by the electrochemical workstation 5; during this stage, the magnetic stirrer remains stationary;

[0057] (c) Piezoelectric property test: turn off the light source 10, adjust the speed of the magnetic stirrer to the target high speed range, and apply controllable mechanical shear force to the sample; simultaneously collect and record the stress-induced current-time (piezoelectric I-T) curve of the working electrode 6 by the electrochemical workstation 5;

[0058] (d) In-situ cleaning and waste liquid recycling: after the test is completed, start the small self-priming pump 2, pump the ultrapure water in the pure water pool 3 into the electrolytic cell 7 through the first passage of the pump for cleaning, and pump the cleaned waste liquid from the electrolytic cell 7 through the second passage of the pump to the sewage pool 4 for recycling and storage.

[0059] In step (a), the ITO glass working electrode 6 is horizontally fixed at the bottom of the electrolytic cell 7, and its surface directly contacts the injected natural environment sample without any conductive adhesive coating pretreatment.

[0060] In steps (b) and (c), the three-electrode system includes: ITO glass working electrode 6, graphite counter electrode 11, and saturated calomel reference electrode 12; the distance 27 between the graphite counter electrode 11 and the ITO glass working electrode 6 is 5-15 mm.

[0061] In step (c), the target high speed range is 200-1000 rpm, and the speed is adjusted in a stepwise increasing manner to simulate a high shear environment and ensure test stability.

[0062] In step (d), the small self-priming pump 2 is of a double-channel design, the first channel connecting the pure water tank 3 and the inlet of the electrolytic cell 7, and the second channel connecting the outlet of the electrolytic cell 7 and the waste water tank 4.

[0063] The method supports parallel operation of multiple electrolytic cells: while the first electrolytic cell performs cleaning and waste liquid recovery in step (d), sample injection and testing in steps (a) to (c) can be performed in parallel in a second electrolytic cell.

[0064] In step (d), when the small self-priming pump 2 is started to perform cleaning, the magnetic stirrer is kept running at a low speed to assist the cleaning liquid in uniformly flushing the inner wall of the electrolytic cell 7 and the surface of the electrode.

[0065] The electrochemical workstation 5 automatically performs at least one of the following functions: detects the steady state of the current and triggers the light source 10 to turn on / off, sends a command to adjust the speed of the magnetic stirrer, controls the start / stop of the small self-priming pump 2, and collects and stores the photoelectric I-T curve and piezoelectric I-T curve data in real time.

[0066] The operation details and working principles of the device are described in further detail below.

[0067] 1. In-situ deployment and environmental adaptation:

[0068] The entire set of devices (including power supply and power module, liquid storage and circulation module, testing and reaction module) is transported to the target site, such as the shore of a contaminated water body, a soil sampling point, or near an industrial discharge area. Choose a stable platform to place the device to ensure smooth operation of the magnetic stirrer. Connect the pipelines and circuits between the modules, and turn on the battery 1 to power the system.

[0069] 2. Sample injection and test start:

[0070] The operator injects the in-situ natural environment sample (such as soil suspension, water suspended particles, sediment extract, etc.) directly into the electrolytic cell 7 through the sample injection hole 8 at the top of the electrolytic cell 7. The injection amount needs to ensure that the working electrode 6 is immersed and reaches the preset liquid level. The electrochemical workstation 5 receives the operation command or the preset program signal, and automatically starts to apply a preset electrochemical test signal to the three-electrode system ITO glass working electrode 6, graphite counter electrode 11, and saturated calomel reference electrode 12 integrated in the electrolytic cell 7.

[0071] 3. Photoelectric property testing phase:

[0072] The electrochemical workstation 5 monitors the response current on the working electrode 6 in real time. Once the system detects that the current signal tends to be stable (e.g., the current fluctuation is less than a set threshold), the electrochemical workstation 5 automatically triggers or manually initiates the light source 10. The light source 10 provides light of specific wavelength and intensity on the sample in the electrolytic cell 7. The light source can use a single-color LED module and be equipped with a light filter to shield certain ultraviolet light (e.g., wavelength < 350 nm), reducing interference from organic matter decomposition. At this stage, the magnetic stirrer remains stationary to avoid mechanical stress interference. The electrochemical workstation 5 synchronously and continuously collects and records the current-time (photocurrent I-T curve) data of the working electrode 6 under light conditions, completing the in-situ rapid analysis of the sample's photo-generated carrier behavior and photo-catalytic / photo-electrochemical response.

[0073] 4. Piezoelectricity testing phase:

[0074] After the photoelectric test is completed, the electrochemical workstation 5 automatically turns off the light source 10 or receives a turn-off instruction. The electrochemical workstation 5 sends a control signal to adjust the speed of the magnetic stirrer from zero to a target high speed (usually 800-1000 rpm) in a stepwise manner, applying controllable high-intensity mechanical shear force (simulating water flow erosion, particle collision, and other environmental stresses) to the natural environment sample in the electrolytic cell 7. The electrochemical workstation 5 synchronously and continuously collects and records the current-time (piezoelectric I-T curve) data of the working electrode 6 under the action of mechanical stress, accurately capturing the polarization response and carrier transport dynamics of the piezoelectric material in the sample under high shear force environment.

[0075] 5. In-situ cleaning and waste liquid recovery:

[0076] After a single test (photoelectric + piezoelectric), the electrochemical workstation 5 stops applying the test signal, but the magnetic stirrer can be kept running at a low speed to assist subsequent cleaning uniformity.

[0077] The operator or system program starts the small self-priming pump 2. The small self-priming pump 2 receives the start signal. The ultrapure water is pumped from the pure water tank 3 through the first passage. The ultrapure water is pumped into the electrolytic cell 7 to thoroughly flush the inner wall of the electrolytic cell and the surface of the electrode. The waste liquid after flushing is extracted from the electrolytic cell 7 by the small self-priming pump 2 through the second passage and is transported to the sewage tank 4 for directional recovery and storage, avoiding secondary pollution of the on-site environment. In the configuration supporting multiple electrolytic cells, when one electrolytic cell 7 is in the above-mentioned automatic cleaning process, the operator can immediately inject a new sample into another clean standby electrolytic cell and repeat steps 2-4 to start the next round of testing, significantly improving the efficiency and throughput of in-situ continuous detection without waiting for the cleaning of a single cell to be completed.

[0078] 6. Data output and application:

[0079] The photoelectric I-T curve and piezoelectric I-T curve data collected during all tests are recorded, stored and preliminarily processed in real time by the electrochemical workstation 5. The test results (original curve or processed key parameters) can be directly viewed and in-depth analyzed through the data interface external device such as a notebook computer or a tablet computer connected with the electrochemical workstation 5. These in-situ rapidly obtained intrinsic photo-piezoelectric response data are directly used to evaluate the photocatalytic activity, piezoelectric catalytic potential, carrier separation efficiency and pollutant degradation kinetics of environmental samples (such as pollutants, natural minerals and functional materials) in the original environmental state, thereby providing immediate and reliable scientific basis for environmental remediation mechanism research and pollution source rapid diagnosis.

[0080] Workflow:

[0081] The device is aimed at the in-situ rapid testing of environmental samples, and follows the process logic of "sample injection-test-cleaning-waste liquid recovery". The specific working steps are as follows: in the sample injection stage, the operator directly injects the in-situ collected environmental sample into the electrolytic cell 7 through the sample injection hole 8 of the electrolytic cell 7. During the injection process, the sample amount is controlled to meet the testing requirements such as immersion of the electrode and reaching the specified liquid level, and the initial filling of the sample is completed. In the test execution stage, the electrochemical workstation 5 is turned on, which applies a preset electrical signal to the working electrode 6 (such as ITO glass) and the counter electrode 11 (such as a graphite electrode) in the electrolytic cell 7, and the reference electrode 12 (such as a saturated calomel electrode) provides a stable potential reference in real time. After the current value stabilizes, the light source 10 is started to create a light environment for the electrolytic cell 7 and adjust the light conditions. The electrochemical workstation 5 synchronously collects and records the electrochemical response signals between the electrodes during the test process, and completes the rapid test and analysis of the photoelectric properties of the sample. After the test is completed, the light source 10 and the electrochemical workstation 5 are turned off, and the magnetic stirrer is started to adjust the speed. The electrochemical workstation 5 synchronously collects and records the electrochemical response signals between the electrodes during the test process, and completes the rapid test and analysis of the piezoelectric properties of the sample. In the electrolytic cell cleaning stage, after the test is completed, the light source 10 and the electrochemical workstation 5 are turned off, and the magnetic stirrer is kept running at low power to assist in cleaning uniformity. The small self-priming pump 2 is started to extract ultrapure water from the ultrapure water pool 3 and deliver it to the electrolytic cell 7 through the pipeline to clean the inner wall of the electrolytic cell and the surface of the electrode. After the cleaning liquid circulates in the electrolytic cell 7 for a certain time or number of times, the small self-priming pump 2 is started again to extract the cleaned waste liquid from the electrolytic cell 7 and deliver it to the sewage pool 4 for storage, thereby completing the cleaning and waste liquid recovery of the electrolytic cell. At the same time, the next sample measurement can be carried out in another electrolytic cell without waiting for the cleaning of the current electrolytic cell to be completed. In standby / repeat test preparation, after cleaning is completed, the small self-priming pump 2 and the magnetic stirrer are turned off, and the device returns to the initial standby state. If a new in-situ sample test is to be carried out, the "sample injection-test-cleaning-waste liquid recovery" process can be repeated.

[0082] The quick test equipment and method for photo piezoelectric performance of in-situ environmental samples without coating of the embodiment of the application directly eliminates the problems of 2-3 hours of pretreatment time and distortion of active sites caused by coating of a traditional conductive adhesive through design of sample processing without coating, and retains the intrinsic characteristics of the material by direct contact of the electrode with the natural environment sample. Further, the three-stage anti-vibration architecture of the rigid fixed electrolytic cell and the stirrer effectively suppresses mechanical vibration and micron-level contact gap under high rotation speed (>1000 rpm), and guarantees the signal-to-noise ratio of the piezoelectric I-T curve in a high shear environment. Combined with the closed-loop cleaning circuit and parallel operation of multiple electrolytic cells, the "injection-photoelectric test-piezoelectric test-cleaning" whole process is continuously executed in-situ. The application can shorten the single sample test time to 5 minutes, and provides a high-fidelity and anti-interference on-site rapid detection tool for pollutant degradation kinetics research and accurate evaluation of environmental self-cleaning ability.

[0083] The above is a further detailed description of the application in combination with specific / preferred embodiments, and cannot be regarded as limiting the specific implementation of the application to these descriptions. For those of ordinary skill in the art to which the application belongs, without departing from the concept of the application, they can make several alternatives or modifications to the described embodiments, and these alternatives or modifications shall be regarded as falling within the protection scope of the application. In the description of the specification, the description of the terms "an embodiment", "some embodiments", "preferred embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in combination with the embodiment or example are included in at least one embodiment or example of the application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Those skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of different embodiments or examples without contradiction. Although the embodiments of the application and its advantages have been described in detail, it should be understood that various changes, substitutions and modifications can be made herein without departing from the scope of the patent application.

Claims

1. A kind of quick test equipment of photo piezoelectric performance in situ environment sample in situ without coating, it is characterized in that, The test device comprises an electrolytic cell (7), an electrochemical test electrode system, a light source (10), a stirrer (9), and an electrochemical workstation (5). The electrochemical test electrode system is arranged in the electrolytic cell (7), the electrolytic cell (7) is provided with a sample injection hole (8) for directly injecting a natural environment sample and directly contacting the sample with the electrochemical test electrode system; the light source (10) is used to provide controllable light on the sample in the electrolytic cell (7) to cooperate with the electrochemical test electrode system to perform photoelectric test, wherein the sample generates a photo-induced current under the action of light, and the current is collected by the electrochemical test electrode system to form a photoelectric I-T curve; the stirrer (9) is used to apply a controllable mechanical shear force to the sample in the electrolytic cell (7) to cooperate with the electrochemical test electrode system to perform piezoelectric test, wherein the sample generates a stress-induced current under the action of mechanical stress, and the current is collected by the electrochemical test electrode system to form a piezoelectric I-T curve; and the electrochemical workstation (5) is used to apply a preset electrical signal to the electrochemical test electrode system, control the opening and closing of the light source (10) and the rotation speed adjustment of the stirrer (9), and collect photoelectric I-T curve and piezoelectric I-T curve data.

2. The test apparatus of claim 1, wherein, The electrochemical test electrode system is a three-electrode system, comprising a horizontally arranged working electrode (6), and a counter electrode (11) and a reference electrode (12).

3. The test apparatus according to claim 1 or 2, characterized in that, The rotation speed adjustment range of the stirrer is 200-1000 rpm, and the electrochemical workstation (5) controls the rotation speed adjustment in a stepwise increasing manner.

4. The test apparatus according to any one of claims 1 to 2, characterized in that, Further comprising: A liquid circulation module comprising a pure water tank (3), a sewage tank (4), and a double-channel small self-priming pump (2), the first channel of the small self-priming pump (2) is connected with the pure water tank (3) and the inlet of the electrolytic cell (7), the second channel is connected with the outlet of the electrolytic cell (7) and the sewage tank (4), forming a closed loop cleaning circuit.

5. The test apparatus of claim 4, wherein, The test device is provided with at least two independent electrolytic cells (7), when the first electrolytic cell performs cleaning, the second electrolytic cell synchronously performs sample injection and test.

6. The test apparatus of any one of claims 1 to 2, wherein, The stirrer (9) is a magnetic stirrer, the electrolytic cell shell (23) is rigidly fixed with the magnetic stirrer to suppress mechanical vibration under high rotation speed working condition, form a dynamic anti-interference module, and guarantee the signal-to-noise ratio of piezoelectric test.

7. The test apparatus of claim 6, wherein, The electrolytic cell shell (23) and the magnetic stirrer are rigidly fixed through an embedded locking mechanism, forming an anti-resonance connection architecture.

8. The test apparatus of any one of claims 1 to 2, wherein, The electrochemical workstation (5) is provided with a current stability detection unit, in the photoelectric property test stage, after detecting that the current is stable, the light source (10) is controlled to be turned on.

9. A method for rapid in-situ optical piezoelectric performance testing of uncoated environmental samples in the field, using the device of any one of claims 1 to 3 and 6 to 8, characterized in that, The test device comprises the following steps: (a) directly injecting a natural environment sample through the sample injection hole (8) of the electrolytic cell (7) to directly contact the sample with the electrochemical test electrode system; (b) turning on the electrochemical workstation (5) to apply an electrical signal, starting the light source (10) to collect a photoelectric I-T curve after the current is stable, and keeping the stirrer (9) stationary in this stage; (c) turning off the light source (10), adjusting the stirrer (9) to a target high rotation speed, and collecting a piezoelectric I-T curve.

10. The test method of claim 9, wherein, The target high rotation speed in step (c) is 200-1000 rpm, and the rotation speed is adjusted in a stepwise increasing manner.

11. The test method according to claim 9 or 10, characterized in that, The test device further comprises a liquid circulation module, which includes a pure water tank (3), a waste water tank (4), and a double-channel small self-priming pump (2), the first channel of the small self-priming pump (2) is connected with the pure water tank (3) and the inlet of the electrolytic cell (7), the second channel is connected with the outlet of the electrolytic cell (7) and the waste water tank (4), forming a closed loop cleaning circuit; the test method further comprises the following steps: (d) Start the small self-priming pump (2) to clean the electrolytic cell (7) by extracting ultrapure water in the pure water tank (3) through the first channel, while delivering waste liquid to the waste water tank (4) for recovery through the second channel.

12. The test method of claim 11, wherein, The test device is configured with at least two independent electrolytic cells (7), when the first electrolytic cell performs cleaning, the second electrolytic cell synchronously performs sample injection and test; wherein, when the first electrolytic cell performs step (d), steps (a) to (c) are performed in the second electrolytic cell in parallel, realizing continuous in-situ test of multiple samples.

13. The test method of claim 11, wherein, The stirrer (9) keeps low speed operation to assist flushing the inner wall of the electrolytic cell (7) and the electrode surface during cleaning in step (d).

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