Equipment and method for rapidly testing optical-piezoelectric properties of coating-free field in-situ environment sample

Abstract

The invention relates to equipment and a method for rapidly testing optical and piezoelectric properties of a coating-free field in-situ environment sample. The equipment comprises an electrolytic tank, an electrochemical testing electrode system, a light source, a stirrer and an electrochemical workstation. The electrolytic tank is provided with a sample injection hole, and a natural environment sample can be directly injected, so that the sample is in direct contact with the internal electrochemical test electrode system. The light source provides controllable illumination and cooperates with the electrode system for photoelectric testing. And the stirrer applies controllable mechanical shearing force to the sample so as to cooperatively complete the piezoelectric test. The electrochemical work station is responsible for applying a preset electric signal, controlling on-off of a light source and the rotating speed of a stirrer and collecting photoelectric and piezoelectric I-T curve data. According to the equipment, the sample is treated without coating, the pretreatment time consumption is reduced, the test can be quickly completed on site, and an effective tool is provided for environmental pollutant degradation mechanism research and environmental capacity evaluation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrochemical testing, and 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 is prone to cause 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 test results.

[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, and to provide a rapid test device and method for photo-piezoelectric performance of a coating-free in-situ environmental sample, which can 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: A kind of quick test equipment of in-situ environmental sample photo piezoelectric performance of exempted from 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 make 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.

[0007] 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.

[0008] Further, the speed regulation range of the magnetic agitator is 200-1000 rpm, and the electrochemical workstation controls the speed regulation in a stepwise increasing manner.

[0009] Further, it further comprises: 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, and constitutes a closed loop cleaning circuit.

[0010] 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.

[0011] 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, forming an anti-resonance connection architecture.

[0012] 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.

[0013] A quick test method of in-situ environmental sample photo piezoelectric performance of exempted from coating, using the device, comprising the following steps: (a) directly injecting natural environment sample through the sample injection hole of electrolytic cell, so that the sample is directly contacted with the electrochemical test electrode system; (b) Turn on the electrochemical workstation to apply an electrical signal, and after the current is stable, start the light source to collect the photoelectric I-T curve, and the stirrer remains stationary during this stage; (c) Turn off the light source, adjust the stirrer to the target high speed, and collect the piezoelectric I-T curve.

[0014] Further, the target high speed in step (c) is 200-1000 rpm, and the speed is adjusted in a stepwise increasing manner.

[0015] Further, the method further comprises the following steps: (d) Start the small self-priming pump to extract ultrapure water in the pure water tank through the first channel to clean the electrolytic cell, and at the same time, through the second channel, the waste liquid is transported to the sewage tank for recovery; Preferably, when the first electrolytic cell performs step (d), steps (a) to (c) are performed in parallel in the second electrolytic cell, realizing continuous in-situ testing of multiple samples; 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).

[0016] The present application has the following beneficial effects: The present application provides a coating-free in-situ environmental sample light piezoelectric performance rapid testing equipment and method, which can measure the I-T curve of the light piezoelectric material of the 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 the pollutants can be analyzed in real time. By in-situ rapid acquisition of the intrinsic light piezoelectric characteristics of the natural environmental sample, 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.

[0017] The light piezoelectric performance testing equipment and method of the present application embodiment has the advantages of coating-free, anti-interference, and supporting in-situ rapid operation. The natural environmental 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, thereby solving the problem caused by sample coating; through the three-level connection structure of rigidly fixed electrolytic cell and stirrer, embedded working electrode and sealed pipeline, mechanical vibration under high speed is effectively inhibited, and the signal-to-noise ratio of piezoelectric testing is guaranteed; an 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 multiple electrolytic cells can be operated in parallel, realizing in-situ rapid continuous testing. The present application reduces the time-consuming of sample pretreatment and mechanical vibration interference, and can complete the measurement of the intrinsic light piezoelectric performance of water and sediment samples in 5 minutes on site, thereby providing an in-situ detection tool for the accurate evaluation of environmental pollutant degradation mechanism and environmental capacity, and having important value for realizing in-situ analysis of environmental material "sampling-test" integration and promoting the application of ecological monitoring equipment.

[0018] Other benefits of embodiments of the present application will be further described below. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 It is a whole schematic diagram of the on-site environment sample light piezoelectricity rapid testing device without coating of the embodiment of the present application.

[0020] Figure 2 It is a whole schematic diagram of the electrolytic cell of the embodiment of the present application.

[0021] Figure 3 It is a flow chart of the testing method of the embodiment of the present application.

[0022] Reference signs: 1, battery; 2, small self-priming pump; 3, pure water pool; 4, sewage pool; 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

[0023] The embodiments of the present application will be described in detail below. It should be emphasized that the following description is only exemplary, but not intended to limit the scope of the present application and its applications.

[0024] It should be noted that when an element is referred to as being "fixed to" or "set 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.

[0025] 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 the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the embodiments of the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0026] In addition, the terms "first", "second", "third", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second", etc. can explicitly or implicitly include one or more of the features. In the description of the embodiments of the present application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0027] Referring to Figure 1 and Figure 2 , the present application provides a kind of quick test equipment for photo piezoelectric performance of coating-free field in-situ environmental sample, including electrolytic cell 7, electrochemical test electrode system, light source 10, agitator 9 and electrochemical workstation 5;The electrochemical test electrode system is arranged in the electrolytic cell 7, the electrolytic cell 7 is opened sample hole 8, for directly injecting natural environment sample and making sample and the electrochemical test electrode system direct contact;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 and carry out photoelectric test, wherein sample generates photoelectric current under the action of light, and the current is collected by electrochemical test electrode system, and photoelectric I-T curve is formed;The agitator 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 and carry out piezoelectric test, wherein sample generates stress-induced current under the action of mechanical stress, and the current is collected by electrochemical test electrode system, and piezoelectric I-T curve is formed;The electrochemical workstation 5 is used to apply preset electrical signal to the electrochemical test electrode system, control the light source 10 opening and closing and the rotational speed adjustment of the agitator 9, and collect photoelectric I-T curve and piezoelectric I-T curve data.

[0028] In some embodiments, the electrochemical test electrode system is a three-electrode system, including horizontally arranged working electrode 6, and counter electrode 11 and reference electrode 12.It is preferred that the horizontal distance between the counter electrode 11 and the working electrode 6 is 5-15 mm.The working electrode surface can be microstructured groove or roughened, and low-speed stirring can be used in the initial stage to promote uniform contact of the sample with the electrode.

[0029] In some embodiments, the rotational speed of the magnetic agitator is adjusted in a stepwise increasing manner to simulate a high shear environment and ensure test stability.

[0030] In some embodiments, a liquid circulation module is further included, which comprises pure water tank 3, sewage tank 4 and 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, and the second channel is connected with the outlet of the electrolytic cell 7 and the sewage tank 4, forming a closed loop cleaning circuit.The pure water tank 3 and the sewage tank 4 in the liquid circulation module constitute a waste liquid directional recovery system driven by the small self-priming pump 2.

[0031] 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.Thus, the closed loop cleaning circuit supports parallel testing of multiple electrolytic cells.

[0032] Referring to Figure 2 In some embodiments, the stirrer 9 is a magnetic stirrer, and the electrolytic cell shell 23 is rigidly fixed therewith to suppress mechanical chatter in high-speed operation, form a dynamic anti-interference module, and guarantee the signal-to-noise ratio of the piezoelectric test; the electrochemical workstation can be embedded with an adaptive filtering algorithm to deduct periodic noise related to the stirring frequency and 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.

[0033] In some embodiments, the electrochemical workstation 5 is provided with a current stabilization detection unit, which controls the light source 10 to be turned on after detecting that the current is stabilized in the photoelectric property test stage.

[0034] Referring to Figures 1 to 3 The embodiments of the present application also provide a rapid test method for the photo-piezoelectric performance of a coating-free in-situ environmental sample, which uses the device of the aforementioned embodiments and comprises the following steps: Step a: a natural environmental sample is directly injected through the sample injection hole 8 of the electrolytic cell 7 so that the sample is in direct contact with the electrochemical test electrode system; Step b: the electrochemical workstation 5 is turned on to apply an electric signal, and the light source 10 is started to collect the photoelectric I-T curve after the current is stabilized; in this stage, the stirrer 9 remains stationary. Step c: the light source 10 is turned off, the stirrer 9 is adjusted to a target high speed, and the piezoelectric I-T curve is collected. After the light source is turned off, a short period of time can be allowed for the recombination of photo-generated carriers before the piezoelectric test is started again to avoid signal superposition.

[0035] The execution sequence of step b and step c is not limited.

[0036] In some embodiments, the target high speed in step c is 200-1000 rpm, and the speed is adjusted in a stepwise increasing manner.

[0037] In some embodiments, the method further comprises step d: a small self-priming pump 2 is started to pump ultrapure water in the pure water pool 3 through the first passage to clean the electrolytic cell 7, and at the same time, the waste liquid is transported to the sewage pool 4 through the second passage for recovery. After cleaning, the background current can be detected by applying a step voltage, and if the fluctuation is greater than a set threshold, a second cleaning is triggered until the current is stabilized. Preferably, when the first electrolytic cell performs step d, the second electrolytic cell performs steps a to c in parallel to realize continuous in-situ testing of multiple samples.

[0038] Preferably, the stirrer 9 keeps running at a low speed to assist in flushing the inner wall of the electrolytic cell 7 and the electrode surface during step d.

[0039] The application embodiment of the coating-free in-situ environmental sample photo-piezoelectric performance rapid testing device and method is executed in natural environment, including but not limited to soil suspension, river / lake sediment, industrial wastewater suspended particles, testing environment of algae or microbial aggregates in natural water body.

[0040] Specifically, the device comprises a power supply and power module (battery 1 drives a small self-priming pump 2), a liquid storage and circulation module (a pure water pool 3 and a sewage pool 4 constitute a closed loop cleaning system) and a testing and reaction module. The core improvement is: coating-free sample processing: a sample injection hole 8 is arranged at the top of the electrolytic cell 7 to directly inject the natural environment sample, and the ITO glass working electrode 6 arranged horizontally directly contacts the sample, avoiding the coating distortion of the active site caused by the traditional conductive adhesive coating; anti-interference dynamic testing: the electrolytic cell shell 23 is rigidly fixed with the magnetic stirrer, which suppresses mechanical vibration under high speed working condition (0-1000 rpm) and ensures the signal-to-noise ratio of the piezoelectric I-T curve; efficient in-situ operation: integrating a three-electrode system (working / counter / reference electrode) and a light source 10, supporting continuous acquisition of photoelectric / piezoelectric I-T curve; the small self-priming pump 2 constructs an automatic cleaning loop of "pure water pool→ electrolytic cell→ sewage pool", realizing parallel testing of multiple samples. The 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, providing an on-site detection tool for the degradation mechanism research of environmental pollutants and the accurate assessment of environmental capacity.

[0041] The operation steps of the device include: a. placing the device horizontally on the ground or platform before testing, and observing whether the level meter 13 is horizontal; b. directly injecting the natural environment sample into the electrolytic cell 7 through the sample injection hole 8; c. starting the light source 10 after the current is stable, and collecting the photoelectric I-T curve; d. closing 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 extract ultrapure water in the pure water pool 3 to clean the electrolytic cell, and the waste liquid is recycled to the sewage pool 4.

[0042] The testing method specifically includes the following steps: (a) Direct sample injection: through the sample injection hole 8 at the top of the electrolytic cell 7, the in-situ collected natural environment sample is directly injected into the electrolytic cell 7, so that the sample directly contacts the horizontally arranged ITO glass working electrode 6; (b) Photoelectric property testing: the electrochemical workstation 5 is turned on to apply a preset electrical signal to the three-electrode system integrated in the electrolytic cell 7; after the working electrode 6 responds to the stable current, the light source 10 is started to provide controllable light, and the photo-induced current-time (photoelectric I-T) curve of the working electrode 6 is collected and recorded by the electrochemical workstation 5; in this stage, the magnetic stirrer remains stationary; (c) Piezoelectricity test: turn off the light source 10, adjust the magnetic stirrer speed to the target high speed range, apply controllable mechanical shear force to the sample; meanwhile, collect and record the stress-induced current-time (piezoelectric I-T) curve of the working electrode 6 by the electrochemical workstation 5; (d) In-situ cleaning and waste recovery: after the test, start the small self-priming pump 2 to pump the ultrapure water in the pure water pool 3 into the electrolytic cell 7 for cleaning through the first passage, and pump the cleaned waste liquid from the electrolytic cell 7 to the sewage pool 4 for storage through the second passage.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] In step (d), the small self-priming pump 2 is a double-passage design, the first passage connects the pure water pool 3 and the inlet of the electrolytic cell 7, and the second passage connects the outlet of the electrolytic cell 7 and the sewage pool 4.

[0047] The method supports multiple electrolytic cells operating in parallel: when the first electrolytic cell performs cleaning and waste recovery in step (d), sample injection and testing in steps (a) to (c) can be performed in parallel in the second electrolytic cell.

[0048] In step (d), when the small self-priming pump 2 is started for cleaning, the magnetic stirrer is kept running at a low speed to assist the cleaning liquid to uniformly flush the inner wall of the electrolytic cell 7 and the electrode surface.

[0049] 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 instructions to adjust the speed of the magnetic stirrer, controls the start and stop of the small self-priming pump 2, and real-time collects and stores the photoelectric I-T curve and piezoelectric I-T curve data.

[0050] The operation details and working principle of the equipment are described in further detail below.

[0051] 1. In-situ deployment and environmental adaptation: The entire device (including power supply and power module, liquid storage and circulation module, test and reaction module) is transported to the target site, such as the shore of a contaminated water body, a soil sampling point, or the vicinity of an industrial discharge area. A stable platform is selected to place the device, ensuring that the magnetic stirrer works smoothly. Connect the pipelines and circuits between the modules, and turn on the battery 1 to supply power to the system.

[0052] 2. Sample injection and test initiation: The operator injects the natural environment sample (such as soil suspension, water suspended particles, sediment extract, etc.) collected on-site and in real time 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 instruction or preset program signal, automatically starts, and begins 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.

[0053] 3. Photoelectric property test phase: 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 (for example, the current fluctuation is less than a set threshold), the electrochemical workstation 5 automatically triggers or the operator manually starts the light source 10. The light source 10 provides light of a 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 filter to shield certain ultraviolet light (such as wavelength <350nm), reducing organic matter decomposition interference. In this phase, the magnetic stirrer remains stationary to avoid mechanical stress interference. The electrochemical workstation 5 synchronously and continuously collects and records the current-time (photoelectric 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 photocatalytic / photoelectrochemical response.

[0054] 4. Piezoelectric property test phase: After the photoelectric test is completed, the electrochemical workstation 5 automatically turns off the light source 10 or receives the shutdown 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, etc. environmental stress) 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 this mechanical stress, accurately capturing the polarization response and carrier transport dynamics of the piezoelectric material in the sample under high shear force environment.

[0055] 5. In-situ cleaning and waste liquid recovery: After the single test (photo + piezo) is completed, the electrochemical workstation 5 stops applying the test signal, but the magnetic stirrer can be kept running at low speed to assist the uniformity of subsequent cleaning.

[0056] 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 fully flush the inner wall and electrode surface of the electrolytic cell. 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 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.

[0057] 6. Data output and application: The photoelectric I-T curve and piezoelectric I-T curve data collected during all tests are recorded, stored and preliminarily processed by the electrochemical workstation 5 in real time. The test results (original curves or processed key parameters) can be directly viewed and deeply analyzed through external devices such as notebook computers and tablet computers connected to the data interface of the electrochemical workstation 5. These intrinsic photo-piezoelectric response data obtained in-situ and quickly 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, functional materials) in the original environmental state, providing immediate and reliable scientific basis for environmental remediation mechanism research and pollution source rapid diagnosis.

[0058] Workflow: The device is aimed at the in-situ environmental sample in the field. The process logic follows the "sample injection-test-cleaning-waste recovery" process. The specific working steps are as follows: in the sample injection stage, the operator injects the environmental sample collected in the field 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 test requirements such as immersion of the electrode, reaching the specified liquid level, and completing the initial filling of the sample. In the test execution stage, the electrochemical workstation 5 is started, 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. 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 end, the light source is turned off, the magnetic stirrer is started to adjust the speed, and 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. 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, and ultrapure water in the pure water pool 3 is pumped 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, completing the cleaning of the electrolytic cell and the recovery of the waste liquid. At the same time, the next sample measurement can be carried out in another electrolytic cell without waiting for the cleaning of the electrolytic cell to be completed. 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 needed, the "sample injection-test-cleaning-waste recovery" process can be repeated.

[0059] The rapid test equipment and method for the photo-piezoelectric properties of the coating-free in-situ environmental sample of the embodiment of the application directly eliminates the 2-3 hour pretreatment time and active site coating distortion problem caused by the traditional conductive adhesive coating through the coating-free sample processing design, and retains the intrinsic characteristics of the material by directly contacting the electrode with the natural environment sample. Further, the three-stage anti-vibration architecture of the rigidly fixed electrolytic cell and the stirrer effectively suppresses mechanical vibration and micron-level contact gap at high rotation speed (>1000 rpm), ensuring the signal-to-noise ratio of the piezoelectric I-T curve in a high shear environment. Combined with the closed-loop cleaning circuit and multi-electrolytic cell parallel operation, the "injection-photoelectric test-piezoelectric test-cleaning" whole process in-situ continuous execution is realized. The application can shorten the single sample test time to 5 minutes, providing a high-fidelity, anti-interference, in-situ rapid detection tool for pollutant degradation kinetics research and accurate evaluation of environmental self-cleaning ability.

[0060] The above further describes the present application in conjunction with specific / preferred embodiments, and cannot be deemed to limit the specific implementation of the present application to these descriptions. For those skilled in the art to which the present application belongs, without departing from the concept of the present application, they can make several substitutions or variations to the described embodiments, and these substitutions or variations shall be deemed to fall within the protection scope of the present application. In the description of the present application, the description of the terms "an embodiment", "some embodiments", "a preferred embodiment", "an example", "a specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the present application, 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 one or more embodiments or examples in a suitable manner. In the case of no mutual contradiction, those skilled in the art can combine and combine the different embodiments or examples described in the present application and the features of the different embodiments or examples. Although the embodiments of the present application and their 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 protection 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 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), and the electrolytic cell (7) is provided with a sample injection hole (8) for directly injecting a natural environment sample and bringing the sample into direct 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. Under the action of light, the sample generates a photo-induced current, which 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. Under the action of mechanical stress, the sample generates a stress-induced current, which 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.

2. The apparatus of claim 1, wherein, 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).

3. The apparatus of claim 1 or 2, wherein, 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 apparatus of any one of claims 1 to 2, wherein, 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 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 sewage tank (4), forming a closed loop cleaning circuit.

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

6. The apparatus of any one of claims 1 to 2, wherein, 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 working condition, form a dynamic anti-interference module, and ensure the signal-to-noise ratio of piezoelectric test. Preferably, the electrolytic cell shell (23) and the magnetic stirrer are rigidly fixed by an embedded locking mechanism to form an anti-resonance connection structure.

7. The 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, the light source (10) is controlled to be turned on after the detection of current stability.

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

9. The method of claim 8, wherein, The target high rotation speed in step (c) is 200-1000 rpm, and the rotation speed is adjusted in a stepwise increasing manner.

10. The method according to claim 8 or 9, characterized in that, The method further comprises the following steps: (d) starting the small self-priming pump (2) to draw the ultrapure water in the pure water tank (3) through the first passage to clean the electrolytic cell (7), and at the same time, the waste liquid is transported to the sewage tank (4) through the second passage for recovery; 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; 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 the cleaning in step (d).

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