An optically-coupled self-illuminating exchangeable plate type photocatalytic device and method

Abstract

The application discloses a self-luminous replaceable plate type photocatalytic experimental device and method with sound-light coupling reinforcement, relates to the technical field of photocatalysis, and comprises a self-luminous catalytic substrate, a reaction tank integrated with an ultrasonic transducer, an online monitoring unit and an external pumping circulation system; the self-luminous catalytic substrate is made of a semi-transparent optical fiber material and has an optical fiber guiding structure inside, can concentrate and guide external light to the inside of the substrate and uniformly transmit the light out of the surface, and serves as not only a support carrier of a catalyst but also an efficient in-situ surface light source; the ultrasonic cavitation reinforces the liquid-solid interface mass transfer and peels off a toxic layer in real time; the online monitoring unit acquires reaction efficiency data in real time and accurately guides physical replacement of the substrate according to a kinetic decay curve; the application realizes full-process zero-loss transmission of light energy and orders-of-magnitude improvement of mass transfer efficiency, solves the problem of low photocatalytic efficiency caused by limited light transmission and mass transfer bottleneck, and is suitable for evaluation of high-performance catalytic materials and research on deep treatment of high-viscosity / high-turbidity systems.

Description

Technical Field

[0001] This invention relates to the field of photocatalysis technology, specifically to a self-luminous replaceable plate photocatalytic device and method based on acoustic-optical coupling enhancement. Background Technology

[0002] Existing fixed-bed photocatalysis systems face two major bottlenecks: 1. High light transmission loss and low utilization rate: In traditional designs, external light passes through the reaction liquid and irradiates from the front of the catalyst layer. When the light is transmitted in the liquid phase, there is severe diffuse reflection loss and selective absorption (especially in high turbidity / high viscosity systems). By the time the light reaches the surface of the catalyst film, the effective light intensity has been greatly attenuated, and the uniformity of illumination is poor due to the limited thickness distribution of the film.

[0003] 2. Limited mass transfer and severe surface poisoning: The macroscopic convection maintained by the circulating pump is insufficient to break the microscopic mass transfer boundary layer on the catalyst surface, making it difficult for reactant molecules to reach the active sites, and the reaction products tend to accumulate on the membrane surface, leading to rapid deactivation (poisoning) of the catalyst membrane.

[0004] Although some studies have used porous glass plates or transparent ITO as carriers, this only solves the separation problem and does not fundamentally change the light transmission path and the interfacial mass transfer environment.

[0005] Therefore, there is an urgent need for a novel experimental platform that abandons the transmission of external light through the liquid phase, utilizes the waveguide inside the carrier to achieve in-situ surface self-luminescence, and introduces an external field to enhance interfacial mass transfer. Summary of the Invention

[0006] The main objective of this invention is to provide a self-luminous replaceable plate photocatalytic device and method based on acoustic-optical coupling enhancement, in order to solve the problems mentioned in the background art.

[0007] To achieve the above objectives, the present invention provides a self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement, comprising: The reaction tank has a chamber for holding the reaction liquid; an ultrasonic transducer is integrated at the bottom of the reaction tank to generate an ultrasonic cavitation field in the chamber. The self-luminescent catalytic substrate is made of a semi-transparent optical fiber composite material. The self-luminescent catalytic substrate has an internal optical fiber waveguide structure that guides external incident light to the main plane of the substrate. The main surface of the self-luminescent catalytic substrate is loaded with a photocatalytic material layer. The edge of the self-luminescent catalytic substrate is provided with a multimode interface for coupling with external light source and rapid positioning. The self-luminescent catalytic substrate can be detachably inserted into the reaction tank. The online monitoring unit includes a sensor probe placed inside the reaction tank to acquire the physicochemical parameters of the reaction solution in real time. An external light source system couples external excitation light into the fiber waveguide structure inside the self-emissive catalytic substrate through the multimode interface.

[0008] As a further improvement of the present invention, the top of the reaction tank is provided with a slot, and a positioning block is provided on the self-luminous catalytic substrate.

[0009] As a further improvement of the present invention, the semi-transparent optical fiber composite material includes at least one of high-transmittance quartz fiber bundle, porous glass fiber plate, or side-emitting polymer fiber array.

[0010] As a further improvement of the present invention, the multimode interface is a standardized SMA, FC or magnetic optical interface, which contains a focusing lens or an aspherical lens group.

[0011] As a further improvement of the present invention, the photocatalytic material layer is deposited in the micropores on the surface of the self-luminous catalytic substrate by sol-gel method, magnetron sputtering, electrochemical deposition or layer-by-layer self-assembly method to form a liquid-solid-light three-phase enhanced interface.

[0012] As a further improvement of the present invention, the ultrasonic transducer operates in the frequency range of 20 kHz-100 kHz, and the ultrasonic waves it generates are perpendicular to the main surface of the self-luminous catalytic substrate, which is used to induce interfacial cavitation effect to break the mass transfer boundary layer.

[0013] As a further improvement of the present invention, the method for preparing the self-emissive catalytic substrate includes the following steps: Step 1: Using a side-emitting polymer fiber (POF) array, a microporous plate with a UV-curable porous adhesive is bonded together to obtain a semi-transparent fiber composite material substrate. The substrate contains a fiber waveguide structure with uniform side-emitting light. Step 2: Integrate a multimode interface containing an SMA focusing lens group and polarization contacts at one end of the substrate; Step 3: After cleaning and drying, the active layer is deposited by sol-gel method. During the deposition process, a weak electric field is applied to induce the TiO2 precursor to assemble in an orderly manner on the POF surface. After drying and high-temperature sintering at 300 ℃ (within the tolerance range of POF) for 30 min, a self-luminous catalytic substrate based on optical fiber guidance with micropores on the surface and uniform side light emission is obtained.

[0014] This invention discloses a method for conducting a photocatalytic cycle experiment using a self-emissive replaceable plate photocatalytic device enhanced by acoustic-optic coupling, comprising the following steps: Step 1: Installation of the self-emissive catalytic substrate and activation of the acousto-optic field: The first self-emissive catalytic substrate loaded with a photocatalytic material layer is vertically inserted into the reaction tank through a slot. The external light source system and the external bias voltage source are connected through a multimode interface. At the same time, the ultrasonic transducer module at the bottom of the reaction tank is activated. The external excitation light is guided by the optical fiber waveguide in the self-emissive catalytic substrate to the surface of the self-emissive catalytic substrate for uniform transmission, making the self-emissive catalytic substrate an in-situ surface light source. The ultrasonic waves generate cavitation microjets at the interface layer of the self-emissive catalytic substrate. Step 2: In-situ field enhancement monitoring and performance assessment: The reaction kinetic curve is recorded using a sensor probe, and the data processing unit calculates the instantaneous reaction rate and activity reduction factor in real time. Step 3: Physical replacement logic trigger for self-emissive catalytic substrate: When the instantaneous rate or activity decrease factor is determined to be continuously lower than the preset activity threshold range, it is determined that the current self-emissive interface has entered an irreversible deactivation state. At this time, physical replacement of the substrate is performed: Under the premise of maintaining the liquid phase system state unchanged, the current self-emissive catalytic substrate is removed and a new or regenerated self-emissive catalytic substrate is inserted. The self-emissiveness and high activity sites of the new interface are used to force the restart of the higher-order reaction. Step 4: Repeat the above steps, using the physical cycling of the self-luminous catalytic substrate and the acoustic field to enhance mass transfer, until the reaction is complete.

[0015] In step 1, in addition to receiving external light excitation, the self-luminescent catalytic substrate also applies an external polarization bias voltage through a multi-mode interface to enhance electron-hole separation and interfacial mass transfer through acoustic-optical-electric multi-field synergy.

[0016] The beneficial effects of this invention are reflected in: 1. The ultrasonic cavitation effect can instantly break the static mass transfer boundary layer, enabling rapid renewal of reactants and products at the liquid-solid-light three-phase enhanced interface, greatly improving the kinetic constant of the deep processing process and completely solving the mass transfer bottleneck.

[0017] 2. The excitation light is transmitted losslessly inside the substrate and is emitted from the surface in situ, eliminating dead zones in light transmission. Even when treating turbid or opaque wastewater systems, it can still maintain high intensity and high uniformity of light excitation.

[0018] 3. The system is not only suitable for activity comparison, but also for optimizing process parameters of high viscosity / turbidity systems. It is also easy to integrate electrochemical (PEC) electrical pathways through multi-mode interfaces to realize acoustic-optical-electric multi-field enhancement research, and is suitable for continuous flow and multi-field synergistic testing. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the overall structure of a self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to the present invention; Explanation of reference numerals in the attached figures: 1. Self-emissive catalytic substrate; 2. Photocatalytic material layer; 3. Reaction tank; 4. Ultrasonic transducer; 5. External light source system; 6. Positioning block; 7. Fiber optic waveguide structure; 8. Sensor probe; 9. Circulation pump; 10. Liquid storage tank; 11. Circulation pipeline; 12. Multimode interface. Detailed Implementation To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the described embodiments are merely some, not all, of the embodiments of this invention. Unless otherwise specified, the embodiments and features described in this application can be combined with each other. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0020] In one embodiment, see Figure 1 The present invention provides a self-luminous replaceable plate photocatalytic device based on acoustic-optical coupling enhancement, comprising a reaction tank 3, a self-luminous catalytic substrate 1, an online inspection unit, and an external light source system 5. The reaction tank 3 contains a chamber for holding the reaction liquid, and an ultrasonic transducer 4 is integrated at the bottom of the reaction tank 3 to generate an ultrasonic cavitation field within the chamber. The self-emissive catalytic substrate 1 is made of a semi-transparent optical fiber composite material and has an internal optical fiber waveguide structure 7 that guides external incident light to the main plane of the substrate. The main surface of the self-emissive catalytic substrate 1 is loaded with a photocatalytic material layer 2. The edge of the self-emissive catalytic substrate 1 is provided with a multimode interface 12 for coupling with an external light source and for rapid positioning. The self-emissive catalytic substrate 1 can be detachably inserted into the reaction tank 3. The online monitoring unit includes a sensor probe 8 placed inside the reaction tank 3 to acquire the physicochemical parameters of the reaction liquid in real time. The external light source system 5 couples external excitation light into the optical fiber waveguide structure 7 inside the self-emissive catalytic substrate 1 through the multimode interface 12.

[0021] The top of the reaction tank 3 is provided with a slot, and the self-luminous catalytic substrate 1 is provided with a positioning block 6. After the self-luminous catalytic substrate 1 is inserted into the reaction tank 3 through the slot, the positioning block 6 is grounded with the top of the reaction tank 3, thereby restricting the position of the self-luminous catalytic substrate 1 on the reaction tank 3.

[0022] Furthermore, the semi-transparent optical fiber composite material includes at least one of high-transmittance quartz fiber bundle, porous glass fiber board, or side-emitting polymer fiber array. Its internal fiber waveguide structure 7 enables external light to be transmitted outward from the main plane loaded with catalytic material with high uniformity. The substrate is both a carrier and a surface emitting light source, which completely eliminates the reflection and absorption loss when the excitation light passes through the reaction liquid, ensuring the consistency of light intensity at the catalytic interface.

[0023] Furthermore, the multimode interface 12 is a standardized SMA, FC, or magnetic optical interface, which contains a focusing lens or aspherical lens group to improve the coupling efficiency of the external light source to the optical fiber in the substrate. Excitation light is injected externally through the SMA interface.

[0024] Furthermore, the photocatalytic material layer 2 is deposited in the micropores on the surface of the self-luminous catalytic substrate 1 by sol-gel method, magnetron sputtering, electrochemical deposition or layer-by-layer self-assembly method to form a liquid-solid-light three-phase enhanced interface.

[0025] Furthermore, the ultrasonic transducer 4 operates in the frequency range of 20 kHz-100 kHz, and the ultrasonic waves it generates are perpendicular to the main surface of the self-luminescent catalytic substrate 1. It is used to induce the interfacial cavitation effect to break the mass transfer boundary layer. The ultrasonic transducer is integrated at the bottom of the reaction tank 3. By utilizing the cavitation effect and micro-jet generated by the ultrasonic waves at the liquid-solid interface, it can not only instantly peel off the deactivated products attached to the surface, but also forcibly refresh the reactant concentration gradient of the interfacial layer, thereby improving the mass transfer efficiency to the order of magnitude.

[0026] Furthermore, the online monitoring unit has a data processing unit that can calculate the reaction rate v_t = -dC / dt in real time. Based on the instantaneous reaction rate or activity reduction factor calculated by the online monitoring sensor probe 8, it can accurately capture the "efficiency inflection point" in the catalyst deactivation process, trigger physical plate replacement, and ensure that the reaction liquid is always in contact with the highly active and highly uniformly illuminated self-luminescent interface.

[0027] A method for conducting a photocatalytic cycle experiment using a self-luminous replaceable plate photocatalytic device enhanced by acoustic-optic coupling includes the following steps: Step 1: Installation of self-emissive catalytic substrate 1 and activation of the acousto-optic field: The first self-emissive catalytic substrate 1 loaded with photocatalytic material layer 2 is vertically inserted into the reaction tank 3 through the slot. The external light source system 5 and the external bias voltage source are connected through the multimode interface 12. At the same time, the ultrasonic transducer module at the bottom of the reaction tank 3 is activated. The external excitation light is guided by the optical fiber waveguide in the self-emissive catalytic substrate 1 to the surface of the self-emissive catalytic substrate 1 and uniformly transmitted, making the self-emissive catalytic substrate 1 an in-situ surface light source. The ultrasonic waves generate cavitation microjets at the interface layer of the self-emissive catalytic substrate 1. Step 2: In-situ field enhancement monitoring and performance assessment: The reaction kinetic curve is recorded using sensor probe 8, and the data processing unit calculates the instantaneous reaction rate and activity reduction factor in real time; Step 3: Physical replacement logic trigger for self-emissive catalytic substrate 1: When the instantaneous rate or activity decrease factor is determined to be continuously lower than the preset activity threshold range, it is determined that the current self-emissive interface has entered an irreversible deactivation state. At this time, physical replacement of the substrate is performed: Under the premise of maintaining the liquid phase system state unchanged, the current self-emissive catalytic substrate 1 is removed and a new or regenerated self-emissive catalytic substrate 1 is inserted. The self-emissiveness of the new interface and the high-activity sites are used to force the restart of the higher-order reaction. Step 4: Repeat the above steps, using the physical cycling of the self-luminous catalytic substrate 1 and the acoustic field to enhance mass transfer, until the reaction is complete.

[0028] Furthermore, in step 1, in addition to receiving external light excitation, the self-luminescent catalytic substrate 1 also applies an external polarization bias voltage through the multi-mode interface 12, thereby enhancing electron-hole separation and interfacial mass transfer through the synergistic effect of acoustic-optical-electric multi-fields.

[0029] In this embodiment, a side-emitting polymer fiber (POF) array is used, which is bonded into a plate with a microporous structure using a UV-curable porous adhesive to obtain a semi-transparent fiber composite substrate. The substrate contains a fiber waveguide structure 7 that emits light uniformly from the side. A multimode interface 12 containing an SMA focusing lens group and polarization contacts is integrated at one end of the substrate. After cleaning and drying, the fiber is then bonded with a sol-gel. The active layer was deposited by gel deposition. During the deposition process, a weak electric field was applied to induce the TiO2 precursor to assemble in an orderly manner on the POF surface. After drying and high-temperature sintering at 300 °C (within the tolerance range of POF) for 30 min, a self-luminous catalytic substrate 1 based on optical fiber guidance with micropores on the surface and uniform side light emission was obtained. The self-luminescent catalytic substrate 1 is vertically inserted into a dedicated slot in the modular reaction tank 3. An external light source injection system is connected via an SMA interface. The liquid storage tank 10, circulation pump 9, circulation pipeline 11 and reaction tank 3 are connected in sequence. The ultrasonic transducer module at the bottom of the reaction tank 3 is turned on and the working frequency is set to 40 kHz. The externally injected 365 nm ultraviolet light is coupled into the POF beam inside the substrate through the multimode interface 12. The light is transmitted along the total internal reflection path and is uniformly transmitted from the translucent light-emitting surfaces on both sides of the self-luminescent catalytic substrate 1 to form an in-situ light-emitting interface, which directly irradiates and excites the active layer under the strong disturbance of the ultrasonic cavitation field. 150 mL of simulated Rhodamine B wastewater (turbid system) with a concentration of 10 mg / L and exhibiting high turbidity due to the addition of 5 g / L kaolin was injected into the system; a 300W ultraviolet light source and circulation pump 9 were turned on; online sensor probe 8 monitored in real time; after 60 min of reaction, the solution rate was monitored to be below the critical threshold of the activity reduction factor (<0.3) for 5 consecutive minutes, and the first derivative approached zero, indicating that the active sites had been completely poisoned by the product; without replacing the reaction solution, the current self-luminescent catalytic substrate 1 was directly removed from the slot and a pre-prepared new self-luminescent catalytic substrate 1 was inserted, instantly restoring the reaction system interface to a highly active, high-intensity in-situ acousto-optic coupling excitation state; the final degradation rate of Rhodamine B reached over 98%. The removed self-luminescent catalytic substrate 1 was regenerated, cleaned, and reused.

[0030] Comparative experiments show that in the treatment of turbid wastewater, the in-situ plate replacement strategy using the acoustic-optical coupling of the present invention can forcibly increase the system activity to more than 80% of the initial velocity in a single physical plate replacement. This solves the problem of total internal reflection loss of light energy caused by traditional external light penetrating high-turbidity liquids. It fully verifies that the device has core advantages such as an order-of-magnitude improvement in mass transfer efficiency, high light energy utilization efficiency, and good fidelity of experimental data in turbid, turbid systems, and deep dynamic tests.

[0031] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement, characterized in that... include: The reaction tank (3) is provided with a chamber for holding the reaction liquid; an ultrasonic transducer (4) is integrated at the bottom of the reaction tank (3) for generating an ultrasonic cavitation field in the chamber. The self-luminescent catalytic substrate (1) is made of a semi-transparent optical fiber composite material; the self-luminescent catalytic substrate (1) has an optical fiber waveguide structure (7) inside to guide external incident light to the main plane of the substrate; the main surface of the self-luminescent catalytic substrate (1) is loaded with a photocatalytic material layer (2); the edge of the self-luminescent catalytic substrate (1) is provided with a multimode interface (12) for coupling with external light source and rapid positioning; the self-luminescent catalytic substrate (1) can be detachably inserted into the reaction tank (3); The online monitoring unit includes a sensor probe (8) placed inside the reaction tank (3) for real-time acquisition of the physicochemical parameters of the reaction solution; An external light source system (5) couples external excitation light into the fiber waveguide structure (7) inside the self-luminous catalytic substrate (1) through the multimode interface (12).

2. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 1, characterized in that: The top of the reaction tank (3) is provided with a slot, and the self-luminous catalytic substrate (1) is provided with a positioning block (6).

3. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 2, characterized in that: The semi-transparent optical fiber composite material includes at least one of high-transmittance quartz fiber bundles, porous glass fiber boards, or side-emitting polymer fiber arrays.

4. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 3, characterized in that: The multimode interface (12) is a standardized SMA, FC or magnetic optical interface, which contains a focusing lens or an aspherical lens group.

5. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 4, characterized in that: The photocatalytic material layer (2) is deposited in the micropores on the surface of the self-luminous catalytic substrate (1) by sol-gel method, magnetron sputtering, electrochemical deposition or layer-by-layer self-assembly method to form a liquid-solid-light three-phase enhanced interface.

6. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 5, characterized in that: The ultrasonic transducer (4) operates in the frequency range of 20 kHz to 100 kHz. The ultrasonic waves it generates are perpendicular to the main surface of the self-luminous catalytic substrate (1) and are used to induce interfacial cavitation effect to break the mass transfer boundary layer.

7. The self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement according to claim 1, characterized in that, The method for preparing the self-luminescent catalytic substrate (1) includes the following steps: Step 1: Using a side-emitting polymer fiber (POF) array, a microporous plate is bonded together with a UV-cured porous adhesive to obtain a semi-transparent fiber composite material substrate. The substrate contains a fiber waveguide structure with uniform side emission (7). Step 2: Integrate a multimode interface (12) containing an SMA focusing lens group and polarization contacts at one end of the substrate. Step 3: After cleaning and drying, the active layer is deposited by sol-gel method. During the deposition process, a weak electric field is applied to induce the TiO2 precursor to assemble in an orderly manner on the POF surface. After drying and high-temperature sintering at 300 ℃ (within the tolerance range of POF) for 30 min, a self-luminous catalytic substrate based on optical fiber guidance with micropores on the surface and uniform side light emission is obtained (1).

8. A method for conducting an acousto-optic coupled enhanced photocatalytic cycle experiment using a self-luminous replaceable plate photocatalytic device according to any one of claims 1-6, comprising the following steps: Step 1: Installation of self-luminous catalytic substrate (1) and activation of the acousto-optic field: The first self-luminous catalytic substrate (1) loaded with photocatalytic material layer (2) is vertically inserted into the reaction tank (3) through the slot. The external light source system (5) and the external bias voltage source are connected through the multimode interface (12). At the same time, the ultrasonic transducer module at the bottom of the reaction tank (3) is activated. The external excitation light is guided by the optical fiber waveguide in the self-luminous catalytic substrate (1) to the surface of the self-luminous catalytic substrate (1) and uniformly transmitted, making the self-luminous catalytic substrate (1) an in-situ surface light source. The ultrasonic waves generate cavitation microjets at the interface layer of the self-luminous catalytic substrate (1). Step 2: In-situ field enhancement monitoring and performance assessment: The reaction kinetic curve is recorded using the sensor probe (8), and the data processing unit calculates the instantaneous reaction rate and activity reduction factor in real time; Step 3: Physical replacement logic trigger of self-luminescent catalytic substrate (1): When the instantaneous rate or activity decrease factor is continuously lower than the preset activity threshold range, it is determined that the current self-luminescent interface has entered an irreversible deactivation state. At this time, physical replacement of the substrate is performed: Under the premise of maintaining the liquid phase system state unchanged, the current self-luminescent catalytic substrate (1) is pulled out and a new or regenerated self-luminescent catalytic substrate (1) is inserted. The self-luminescence of the new interface and the high activity site are used to force the restart of the higher-order reaction. Step 4: Repeat the above steps, through the physical cycle replacement of the self-luminous catalytic substrate (1) and the enhanced mass transfer of the acoustic field, until the reaction is completed.

9. A method for conducting an acousto-optic coupled enhanced photocatalytic cycle experiment using a self-luminous replaceable plate photocatalytic device based on acousto-optic coupling enhancement, as described in claim 8, characterized in that: In step 1, the self-luminescent catalytic substrate (1) not only receives external light excitation, but also applies an external polarization bias through a multi-mode interface (12) to enhance electron-hole separation and interface mass transfer through acoustic-optical-electric multi-field synergy.

Images