A photoelectric synergistic catalytic organic dye detection-degradation integrated device based on a roller type friction nanogenerator

Abstract

The application discloses a kind of based on drum type friction nanogenerator photoelectric synergistic catalysis organic dye detection-degradation integrated device, belong to water environment management and self-driven sensing technical field.The device includes drum type friction nanogenerator, single electrode bearing assembly, illumination unit and signal acquisition unit;Drum surface is loaded titanium-based titanium dioxide nanowire array photocatalyst, single electrode bearing assembly is assembled by TiO2-PDMS composite film, copper foil, bearing and wire, and is sleeved in the outer side of drum and is opposite photocatalyst radially.The application utilizes water flow to drive drum rotation to realize self-driven power supply, through the functional coupling of TiO2-PDMS composite film and photocatalyst, simultaneously complete organic dye photocatalytic degradation and concentration real-time detection, and, device stable operation, simple preparation, strong environmental adaptability, provide a kind of self-driven, integrated intelligent management technical scheme for water organic dye pollution.

Description

Technical Field

[0001] This invention relates to the field of triboelectric nanogenerators and environmental monitoring and remediation technologies, and in particular to an integrated photoelectric synergistic catalytic detection-degradation device based on a roller-type triboelectric nanogenerator. Background Technology

[0002] With the acceleration of industrial production and urbanization, the discharge of mixed pollutants such as organic dyes and heavy metal ions into water bodies has become a prominent environmental problem. Traditional pollutant treatment technologies generally suffer from shortcomings such as limited functionality, high energy consumption, and separation of detection and degradation processes, making it difficult to meet the actual needs of efficient, real-time, and integrated treatment in complex aquatic environments.

[0003] Triboelectric nanogenerators (TENGs), as a novel energy conversion technology, can convert environmental mechanical energy such as water flow and vibration into electrical energy, providing a new approach for self-driven sensing and catalysis systems. Among them, the drum-type triboelectric nanogenerator has significant advantages in the field of mechanical energy harvesting in aquatic environments due to its stable structure and high energy output efficiency.

[0004] However, existing technologies still have significant limitations: most catalytic systems based on triboelectric nanogenerators only achieve pollutant degradation and lack synchronous detection capabilities, making it impossible to monitor degradation effects and pollutant concentration changes in real time; the interfacial bonding strength between polydimethylsiloxane (PDMS) and catalytic materials is low, and long-term water flow erosion can easily cause the catalytic layer to detach, reducing the stability of system operation; in addition, the coupling efficiency between the electrical energy output of triboelectric nanogenerators and the photocatalytic process is insufficient, resulting in a low overall energy utilization level.

[0005] Therefore, developing an integrated device that combines self-driven detection, efficient photocatalytic degradation, and stable operation to achieve real-time monitoring and simultaneous treatment of mixed pollutants has become a key technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The purpose of this invention is to provide an integrated photoelectric synergistic catalytic detection-degradation device based on a roller-type triboelectric nanogenerator, to solve the problems of separation between organic pollutant detection and degradation processes, poor interface stability, and low energy utilization efficiency in existing technologies. This invention constructs an integrated device by coupling a TiO2-PDMS composite film with a roller-type triboelectric nanogenerator, enabling simultaneous self-driven electrical signal detection and photocatalytic degradation. It possesses high-efficiency degradation performance, real-time monitoring capabilities, and good operational stability, and can be used for the detection and treatment of mixed pollutants in water bodies.

[0007] To achieve the above objectives, the present invention provides the following solution: This invention provides an integrated device for the photoelectric synergistic catalytic detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, characterized in that it comprises: Roller-type triboelectric nanogenerator, single-electrode bearing assembly, illumination unit, and signal acquisition unit; The roller-type triboelectric nanogenerator consists of a roller shell, fins (PMMA, polymethyl methacrylate), a circular acrylic plate, a conductive aluminum foil fixed friction layer, a FEP fixed friction layer (fluorinated ethylene propylene copolymer), a stainless steel rod, and a conductive copper foil.

[0008] The drum shell of the roller-type triboelectric nanogenerator is loaded with a titanium-based titanium dioxide nanowire array photocatalyst. The single-electrode bearing assembly is assembled from a TiO2-PDMS composite film, copper foil, a bearing (POM plastic full-ball bearing), and wires; it can be fixed with conductive adhesive. The single-electrode bearing assembly is fitted onto the outside of the drum of the roller-type triboelectric nanogenerator, and the TiO2-PDMS composite film is coaxially wrapped around the outside of the drum, radially opposite to the titanium-based titanium dioxide nanowire array photocatalyst loaded on the surface of the drum. The signal acquisition unit is electrically connected to the single-electrode bearing assembly via a wire to acquire triboelectric signals, thereby enabling real-time detection of organic dye concentration in the water. The illumination unit is arranged facing the surface of the roller to excite the titanium-based titanium dioxide nanowire array photocatalyst to achieve in-situ degradation of organic dyes.

[0009] The device of this invention relies on the PMMA fins of the roller-type triboelectric nanogenerator to drive the roller to rotate, converting the mechanical energy of the water flow into electrical energy. It does not require an external power source and achieves self-driven detection and photocatalytic degradation simultaneously.

[0010] Furthermore, the mass fraction of nano-titanium dioxide in the TiO2-PDMS composite film is 0 wt% to 7 wt%, and is not 0 wt%.

[0011] Furthermore, the TiO2-PDMS composite film is prepared by coating a slurry of PDMS and nano-titanium dioxide and then curing it at 80-100 °C for 1-2 h.

[0012] Furthermore, the signal acquisition unit is an electrometer, and the electrometer's electrical signal sampling frequency is 1 to 3 Hz, which is used to acquire the electrical signal generated by a single electrode in real time to realize pollutant concentration detection.

[0013] Furthermore, the illumination unit is a xenon lamp with an illumination intensity of 300–1000 W / m², used to excite the photocatalytic degradation activity of titanium dioxide nanowires.

[0014] The TiO2-PDMS composite film of the present invention has multiple functions including tribological sensing, charge conduction, auxiliary photocatalysis and structural stability: on the one hand, it acts as a tribological sensing layer to generate triboelectric signals related to pollutant concentration, realizing self-driven real-time detection; on the other hand, it relies on its own titanium dioxide component to play an auxiliary photocatalytic role, forming a photoelectric synergistic degradation system with the photocatalyst on the roller surface; at the same time, it utilizes the flexible PDMS substrate to improve water resistance, erosion resistance and interface stability.

[0015] The present invention also provides the application of the above-mentioned integrated device for photoelectric synergistic catalytic detection and degradation of organic dyes based on roller-type triboelectric nanogenerator in the catalytic degradation of organic dyes.

[0016] Furthermore, the organic dyes include methylene blue, crystal violet, or sunset yellow.

[0017] This invention also provides an integrated method for the detection and degradation of organic dyes, utilizing the aforementioned photoelectric synergistic catalytic device for the detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, comprising the following steps: The photoelectric synergistic catalytic organic dye detection-degradation integrated device based on roller triboelectric nanogenerator is placed in an aqueous solution containing organic dye to be treated. The roller triboelectric nanogenerator is driven to operate by the water flow to generate triboelectric signals. The titanium-based titanium dioxide nanowire array photocatalyst on the surface of the drum of the drum-type triboelectric nanogenerator is irradiated by the light unit to initiate a photoelectrocatalytic reaction. The signal acquisition unit collects electrical signals in real time, correlates them with changes in the concentration of organic dyes, and simultaneously completes the photocatalytic degradation of organic dyes.

[0018] The present invention discloses the following technical effects: (1) This invention enables the device to simultaneously complete the photocatalytic degradation and real-time concentration detection of organic pollutants under water flow drive by functional coupling of titanium-based titanium dioxide nanowire array and TiO2-PDMS single electrode; the degradation efficiency of organic dyes can reach more than 95%, and the average response time of the sample detected by the CNN model is less than 10 milliseconds. The overall performance is significantly better than the traditional detection and degradation phase separation processing technology.

[0019] (2) The roller-type triboelectric nanogenerator of the present invention can efficiently collect the mechanical energy of water flow and convert it into electrical energy, providing continuous power for single-electrode sensing and detection; at the same time, the titanium-based titanium dioxide nanowire array can directly use light energy to excite photocatalytic reaction. The whole system does not require external power supply, realizing energy self-sufficiency and photoelectric energy synergistic utilization.

[0020] (3) The device of the present invention has good operational stability and strong environmental adaptability. After 3,000 continuous cycles, the device can still retain more than 90% of its initial performance. At the same time, it can work stably for a long time in a wide range of water environments with a flow velocity of 0.1 to 0.5 m / s, and is applicable to a wide range of scenarios.

[0021] (4) The present invention adopts a preparation process of hydrothermal calcination combined with solution coating. The process conditions are mild, the process is simple and the parameters are controllable. Each functional component adopts a modular structure design, which is convenient to assemble and easy to mass-produce and deploy in engineering sites. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is a schematic diagram of the integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to the present invention.

[0024] Figure 2 Fourier transform infrared spectra of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1.

[0025] Figure 3 Scanning electron microscope images of the titanium-based titanium dioxide nanowire array photocatalyst prepared in Example 1: (a) is a low-magnification surface morphology image of the titanium-based titanium dioxide nanowire array; (b) is a high-magnification surface morphology image of the titanium-based titanium dioxide nanowire array; and (c) is a cross-sectional morphology image of the titanium-based titanium dioxide nanowire array.

[0026] Figure 4 Scanning electron microscope images of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1, wherein (a) is nano-TiO2 powder, (b) is pure PDMS, (c) is 1 wt% TiO2-PDMS, (d) is 3 wt% TiO2-PDMS, (e) is 5 wt% TiO2-PDMS, and (f) is 7 wt% TiO2-PDMS.

[0027] Figure 5The water contact angle test results are shown for TiO2-PDMS films prepared with different mass fractions of nano-TiO2 powder prepared in Example 1. Among them, (a) is pure PDMS, (b) is 1 wt% TiO2-PDMS, (c) is 3 wt% TiO2-PDMS, (d) is 5 wt% TiO2-PDMS, and (e) is 7 wt% TiO2-PDMS.

[0028] Figure 6 The following are electrical signal detection diagrams of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1, where (a) is a voltage-time diagram, (b) is a current-time diagram, (c) is a charge-time diagram, and (d) is the output voltage of 1 wt% TiO2-PDMS after 3000 cycles.

[0029] Figure 7 In Example 2, a 1 wt% TiO2-PDMS film was used as the negative electrode material of the detection device to detect the electrical signals of methylene blue solutions of different concentrations in the "detection-degradation" integrated experiment. Among them, (a) is the concentration gradient diagram of methylene blue solutions of different concentrations, (b) is the voltage-time diagram, (c) is the current-time diagram, and (d) is the charge-time diagram.

[0030] Figure 8 In Example 2, the methylene blue solution was degraded for 4 hours and monitored in real time during the integrated "detection-degradation" experiment. Among them, (a) is the degradation kinetic curve, (b) is the voltage of the methylene blue solution changing with degradation time, (c) is the current of the methylene blue solution changing with degradation time, and (d) is the charge of the methylene blue solution changing with degradation time.

[0031] Figure 9 In Example 3, a 1 wt% TiO2-PDMS film was used as the negative electrode material of the detection device to detect the electrical signals of Sunset Yellow solutions of different concentrations in the "detection-degradation" integrated experiment. Among them, (a) is the concentration gradient diagram of Sunset Yellow solutions of different concentrations, (b) is the voltage-time diagram, (c) is the current-time diagram, and (d) is the charge-time diagram.

[0032] Figure 10 In Example 3, the Sunset Yellow solution was degraded for 4 hours and monitored in real time during the integrated "detection-degradation" experiment. Among them, (a) is the degradation kinetic curve, (b) is the voltage of Sunset Yellow solution changing with degradation time, (c) is the current of Sunset Yellow solution changing with degradation time, and (d) is the charge of Sunset Yellow solution changing with degradation time.

[0033] Figure 11In Example 4, a 1 wt% TiO2-PDMS film was used as the negative electrode material of the detection device to detect the electrical signals of crystal violet solutions of different concentrations in an integrated "detection-degradation" experiment. Among them, (a) is the concentration gradient diagram of crystal violet solutions of different concentrations, (b) is the voltage-time diagram, (c) is the current-time diagram, and (d) is the charge-time diagram.

[0034] Figure 12 In Example 4, the crystal violet solution was degraded for 4 hours and monitored in real time during the integrated "detection-degradation" experiment. Among them, (a) is the degradation kinetic curve, (b) is the voltage of the crystal violet solution changing with degradation time, (c) is the current of the crystal violet solution changing with degradation time, and (d) is the charge of the crystal violet solution changing with degradation time.

[0035] Figure 13 The pseudo-first-order kinetics of the degradation of three organic dyes over 4 hours were fitted in the integrated "detection-degradation" experiment of Examples 2 and 3-4.

[0036] Figure 14 The training (a) and testing (b) iteration curves, single-sample continuous prediction response time curve (c), and response time distribution histogram (d) of the CNN-1D model constructed by mixing methylene blue, sunset yellow, and crystal violet in Examples 2-4 are shown.

[0037] Figure 15 The confusion matrix (a) shows the accuracy of CNN-1D for different types of organic dyes in Examples 2 and 3-4, and the three-dimensional waterfall plot of output voltage-time for organic dyes under different label types (b).

[0038] Figure 16 Mechanical properties of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1 were tested. Detailed Implementation

[0039] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0040] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included within the scope of this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0041] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0042] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0043] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0044] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0045] In a first aspect, the present invention provides an integrated device for the photoelectric synergistic catalytic detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, characterized in that it comprises: Roller-type triboelectric nanogenerator, single-electrode bearing assembly, illumination unit, and signal acquisition unit; The roller-type triboelectric nanogenerator comprises a roller shell, fins (PMMA, polymethyl methacrylate), a circular acrylic plate, a conductive aluminum foil fixed friction layer, a FEP fixed friction layer (fluorinated ethylene propylene copolymer), a stainless steel rod, and a conductive copper foil. The surface of the roller shell of the roller-type triboelectric nanogenerator is loaded with a titanium-based titanium dioxide nanowire array photocatalyst. The single-electrode bearing assembly is assembled from a TiO2-PDMS composite film, copper foil, bearing, and wires; it can be fixed with conductive adhesive. The single-electrode bearing assembly is fitted onto the outside of the drum of the roller-type triboelectric nanogenerator, and the TiO2-PDMS composite film is coaxially wrapped around the outside of the drum, radially opposite to the titanium-based titanium dioxide nanowire array photocatalyst loaded on the surface of the drum. The signal acquisition unit is electrically connected to the single-electrode bearing assembly via a wire to acquire triboelectric signals, thereby enabling real-time detection of organic dye concentration in the water. The illumination unit is arranged facing the surface of the roller to excite the titanium-based titanium dioxide nanowire array photocatalyst to achieve in-situ degradation of organic dyes.

[0046] The device of this invention relies on the PMMA fins of the roller-type triboelectric nanogenerator to drive the roller to rotate, converting the mechanical energy of the water flow into electrical energy. It does not require an external power source and achieves self-driven detection and photocatalytic degradation simultaneously.

[0047] Preferably, the mass fraction of nano-titanium dioxide in the TiO2-PDMS composite film is 0 wt% to 7 wt%, and is not 0 wt%.

[0048] Preferably, the TiO2-PDMS composite film is prepared by coating a slurry of PDMS and nano-titanium dioxide and then curing it at 80-100 °C for 1-2 h.

[0049] Preferably, the signal acquisition unit is an electrometer, and the electrometer's electrical signal sampling frequency is 1 to 3 Hz, used to acquire the electrical signal generated by a single electrode in real time to realize pollutant concentration detection.

[0050] Preferably, the illumination unit is a xenon lamp with an illumination intensity of 300–1000 W / m², used to excite the photocatalytic degradation activity of titanium dioxide nanowires.

[0051] Preferably, in this invention, the titanium-based titanium dioxide nanowire array photocatalyst can be prepared using the following steps: Industrial pure titanium foil is immersed in anhydrous ethanol or acetone and ultrasonically cleaned at 50-70 ℃ for 8-15 min. After cleaning, it is immersed in an etching solution for micro-thinning and surface texturing treatment. The treated titanium foil was immersed in a hydrothermal reaction mixture containing 1-5 mol / L sodium hydroxide and graphene quantum dot solution (0.25-1 g / L), and then transferred to a stainless steel reactor with a polyphenol (PPL) liner. The reaction was carried out in an oven at 200-220℃ for 18-24 h. After cooling to room temperature, the foil was removed and rinsed with deionized water to obtain the intermediate product Na2Ti3O7•H2O nanowire film. The prepared intermediate product Na2Ti3O7•H2O nanowire film was immersed in 0.1-1 mol / L dilute hydrochloric acid or 0.1-1 mol / L dilute nitric acid solution for 5-10 min to obtain the intermediate product H2Ti3O7•H2O nanowire film. The prepared H2Ti3O7•H2O nanowire film was calcined in air in a muffle furnace at 500-600 ℃ for 1-2 h, and then naturally cooled to room temperature to obtain a one-dimensional ordered titanium-based titanium dioxide nanowire array film, which can be used as a photocatalyst. Preferably, the titanium dioxide nanowires grow in a one-dimensional normal direction without two-dimensional or branched structures; the nanowires are well separated from each other, uniformly distributed without agglomeration; the diameter range is 15-25 nm, the length range is 10-15 μm, and the thickness is about 8-10 μm. Preferably, the purity of the industrial pure titanium foil is not less than 99%, and it can also be elemental titanium such as titanium mesh, titanium plate, titanium block, titanium particles, or titanium microspheres.

[0052] Preferably, the etching solution is a mixed solution containing 3-6 mol / L hydrogen peroxide, 1-3 mol / L ammonium fluoride, and 2-4 mol / L nitric acid; or a mixed solution containing 2-4 mol / L nitric acid and 1-2.5 mol / L hydrofluoric acid.

[0053] Preferably, the graphene quantum dot solution is prepared using a small molecule sugar carbon source, such as glucose, fructose, sucrose, etc. 0.1-0.5 mol of this carbon source is transferred to a hydrothermal reactor with a polyphenol (PPL) or polytetrafluoroethylene (PTFE) liner, reacted in an oven at 180-200 °C for 10-12 h and then cooled to room temperature. After the hydrothermal reaction, the solution is filtered and centrifuged to separate a brownish-yellow or yellow supernatant.

[0054] In the single-electrode bearing assembly of the present invention, copper foil serves as a conductive substrate, and TiO2-PDMS composite film serves as a negative electrode material and a friction layer. The two are tightly bonded together by conductive silver paste to ensure stable electrical signal transmission.

[0055] Preferably, nano-titanium dioxide powder with different mass fractions (0-7 wt%) is mixed with polydimethylsiloxane (PDMS), and then ultrasonically dispersed for 3-5 min and mechanically stirred for 3-5 min to obtain a uniform TiO2-PDMS composite slurry.

[0056] Preferably, the water flow velocity is 0.1-0.5 m / s, used to drive the drum to rotate and wash the surface of the single electrode bearing assembly.

[0057] The present invention also provides the application of the above-mentioned integrated device for photoelectric synergistic catalytic detection and degradation of organic dyes based on roller-type triboelectric nanogenerator in the catalytic degradation of organic dyes.

[0058] Preferably, the organic dye includes methylene blue, crystal violet, or sunset yellow.

[0059] This invention also provides an integrated method for the detection and degradation of organic dyes, utilizing the aforementioned photoelectric synergistic catalytic device for the detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, comprising the following steps: The photoelectric synergistic catalytic organic dye detection-degradation integrated device based on roller triboelectric nanogenerator is placed in an aqueous solution containing organic dye to be treated. The roller triboelectric nanogenerator is driven to operate by the water flow to generate triboelectric signals. The titanium-based titanium dioxide nanowire array photocatalyst on the surface of the drum of the drum-type triboelectric nanogenerator is irradiated by the light unit to initiate a photoelectrocatalytic reaction. The signal acquisition unit collects electrical signals in real time, correlates them with changes in the concentration of organic dyes, and simultaneously completes the photocatalytic degradation of organic dyes.

[0060] The device of this invention operates as follows: water flow washes the fins to drive the drum to rotate, while light simulates sunlight to irradiate the titanium dioxide nanowire catalyst on the surface of the drum, thereby achieving pollutant degradation; the single-electrode bearing assembly is washed by the liquid to generate an electrical signal, and the electrical signal is collected by an electrometer to achieve pollutant detection, thus completing the integrated detection-degradation process.

[0061] This invention ingeniously introduces a titanium-based titanium dioxide nanowire array as the core photocatalytic unit, and simultaneously utilizes a TiO2-PDMS composite film and copper foil to construct a single-electrode sensing layer, thus realizing the integrated dual function of catalytic degradation and self-driven sensing designed in this invention. Details are as follows: (1) Photocatalytic degradation: Titanium-based titanium dioxide nanowire arrays have high specific surface area and excellent photocatalytic activity. Under simulated sunlight irradiation, they can efficiently generate photogenerated carriers and directly participate in the redox degradation of mixed pollutants in water. At the same time, their one-dimensional ordered structure provides sufficient adsorption and reaction sites for pollutant molecules.

[0062] (2) Self-driven sensing: The TiO2-PDMS composite film, as the core layer of the single electrode, can generate triboelectric signals with the liquid as a friction layer, providing self-driven energy for detection. On the other hand, the TiO2 nanoparticles on its surface can interact specifically with pollutants, and reflect the changes in pollutant concentration in real time through changes in electrical signals, so as to achieve accurate detection.

[0063] Through this integrated "detection-degradation" design strategy, the titanium dioxide nanowire array and the TiO2-PDMS single electrode are tightly coupled at the functional level, while the entire device system is supported and driven by the mechanical structure of the roller-type triboelectric nanogenerator. This design creates a highly integrated device that is self-powered and functionally synergistic, fundamentally solving the problems of separation of detection and degradation, poor interface stability, and low energy utilization efficiency in traditional technologies.

[0064] This invention innovatively proposes an integrated detection-degradation design concept, which selects titanium-based titanium dioxide nanowire arrays as highly efficient photocatalytic functional materials, and uses TiO2-PDMS composite films and copper foil to synergistically construct a single-electrode sensing unit.

[0065] Specifically, this invention uses a titanium-based substrate as the base, and prepares a high aspect ratio titanium dioxide nanowire array through a hydrothermal reaction combined with high-temperature calcination. This material possesses a large specific surface area and excellent photocatalytic activity, providing sufficient reactive sites for the degradation of organic pollutants. Simultaneously, the TiO2-PDMS composite film, as the core functional layer of the single electrode, can act as both a triboelectric sensing layer interacting with water flow to generate characteristic electrical signals and an auxiliary catalytic layer participating in pollutant degradation. This dual-functional design organically couples the detection and degradation processes at the structural level, constructing a highly integrated functional device system.

[0066] This invention fundamentally overcomes the shortcomings of traditional treatment devices, such as the separation of detection and degradation, weak bonding at composite interfaces, and poor long-term operational stability, through the rational design of the material interface microstructure. Simultaneously, the roller-type triboelectric nanogenerator converts mechanical energy into electrical energy using natural water flow, providing self-powered energy for single-electrode sensing. Under illumination, photogenerated carriers generated by titanium dioxide nanowires can directly participate in the oxidative degradation reaction of organic pollutants, enabling the entire system to achieve efficient energy utilization and multifunctional synergistic effects.

[0067] The integrated device constructed in this invention has excellent organic pollutant degradation efficiency and real-time concentration detection capability, while also possessing good mechanical structural stability and adaptability to complex aquatic environments. It can provide a novel, energy-saving, and self-driven integrated technical solution for the treatment of mixed pollutants such as organic dyes in water bodies.

[0068] Example 1: Preparation of TiO2-PDMS composite thin film and assembly of single-electrode bearing assembly An integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator is prepared and assembled according to the following steps: Step S1: Preparation of titanium-based titanium dioxide nanowire array photocatalyst (1) Immerse industrial pure titanium foil in anhydrous ethanol or acetone and ultrasonically clean it for 8-15 minutes at 50-70 ℃ to remove surface oil and impurities; after cleaning, immerse the titanium foil in etching solution for micro-thinning and surface roughening treatment; after treatment, rinse it with deionized water and air dry. (2) The titanium foil treated above is immersed in a mixed hydrothermal reaction solution containing 1-5 mol / L sodium hydroxide and 0.25-1 g / L graphene quantum dot solution; then the titanium foil and the mixed solution are transferred together to a stainless steel reactor with a polyphenol (PPL) liner and placed in an oven at 200-220 ℃ for constant temperature reaction for 18-24 h; (3) After the reaction is complete, the reactor is cooled to room temperature, the titanium foil is removed, and the surface residual solution is repeatedly rinsed with deionized water to obtain the intermediate product Na2Ti3O7•H2O nanowire film. (4) Immerse the prepared Na2Ti3O7•H2O nanowire film in 0.1-1 mol / L dilute hydrochloric acid or 0.1-1 mol / L dilute nitric acid solution for 5-10 min for acidification treatment to obtain the intermediate product H2Ti3O7・H2O nanowire film; (5) The acidified Na2Ti3O7•H2O nanowire film was placed in a muffle furnace at 500-600 ℃ and calcined in air atmosphere for 1-2 h. After calcination, it was naturally cooled to room temperature to obtain a one-dimensional ordered titanium-based titanium dioxide nanowire array film, which was used as a photocatalyst.

[0069] Step S2: Preparation of TiO2-PDMS composite thin film (1) Take 5.5 g of polydimethylsiloxane (PDMS) and add nano titanium dioxide powder with a mass fraction of 1 wt%, 3 wt%, 5 wt% and 7 wt%, respectively. After mixing, perform ultrasonic dispersion and mechanical stirring to obtain a uniform slurry. (2) The mixed slurry is uniformly coated on the surface of the acrylic sheet and heated and cured in an oven at 100°C for 1 hour to obtain TiO2-PDMS composite film.

[0070] Step S3: Assemble the single-electrode bearing assembly The obtained TiO2-PDMS composite film and copper foil were assembled together on a bearing with an inner diameter of 55 mm that matched the inner diameter of the drum. The wires were connected and sealed with waterproof glue to obtain a single-electrode bearing assembly.

[0071] Step S4: Integrated assembly of the entire machine (1) An acrylic cylindrical shell is used as the main body of the roller-type triboelectric nanogenerator; a triboelectric power generation system consisting of a conductive aluminum foil fixed friction layer, an FEP fixed friction layer, a conductive copper foil and a stainless steel rod is arranged inside the roller shell; a circular acrylic plate matching the outer diameter radius of the roller is selected and the two ends of the roller are sealed with waterproof glue; PMMA fins are attached and fixed at equal intervals around one end of the outer side of the roller, and the prepared titanium-based titanium dioxide nanowire array photocatalyst is loaded and fixed on the surface of the other end of the outer side of the roller to complete the assembly of the main structure of the roller-type triboelectric nanogenerator.

[0072] (2) The single electrode bearing assembly is sleeved on the outside of the drum of the roller-type triboelectric nanogenerator, and the TiO2-PDMS composite film is coaxially wrapped around the outside of the drum, and is radially opposite to the titanium-based titanium dioxide nanowire array photocatalyst loaded on the surface of the drum.

[0073] The aforementioned integrated device is placed in a glass tank, and the single-electrode bearing assembly is connected to an electrometer via wires to achieve electrical signal acquisition and detection of organic dye pollutants.

[0074] Example 2: Integrated experiment on methylene blue detection and degradation The integrated device prepared in Example 1 was used to conduct detection and degradation experiments on methylene blue dye. The steps are as follows: (1) Prepare 300 mL of methylene blue solution with a concentration of 60 μmol / L and place it in a glass reaction vessel; (2) Place the integrated device in the above solution, turn on the water pump to drive the water flow at a flow rate of 0.3 m / s to flush the PMMA fins, and drive the roller-type triboelectric nanogenerator to rotate continuously; (3) Use a xenon lamp to simulate sunlight and irradiate the titanium-based titanium dioxide nanowire array photocatalyst on the surface of the roller with a light intensity of 300-1000 W / m² to initiate the photoelectrocatalytic reaction; (4) Connect the single-electrode bearing assembly to the electrometer through wires, set the sampling frequency to 1–3 Hz, and collect voltage, current and charge signals in real time to realize real-time detection of pollutant concentration; (5) The reaction was carried out continuously for 4 hours under the combined effect of water flow and light, and the solution concentration and electrical signal were sampled and tested every 1 hour.

[0075] Example 3: Integrated Sunset Yellow Detection-Degradation Experiment The integrated device prepared in Example 1 was used to conduct detection and degradation experiments on Sunset Yellow dye. The steps are as follows: (1) Prepare 300 mL of Sunset Yellow solution with a concentration of 60 μmol / L and place it in a glass reaction vessel; (2) Place the integrated device in the above solution, turn on the water pump to drive the water flow at a flow rate of 0.3 m / s to flush the PMMA fins, and drive the roller-type triboelectric nanogenerator to rotate continuously; (3) Use a xenon lamp to simulate sunlight and irradiate the titanium-based titanium dioxide nanowire array photocatalyst on the surface of the roller with a light intensity of 300-1000 W / m² to initiate the photoelectrocatalytic reaction; (4) Connect the single-electrode bearing assembly to the electrometer via wires, set the sampling frequency to 1–3 Hz, and collect voltage, current, and charge signals in real time; (5) The reaction was carried out continuously for 4 hours under the combined effect of water flow and light, and the solution concentration and electrical signal were sampled and tested every 1 hour.

[0076] Example 4: Integrated Experiment for the Detection and Degradation of Crystal Violet The integrated device prepared in Example 1 was used to detect and degrade crystal violet dye. (1) Prepare 300 mL of crystal violet solution with a concentration of 60 μmol / L and place it in a glass jar; (2) Place the integrated device into the solution and use a water pump to drive the water flow at a speed of 0.3 m / s to flush the PMMA fins, thereby driving the drum to rotate; (3) Use a xenon lamp to simulate sunlight and irradiate the photocatalyst on the surface of the roller with a light intensity of 300–1000 W / m² to initiate photoelectrocatalytic synergy; (4) Connect the single-electrode bearing assembly to the electrometer, set the sampling frequency to 1–3 Hz, and collect voltage, current, and charge signals in real time; (5) The reaction was carried out continuously for 4 hours, and samples were taken every 1 hour to detect changes in concentration and electrical signal.

[0077] Test Example 1 Figure 1 This is a schematic diagram of the integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to the present invention; a xenon lamp simulating sunlight is arranged facing the roller surface to excite the photocatalyst; the signal acquisition unit is electrically connected to the single-electrode bearing assembly through wires to acquire triboelectric signals in real time.

[0078] Figure 2 Fourier transform infrared (FTIR) spectra of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1. These FTIR spectra systematically characterize the chemical structure of pure polydimethylsiloxane (PDMS) and TiO2-PDMS composite films with different mass fractions (1 wt%, 3 wt%, 5 wt%, 7 wt%). At 2963 cm⁻¹... -1With 2906 cm -1 The characteristic absorption peaks at 1270 cm⁻¹ correspond to the asymmetric CH stretching vibrations and symmetric CH stretching vibrations of the methyl group in the PDMS molecular chain, respectively. -1 and 1409 cm -1 The absorption peak at 609 cm⁻¹ originates from the deformation vibration of the methyl group in PDMS. These characteristic peaks were clear and stable in all samples, confirming that the molecular structure of the PDMS matrix remained intact during the recombination process. With increasing TiO₂ mass fraction, the absorption peak at 609 cm⁻¹... -1 The emerging and significantly enhanced new characteristic peaks can be attributed to the stretching vibrations of the Ti-O-Ti framework in nano-TiO2. The peak intensity is positively correlated with the TiO2 doping amount, indicating that TiO2 nanoparticles have been successfully introduced and uniformly dispersed in the PDMS matrix. Overall, all composite samples fully retained the typical infrared characteristics of PDMS, while adding characteristic absorption peaks of TiO2. Furthermore, the peak positions showed no significant shift, indicating that the relationship between TiO2 and PDMS is primarily physical recombination, without significant chemical bonding. The introduction of TiO2 did not disrupt the molecular framework structure of PDMS.

[0079] Figure 3 Scanning electron microscope images of the titanium-based titanium dioxide nanowire array photocatalyst (TNWAs) prepared in Example 1 are shown. (a) is a low-magnification surface morphology image of the titanium-based titanium dioxide nanowire array, (b) is a high-magnification surface morphology image of the titanium-based titanium dioxide nanowire array, and (c) is a cross-sectional morphology image of the titanium-based titanium dioxide nanowire array. As can be seen from Figures (a)-(b), the TNWAs prepared by the hydrothermal method grow in a one-dimensional normal direction without two-dimensional or branched structures. The nanowires are well separated from each other, uniformly distributed, and without agglomeration. The diameters are mostly between 15-25 nm. As can be seen from Figure (c), its thickness is about 8.4 μm.

[0080] Figure 4Scanning electron microscope (SEM) images of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1 are shown. (a) shows nano-TiO2 powder, (b) shows pure PDMS, (c) shows 1 wt% TiO2-PDMS, (d) shows 3 wt% TiO2-PDMS, (e) shows 5 wt% TiO2-PDMS, and (f) shows 7 wt% TiO2-PDMS. The images show that the nano-TiO2 powder is stacked in irregular flakes. The pure PDMS surface is uniform, smooth, and free of pores; while the TiO2-PDMS surface is relatively rough, exhibiting regular ripples. With increasing TiO2 mass fraction, significant agglomeration of nano-titanium dioxide powder occurs on the composite film surface, but the complete and continuous surface structure is still maintained. This indicates that the TiO2 nanoparticles are well dispersed in the PDMS matrix, only slightly altering the surface wrinkle density without compromising the film-forming properties of the matrix.

[0081] Test Example 2 Figure 5 The figures show the water contact angles of TiO2-PDMS films prepared from different mass fractions of nano-TiO2 powder prepared in Example 1. (a) is pure PDMS, (b) is 1 wt% TiO2-PDMS, (c) is 3 wt% TiO2-PDMS, (d) is 5 wt% TiO2-PDMS, and (e) is 7 wt% TiO2-PDMS. As can be seen from the figures, the water contact angles of the different composite films are: CA1 wt% TiO2-PDMS > CAPDMS > CA7 wt% TiO2-PDMS > CA5 wt% TiO2-PDMS > CA3 wt% TiO2-PDMS. All films have water contact angles greater than 90°, exhibiting good hydrophobicity. When the TiO2 powder content is low, TiO2 and PDMS are relatively uniformly dispersed. As the mass fraction of TiO2 powder gradually increases, more agglomeration occurs in the composite film, and the local roughness increases. However, the proportion of voids between agglomerates and exposed hydrophilic interfaces increases, and the overall hydrophobic performance cannot be restored to the optimal level at 1 wt%. This indicates that appropriate doping and ensuring uniform particle dispersion are key to maintaining the excellent hydrophobic properties of PDMS. Agglomeration caused by excessive doping will significantly damage the surface hydrophobic stability.

[0082] Test Example 3 a. Electrical signal detection and photoelectrocatalytic degradation: All tests were conducted at room temperature. During testing, the integrated device prepared in Example 1 was placed in a glass tank containing 300 mL of organic dyes. The device's operation relied on the power of water flow. A DC regulated power supply (model: KUAIQUSPS-305) drove a water pump (model: Kamoer KLP40-00Y) to draw liquid from the glass tank. The water flow velocity was set to 0.3 m / s, allowing it to directly wash over the fins. As the water flow impacted the fins, the entire system was rotated. The positive electrode of an electrometer (model: Keithley 6514) was connected to a 1 wt% TiO2-PDMS composite film single electrode mounted on a roller-type triboelectric nanogenerator. The rotation of the roller caused the water flow to wash over the fins, generating electrical signals related to different organic dyes. Deep learning models and convolutional neural networks were used to achieve detection and identification. Simultaneously, under simulated sunlight (a 500 W xenon lamp as the light source, with an intensity set to 100 mW / cm²), the system was tested. 2 The reaction solution was degraded for 4 hours, and the absorbance of the reaction solution after different times was measured using a UV-Vis spectrophotometer (model: Lambda750), with a scanning range of 250 nm-800 nm.

[0083] Figure 6 The figures (a)-(c) show the electrical signal detection of TiO2-PDMS films prepared with different mass fractions of nano-TiO2 powder prepared in Example 1. As can be seen from the figures (a)-(c), the voltage of the pure PDMS film under system operation is around 10 V. When 1 wt% TiO2 is introduced, the output voltage is significantly increased to about 20 V. The short-circuit current and transfer voltage show the same trend. It can be seen that an appropriate amount of TiO2 doping (1 wt%) can significantly improve the electrical output performance of the triboelectric nanogenerator. This is because the uniformly dispersed TiO2 nanoparticles introduce more charge trapping sites, which enhances the efficiency of interfacial triboelectric charging and charge transfer. However, when the doping amount exceeds 1 wt%, the electrical output performance continues to decrease with the increase of content. This is related to the agglomeration of TiO2 powder, which leads to the obstruction of charge transport path, the reduction of effective charge trapping sites, and the destruction of the uniformity and interfacial stability of the film. Figure 6 (d) is the output voltage of 1 wt% TiO2-PDMS after 3000 cycles of system operation. The results show that the open circuit voltage hardly changed after about 3000 cycles, indicating that the system has good stability.

[0084] Figure 7In Example 2, an integrated "detection-degradation" experiment was conducted using a 1 wt% TiO2-PDMS film as the negative electrode material of the detection device to detect electrical signals in methylene blue solutions of different concentrations. (a) shows the concentration gradient of methylene blue solutions at different concentrations, (b) shows the voltage-time curve, (c) shows the current-time curve, and (d) shows the charge-time curve. The fitted curves of the concentration gradient show a good linear negative correlation between the output voltage and the methylene blue concentration, indicating that the voltage steadily decreases with increasing concentration, enabling quantitative detection of methylene blue. The peak values ​​of output voltage, current, and charge all decrease sequentially with increasing methylene blue concentration. This is because methylene blue molecules are adsorbed on the film surface, shielding some of the charge and weakening the interfacial triboelectric effect. This result verifies that the device has a relatively sensitive concentration response for methylene blue detection, and there is a strong linear correlation between the electrical signal and its concentration.

[0085] Figure 8 In Example 2, a methylene blue solution was degraded for 4 hours and monitored in real time during the integrated "detection-degradation" experiment. (a) shows the degradation kinetics curve, (b) shows the voltage of the methylene blue solution as a function of degradation time, (c) shows the current of the methylene blue solution as a function of degradation time, and (d) shows the charge of the methylene blue solution as a function of degradation time. The degradation kinetics curve shows that the concentration of methylene blue gradually decreased during the 4-hour photoelectrocatalytic degradation, and it was almost completely degraded after 4 hours, demonstrating the excellent degradation performance of RF-TENG. Figure 8 (b)-(d) show that the electrical signal after 4 h of degradation is basically consistent with that of deionized water, indicating that methylene blue has been effectively removed. This result directly verifies that the device can simultaneously achieve efficient photocatalytic degradation of pollutants and real-time electrical signal monitoring.

[0086] Figure 9 In Example 3, a 1 wt% TiO2-PDMS thin film was used as the negative electrode material of the detection device to detect the electrical signals of Sunset Yellow solutions of different concentrations. (a) shows the concentration gradient of Sunset Yellow solutions at different concentrations, (b) shows the voltage-time curve, (c) shows the current-time curve, and (d) shows the charge-time curve. The fitting curves of Sunset Yellow concentration and output voltage show a good linear relationship, indicating that the device can achieve quantitative detection of Sunset Yellow dye. Figure 9 The voltage, current and charge time-domain signals of (b)-(d) all decrease stepwise with increasing Sunset Yellow concentration, and the trend is consistent with that of the methylene blue system. Compared with methylene blue, Sunset Yellow has a relatively weaker influence on the electrical signal, indicating that the device has higher detection sensitivity for methylene blue.

[0087] Figure 10In Example 3, a sunset yellow solution was degraded for 4 hours using an integrated "detection-degradation" experiment, with real-time monitoring. (a) shows the degradation kinetics curve; (b) shows the voltage of the sunset yellow solution as a function of degradation time; (c) shows the current of the sunset yellow solution as a function of degradation time; and (d) shows the charge of the sunset yellow solution as a function of degradation time. The degradation kinetics curves indicate that 4 hours of photocatalytic degradation can achieve highly efficient removal of sunset yellow, with a degradation efficiency comparable to that of the methylene blue system. Figure 10 Real-time electrical signal monitoring (b)-(d) shows that as the concentration of Sunset Yellow decreases, the output voltage, current, and charge all gradually recover, and the signal approaches the level of deionized water (DI) after 4 hours. This evolution pattern is consistent with the methylene blue degradation process in Example 2, indicating that after the pollutant is degraded, the surface charge shielding effect weakens, and the triboelectric process is restored. This directly verifies that the device can simultaneously achieve photocatalytic degradation of Sunset Yellow and real-time electrical signal monitoring.

[0088] Figure 11 In Example 4, a 1 wt% TiO2-PDMS thin film was used as the negative electrode material of the detection device to detect electrical signals in crystal violet solutions of different concentrations. (a) shows the concentration gradient of crystal violet solutions at different concentrations, (b) shows the voltage-time curve, (c) shows the current-time curve, and (d) shows the charge-time curve. The fitting curves of crystal violet concentration and output voltage show a similar linear relationship to those in Examples 2 and 3. Figure 11 The voltage, current and charge time-domain curves of (b)-(d) all gradually decrease with increasing crystal violet concentration. This trend is consistent with the methylene blue and sunset yellow system, which reflects the rationality of the device's ability to quantitatively detect and identify the three dyes.

[0089] Figure 12 In Example 4, a crystal violet solution was degraded for 4 hours using an integrated "detection-degradation" experiment, with real-time monitoring. (a) shows the degradation kinetics curve; (b) shows the voltage of the crystal violet solution as a function of degradation time; (c) shows the current of the crystal violet solution as a function of degradation time; and (d) shows the charge of the crystal violet solution as a function of degradation time. It can be seen that the catalytic degradation efficiency of crystal violet is comparable to that of methylene blue in Example 2 and sunset yellow in Example 3, demonstrating the excellent catalytic degradation performance of RF-TENG. Figure 12 The output electrical signals in (b)-(d) also verified the results of catalytic degradation after 4 hours. The three dyes all showed similar trends, indicating the versatility of the device system and providing experimental evidence for the treatment of complex water bodies.

[0090] Figure 13For the pseudo-first-order kinetic fitting of the degradation of three organic dyes over 4 hours in the integrated "detection-degradation" experiment of Examples 2-4, the fitting equation is as follows: In the formula, C0 is the initial concentration, Ct is the pollutant concentration at time t, and Kobs is the apparent reaction rate constant in h⁻¹. Calculations show that the rate constants Kobs for MB, SY, and CV are 1.01 h⁻¹, 0.78 h⁻¹, and 0.66 h⁻¹, respectively, indicating that the catalytic degradation effect of methylene blue is better in this system.

[0091] Figure 14 The training (a) and testing (b) curves of the CNN-1D model for different types of organic dyes in Examples 2-4 are shown, along with sample response time curves (c) and response time distribution histograms (d). To achieve accurate classification of methylene blue, sunset yellow, and crystal violet, these three organic dyes are labeled as 1-3 respectively. The training iteration process of the deep learning model is as follows... Figure 14 As shown in (a)-(b), the model training exhibits extremely fast convergence. After only about 500 iterations, the recognition accuracy rapidly approaches 100%, and the loss value simultaneously drops to an extremely low level. In subsequent iterations, the model performance remains highly stable, with no significant fluctuations in accuracy and the loss value remaining stable at a low level, demonstrating excellent fitting efficiency, accuracy, and training stability. The final classification results are as follows: Figure 14 (b) shows that the dye samples corresponding to various labels were accurately identified, and the overall average recognition accuracy of the model reached 100%. Figure 14 (c)-(d) show the response time variation curves and response time distribution histograms for 100 consecutive predictions of a single sample using CNN-1D. The average response time of the sample is approximately 7.195 ms. All prediction times are highly concentrated in the range of 6.0–7.5 ms, exhibiting typical concentrated distribution characteristics without obvious tailing or outliers. This result fully verifies the efficient identification capability of the deep learning model for the molecular features of organic dyes. Even in the scenario of repeated and continuous prediction, the model can still output results stably, confirming the efficiency and reliability of the intelligent classification method and providing core technical support for the automated operation of the "detection-degradation" integrated system.

[0092] Figure 15 The confusion matrix (a) shows the accuracy of tag recognition for different types of organic dyes running CNN-1D in Examples 2-4, and the three-dimensional waterfall plot of output voltage-time for organic dyes under different tag types (b). The peak values ​​of the voltage and current output signals of Sunset Yellow, Methylene Blue, and Crystal Violet solutions with a concentration of 60 μmol / L were selected and defined as tags 1-3. Figure 15As shown in (a), the recognition results for each label have high prediction values ​​and accuracy, with an overall average recognition accuracy of 100%. The recognition accuracy for Sunset Yellow, Methylene Blue, and Crystal Violet labels all reached 100%. Among them, 1 is a 60 μmol / L Sunset Yellow solution, 2 is a 60 μmol / L Methylene Blue solution, and 3 is a 60 μmol / L Crystal Violet solution.

[0093] Test Example 4 To quantitatively evaluate the mechanical strength and structural stability of the material, the mechanical properties of the TiO2-PDMS composite film prepared in Example 1 were tested using a universal testing machine and a compression testing device. Before the test, the composite film was cut into a rectangle with dimensions of 10 mm wide × 50 mm long × 0.25 mm thick.

[0094] Figure 16 Mechanical properties of TiO2-PDMS composite films prepared with different mass fractions of nano-TiO2 powder as described in Example 1 were tested. The tensile stress-strain curves of the TiO2-PDMS composite films are shown in the figure. It can be seen that the 1 wt% TiO2-PDMS film has the highest tensile strength. The fact that the pure PDMS film is most prone to fracture indicates that an appropriate amount of TiO2 nanoparticles can effectively enhance the PDMS matrix, achieving a synergistic improvement in strength and toughness. The fracture stress of the 3 wt% sample decreased slightly, but was still significantly higher than that of pure PDMS, maintaining good mechanical properties. When the TiO2 content was further increased to 5 wt% and 7 wt%, both the fracture stress and fracture strain continued to decrease. The fracture stress of the 7 wt% sample was only about 10 MPa, and the fracture strain was also significantly reduced. This is because the particle agglomeration caused by excessive TiO2 disrupted the continuous structure of the PDMS molecular chains, forming stress concentration sites, leading to a decrease in the strength and toughness of the composite film.

[0095] This invention innovatively proposes an integrated device for photoelectric synergistic catalytic detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, belonging to the fields of water environment management and self-driven sensing technology. The device uses a hydrothermal calcination method to prepare a titanium-based titanium dioxide nanowire array as the photocatalytic functional layer; it then prepares a single-electrode functional film by combining nano-titanium dioxide with polydimethylsiloxane (PDMS) at different mass fractions, which is then assembled with copper foil and bearings, and the entire assembly is placed on the outside of the roller-type triboelectric nanogenerator to construct an integrated functional system.

[0096] The device of this invention relies on natural water flow to drive the drum rotation, enabling self-driven operation. Under illumination, the titanium-based titanium dioxide nanowire array can efficiently degrade organic dyes such as methylene blue, sunset yellow, and crystal violet in water. Simultaneously, the 1 wt% doped TiO2-PDMS composite film, under the action of water flow, generates a triboelectric signal correlated with pollutant concentration. After signal acquisition by an electrometer, combined with a one-dimensional convolutional neural network deep learning algorithm, real-time identification and quantitative detection of organic pollutants are achieved, with a pollutant classification accuracy of up to 100%.

[0097] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A photoelectric synergistic catalytic device for the detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator, characterized in that, include: Roller-type triboelectric nanogenerator, single-electrode bearing assembly, illumination unit, and signal acquisition unit; The roller surface of the roller-type triboelectric nanogenerator is loaded with a titanium-based titanium dioxide nanowire array photocatalyst. The single-electrode bearing assembly is assembled from a TiO2-PDMS composite film, copper foil, bearing, and wires. The single-electrode bearing assembly is fitted onto the outside of the drum of the roller-type triboelectric nanogenerator, and the TiO2-PDMS composite film is coaxially wrapped around the outside of the drum, radially opposite to the titanium-based titanium dioxide nanowire array photocatalyst loaded on the surface of the drum. The signal acquisition unit is electrically connected to the single-electrode bearing assembly via a wire to acquire triboelectric signals, thereby enabling real-time detection of organic dye concentration in the water. The illumination unit is arranged facing the surface of the roller to excite the titanium-based titanium dioxide nanowire array photocatalyst to achieve in-situ degradation of organic dyes.

2. The integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to claim 1, characterized in that, The mass fraction of nano-TiO2 in the TiO2-PDMS composite film is 0wt% to 7wt%, and is not 0wt%.

3. The integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to claim 1, characterized in that, The TiO2-PDMS composite film is prepared by coating a slurry of PDMS and nano-TiO2 and then curing it at 80-100 °C for 1-2 h.

4. The integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to claim 1, characterized in that, The signal acquisition unit is an electrometer.

5. The integrated device for photoelectric synergistic catalysis of organic dye detection and degradation based on a roller-type triboelectric nanogenerator according to claim 1, characterized in that, The illumination unit is a xenon lamp with an illumination intensity of 300–1000 W / m².

6. The application of the integrated device for photoelectric synergistic catalytic detection and degradation of organic dyes based on a roller-type triboelectric nanogenerator as described in any one of claims 1-5 in the catalytic degradation of organic dyes.

7. The application according to claim 6, characterized in that, The organic dyes include methylene blue, crystal violet, or sunset yellow.

8. An integrated method for the detection and degradation of organic dyes, characterized in that, The integrated photoelectric synergistic catalytic organic dye detection-degradation device based on a roller-type triboelectric nanogenerator as described in any one of claims 1-5 includes the following steps: The photoelectric synergistic catalytic organic dye detection-degradation integrated device based on roller triboelectric nanogenerator is placed in an aqueous solution containing organic dye to be treated. The roller triboelectric nanogenerator is driven to operate by the water flow to generate triboelectric signals. The titanium-based titanium dioxide nanowire array photocatalyst on the surface of the drum of the drum-type triboelectric nanogenerator is irradiated by the light unit to initiate a photoelectrocatalytic reaction. The signal acquisition unit collects electrical signals in real time, correlates them with changes in the concentration of organic dyes, and simultaneously completes the photocatalytic degradation of organic dyes.

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