Application and method of CsCuX3 microwire in degradation of antibiotics / perfluorocarboxylic acid organic matters, catalyst and immobilization reactor

Abstract

The invention provides application of a CsCuX3 microwire in degradation of antibiotics / perfluorocarboxylic acid organic matters, a method, a catalyst and an immobilization reactor, the inorganic cesium-copper halide perovskite CsCuX3 microwire is used as a photo-thermal catalytic material, antibiotics and / or perfluorocarboxylic acid organic matters in water are / is degraded under the illumination condition, and the degradation rate of the antibiotics / perfluorocarboxylic acid organic matters is increased. The obvious degradation of antibiotics and PFOA can be realized in a relatively short time. And the CsCuX3 microwire can be loaded on an inert carrier to prepare a recyclable granular catalyst or a fixed bed reactor, so that the CsCuX3 microwire can be separated and recycled from treated water. The CsCuX3 micron wire does not contain precious metal, is low in material cost, high in stability and suitable for degradation treatment of various water bodies.

Description

Technical Field

[0001] This invention relates to the field of environmental catalytic materials and water treatment technology, particularly to the application of copper-based halide perovskite materials in photothermal catalytic purification of water. Specifically, this invention provides the use, method, catalyst, and immobilized reactor of CsCuX3 microwires in the degradation of antibiotics / perfluorocarboxylic acids. Background Technology

[0002] Antibiotic pollution has become a global environmental concern. Sulfonamide antibiotics, such as sulfamethoxazole (SMX), are widely used in medical treatment and animal husbandry, leading to their persistent and difficult-to-degrade residues in the environment. Studies show that antibiotics are listed as one of the key new pollutants under control in my country, and their environmental hazard lies in the ability to spread drug resistance genes through environmental media, thereby causing bacterial resistance problems. Sulfonamide antibiotics are frequently detected in surface water, although the concentrations are mostly at the ng / L to μg / L level. However, due to continuous discharge, their "pseudo-persistent" pollution characteristics cannot be ignored. These antibiotics mainly originate from livestock and poultry wastewater, domestic sewage, and wastewater treatment plant discharges, and their long-term presence poses a potential threat to aquatic ecosystems and human health.

[0003] Perfluorooctanoic acid (PFOA) is a typical new perfluorinated pollutant with extremely high chemical inertness and bioaccumulation, and is widely present in environmental media. PFOA is highly toxic and difficult to degrade, and can persist in the environment for extended periods, posing serious threats to ecological security and human immune, neurological, and reproductive health. Due to the extreme stability of the carbon-fluorine bonds in PFOA, traditional treatment methods are inefficient in removing it. Existing degradation technologies include advanced oxidation (such as ozone and photocatalysis), electrochemical flocculation, and adsorption, but these often suffer from high costs, low efficiency, or incomplete treatment, hindering their widespread application. Photocatalysis technology demonstrates advantages in PFOA degradation, offering mild conditions, high efficiency, and no secondary pollution. However, conventional photocatalytic materials (such as TiO2) typically only respond to UV light, resulting in low solar energy utilization, and some materials exhibit poor stability, limiting their effectiveness in practical water treatment. Therefore, in recent years, researchers have focused on developing new photocatalytic materials that simultaneously possess high activity, good visible light absorption performance, and high stability, aiming to achieve efficient degradation of PFOA in water. For example, a review of various PFOA photocatalytic degradation materials over the past 20 years has summarized their characteristics and shortcomings, and elucidated the possible degradation pathways of PFOA. It is evident that improving the responsiveness and stability of photocatalytic materials in the visible and even infrared light regions is a key direction for solving the challenge of degrading new pollutants.

[0004] Perovskite photocatalytic materials have attracted much attention due to their excellent photoelectric properties. While traditional lead-based halide perovskites possess suitable band gaps and high carrier mobility, they suffer from poor photostability and lead toxicity. Copper-based halide perovskites (CsCuCl3), as an emerging lead-free perovskite material, offer advantages such as environmental friendliness and high thermal stability, and are gradually becoming a research hotspot. Furthermore, preliminary photocatalytic studies have demonstrated the good catalytic activity of copper-based perovskites: for example, Zn-doped CsCuCl3 exhibits high yield and selectivity in the selective oxidation of toluene to benzaldehyde under visible light; and the in-situ loading of CsCuCl3 with Cu nanocrystals to construct heterojunctions can be used for the selective photocatalytic reduction of CO2 to methane. These advances indicate that copper-based perovskites have considerable potential in the field of photocatalysis. However, systematic research on the application of copper-based halide perovskites in photothermal synergistic catalytic purification of water remains scarce. Traditional photocatalytic research has largely focused on pure photogenerated carrier processes, with less attention paid to the role of photothermal effects in catalysis. Photothermal catalysis refers to the conversion of some light energy into heat energy by a material under illumination, thereby increasing the reaction temperature and synergistically catalyzing the reaction. Compared with simple photocatalysis, the photothermal synergy holds promise for accelerating the decomposition of recalcitrant pollutants. However, to date, there is a lack of systematic research on the application of copper-based perovskites in the photothermal catalytic degradation of antibiotics and perfluorinated compounds in water. This is precisely the technological gap that this invention aims to fill. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides the application, method, catalyst, and immobilized reactor of CsCuX3 microwires in the degradation of antibiotics / perfluorocarboxylic acids. In the photothermal catalytic purification of antibiotics / perfluorocarboxylic acid organic pollutants in water using CsCuX3 microwire materials, the combination of light irradiation and photothermal conversion with the catalyst achieves rapid degradation of recalcitrant antibiotics and perfluorocarboxylic acids. Compared with existing pure photocatalytic or thermocatalytic methods, this invention utilizes the synergistic effect of photogenerated carrier catalysis and photothermal effect to significantly improve pollutant removal efficiency under moderate temperature conditions.

[0006] The technical solution of the present invention is as follows:

[0007] The use of inorganic cesium copper halide perovskite microwires in photothermal catalytic degradation of antibiotics / perfluorinated carboxylic acids is characterized in that the inorganic cesium copper halide perovskite CsCuX3 microwires are used as photothermal catalytic materials to degrade antibiotics and / or perfluorinated organics in water, wherein X is one of Cl, Br, and I.

[0008] Furthermore, the CsCuX3 micron-wire catalyst is supported on an inert support to form a fixed-bed photothermal catalytic reactor, or it is combined with an inert particulate support to form a recyclable particulate catalyst for the degradation of antibiotics and / or perfluorinated organics in water by photothermal catalytic materials.

[0009] Furthermore, the diameter of the micron wire is 100-300 micrometers and the length is 3-10 millimeters.

[0010] Furthermore, the water undergoing degradation treatment is domestic sewage, aquaculture wastewater, surface water, or groundwater contaminated with antibiotics and / or perfluorocarboxylic acid organic compounds; the antibiotics are one or more of sulfamethoxazole, sulfadiazine, sulfamethazine, and sulfadiazine; and the perfluorocarboxylic acid organic compounds are one or more of perfluorooctanoic acid, perfluorobutyric acid, perfluorohexanoic acid, perfluorononanoic acid, and perfluorodecanoic acid.

[0011] The inorganic cesium copper halide perovskite microwire catalyst for use in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids is characterized by being composed of CsCuX3 microwires and an inert support, wherein the inert support is selected from one or more of the following: quartz sheets, quartz beads, glass beads, quartz sand, alumina spheres, alumina rings, alumina foam, honeycomb ceramics, cordierite honeycomb, glass fiber mat, and quartz fiber mat; and the CsCuX3 microwires are loaded onto the surface of the inert support by one or more of the following methods: dip coating, spray coating, drop coating, vacuum impregnation, spin coating, and brush coating.

[0012] Furthermore, the catalyst is a recyclable particulate catalyst, consisting of an inert particle core and a CsCuCl3 micron-sized active layer coated on its surface. The inert particle core is selected from one or more of alumina particles, quartz particles, glass particles, or ceramic particles. The particulate catalyst is prepared by one or more of the following methods: roller coating, disc granulation, spray coating, impregnation coating, or extrusion granulation. In practical applications, the obtained particulate catalyst can be rapidly recovered from the reaction solution through sieving, sedimentation, filtration, or basket separation, and can be reused in subsequent pollutant degradation processes, thus balancing catalytic activity with recyclability and stability in engineering applications.

[0013] Furthermore, an intermediate adhesion layer is introduced during the loading process to improve the bonding strength between the CsCuX3 microwires and the carrier. The intermediate adhesion layer is selected from one or more of silica sol, alumina sol, boehmite sol, polyvinylidene fluoride, polytetrafluoroethylene, and polyvinylpyrrolidone.

[0014] A fixed-bed photothermal catalytic reactor for use in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids is characterized by comprising a reactor shell and an immobilized catalyst carrier filled inside the shell; the reactor shell is made of a light-transmitting material; the water to be treated passes through the fixed bed in an intermittent, circulating, or continuous flow manner to achieve photothermal catalytic degradation of pollutants under light conditions.

[0015] A method for photothermal degradation of antibiotics / perfluorocarboxylic acids using inorganic cesium copper halide perovskite microwires is characterized by comprising the following steps: S1. Add the CsCuX3 micron-sized catalyst to the water sample to be degraded; S2. Photothermal catalytic degradation under illumination for 30-90 minutes; during this process, the CsCuX3 micron-wire catalyst is photoexcited to generate photogenerated electron-hole pairs, and part of the invisible light is converted into heat energy, causing the solution temperature to rise. On the one hand, the photogenerated charge carriers drive the photocatalytic oxidation / reduction reaction of antibiotics and / or perfluorocarboxylic acids; on the other hand, the temperature rise accelerates the reaction kinetics and increases the decomposition rate of pollutants.

[0016] Furthermore, the dosage of the CsCuX3 micron-wire catalyst is 5-50 mg per 100 mL water sample; preferably, the light intensity of the illumination is one solar constant, and the spectral range covers UV to visible light.

[0017] This invention selects the all-inorganic cesium copper halide perovskite CsCuX3 as a photothermal catalyst. This material exists in the form of one-dimensional microcrystals with microwires. The large aspect ratio and single-crystal structure of the microwires are beneficial for multiple scattering absorption of light and carrier transport along the wire direction, reducing the photogenerated electron-hole recombination rate. Furthermore, these copper-based perovskites do not contain toxic elements such as lead, and the abundance and low cost of copper and halogens make them environmentally friendly. CsCuX3 material exhibits excellent photothermal conversion performance; under simulated sunlight irradiation, the temperature rise of CsCuCl3-based microcrystals can reach 16°C within 1 minute, significantly higher than the control sample without this material. This indicates that copper-based perovskites can efficiently convert light energy into heat energy, providing additional temperature driving force for the photothermal catalytic reaction. At the same time, the CsCuX3 crystal structure is stable, not easily undergoing phase transitions or decomposition under light and heating conditions, and also exhibits good chemical stability in aqueous solutions. Therefore, this invention selects CsCuX3 micron wires as the catalyst material, which has both a wide spectral response, excellent thermal stability and environmental friendliness.

[0018] The photothermal catalytic degradation reaction of this invention is carried out under simulated solar illumination conditions. A standard solar simulator is used to provide approximately one solar constant (1 sun, ~100 mW / cm²). 2The light intensity is high, and the spectral range covers UV to visible light. CsCuX3 micron-wire catalyst is added to the water sample to be treated, preferably at a dosage of 20 mg per 100 mL of water sample. Target pollutants to be degraded include representative antibiotics, such as sulfamethoxazole (SMX), and typical perfluorocarboxylic acids, such as PFOA. The initial concentrations of both sulfamethoxazole (SMX) and PFOA can be determined based on the actual pollution situation (e.g., from tens of μg / L to several mg / L). During the photo-induced reaction, the inorganic cesium copper halide perovskite catalyst is photoexcited to generate photogenerated electron-hole pairs, converting some of the invisible light into heat energy, causing a slight increase in solution temperature. This photothermal synergistic effect can activate more reaction pathways: on the one hand, photogenerated carriers drive the photocatalytic oxidation / reduction reactions of SMX and PFOA; on the other hand, the temperature rise accelerates reaction kinetics and increases the decomposition rate of pollutants. Under simulated sunlight irradiation for approximately one hour, the degradation rate of sulfamethoxazole reached over 90%, with a mineralization rate (COD / TOC removal rate) exceeding 80%. The degradation rate of PFOA also exceeded 50%, and fluoride ion release was detected, indicating the breaking of its carbon-fluorine bonds and partial mineralization. Extending the irradiation time to 90 minutes further improved the PFOA removal rate. This performance surpasses traditional single photocatalytic or thermocatalytic methods, enabling significant degradation of antibiotics and PFOA in a shorter time.

[0019] It has been reported that the UV / TiO2 system alone has a very low removal rate for PFOA, making it difficult to effectively break the CF bond. However, this invention utilizes photothermal synergy to increase the generation of reactive oxygen species and the reaction temperature, thereby effectively overcoming the stable structure of PFOA. Furthermore, compared to current methods that require the addition of strong oxidants (such as persulfate) or high-temperature incineration, the method of this invention is more environmentally friendly and energy-efficient. Regarding antibiotic degradation, the material of this invention responds to visible light, enabling it to efficiently generate reactive species such as •OH and •O2⁻ to attack SMX molecules, avoiding the inconvenience of adding peroxides required in the traditional Fenton reagent method. In summary, this invention has significant advantages in terms of pollutant removal efficiency, energy consumption, and applicability.

[0020] This invention is applicable to various water body types, including domestic sewage, aquaculture wastewater, and surface water and groundwater contaminated with antibiotics or perfluorinated compounds. For actual water samples with high organic matter content or complex water quality, simple filtration or pH adjustment can be performed before light exposure to optimize the degradation effect.

[0021] For practical applications, CsCuX3 microwires can be loaded onto an inert support to form a fixed-bed reactor, or they can be made into recyclable particulate catalysts for easy separation and recovery from treated water.

[0022] Because the catalyst of this invention does not contain precious metals, the material cost is low, and copper-based perovskite responds to both visible and infrared light, making full use of natural sunlight, thus possessing excellent practical application potential. Compared to currently widely studied precious metal photothermal materials (such as nano-gold and nano-silver), copper-based perovskite is cheaper and has higher thermal stability. Furthermore, the catalyst of this invention has a one-dimensional micron-wire structure, exhibiting good dispersion stability in water, resisting aggregation and sedimentation, and easily separated after the reaction by simple precipitation or filtration. In summary, the CsCuCl3 micron-wire photothermal catalysis method provided by this invention achieves broad-spectrum solar energy utilization and efficient degradation of recalcitrant pollutants, demonstrating significant environmental and economic benefits. Attached Figure Description

[0023] Figure 1 This is the ultraviolet-visible absorption spectrum of the CsCuCl3 micron-sized wire prepared in Example 1 of the present invention.

[0024] Figure 2 The X-ray diffraction (XRD) pattern of the CsCuCl3 micron-wire material is shown.

[0025] Figure 3 The image shows the photothermal effect of the CsCuCl3 micron-wire.

[0026] Figure 4 The curve showing the relative concentration change of sulfamethoxazole during the photothermal catalytic degradation process under the degradation conditions of Example 2 is shown.

[0027] Figure 5 The graph shows the photothermal catalytic degradation kinetics of PFOA under the degradation conditions of Example 2. Detailed Implementation

[0028] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0029] Example 1: Preparation of CsCuCl3 microwire catalyst

[0030] In this embodiment, CsCuCl3 microwires were prepared by a hydrothermal method. Anhydrous cesium chloride (CsCl) and cuprous chloride (CuCl) were weighed and dissolved in deionized water according to their stoichiometric ratio. The solution was transferred to a high-pressure sealed polytetrafluoroethylene-lined reactor and hydrothermally reacted at 180 °C for 24 hours, followed by natural cooling. The resulting precipitate was repeatedly washed with deionized water and anhydrous ethanol to remove unreacted substances and byproducts. Finally, it was vacuum dried at 60 °C to obtain white CsCuCl3 microwire powder. The prepared CsCuCl3 microwires had a diameter of 100-300 μm and a length of 3-10 mm.

[0031] Figure 1The UV-vis absorption results shown indicate that the CsCuCl3 micrometer wire exhibits a significant optical response in the ultraviolet to visible light region, and retains certain absorption / response characteristics in longer wavelength bands. This demonstrates that the material possesses a broad spectral range of light-harvesting capabilities, providing a foundation for its photo-driven reactions and potential photothermal conversion behavior. Figure 2 The XRD results shown indicate that the CsCuCl3 micrometer lines possess a series of clear and sharp diffraction peaks, suggesting that the prepared material exhibits high crystallinity. This excellent crystal order provides the structural basis for its optical response and energy conversion behavior under illumination. Figure 3 The infrared thermal imaging results show that, under sunlight illumination, at a distance of approximately 20 cm from the light source, the temperature of the CsCuCl3 microwire region is significantly higher than the surrounding background region. This indicates that CsCuCl3 can effectively convert absorbed light energy into heat energy through a non-radiative relaxation pathway, exhibiting significant photothermal response behavior. Combined with its broad-spectrum absorption characteristics, this result demonstrates the potential of CsCuCl3 as a photothermal assisted catalytic material.

[0032] By adjusting the source of halides in the precursors, such as replacing CsCl with cesium bromide (CsBr) and adding an appropriate amount of sodium bromide to provide Br⁻, or replacing it with cesium iodide (CsI) and adding sodium iodide, corresponding CsCuBr₃ and CsCuI₃ microwires can be prepared respectively. All the prepared microwires are stable in air, without obvious deliquescence or decomposition.

[0033] Example 2: Photothermal catalytic degradation of sulfamethoxazole

[0034] A certain amount of sulfamethoxazole (SMX) was dissolved in deionized water to prepare a simulated contaminated water sample with a concentration of 10 mg / L. 100 mL of this simulated contaminated water sample was added to a quartz beaker. 20 mg of the CsCuCl3 micron-wire catalyst prepared in this invention was added, and the mixture was magnetically stirred to form a homogeneous suspension. First, magnetic stirring was continued in the dark. Then, a xenon lamp solar simulator with an irradiation distance of approximately 10 cm was used to provide light with an intensity of approximately 100 mW / cm² and a spectral range including UV-Vis. Magnetic stirring was continued under this illumination. Throughout the entire process, 5 mL of the water sample was taken every 15 minutes during the degradation process. After filtration through a 0.45 μm filter membrane, the remaining concentration of SMX was determined using a UV-Vis spectrophotometer. The absorbance of the characteristic absorption peak of SMX was read at a wavelength λ≈258 nm, and the relative concentration was compared.

[0035] Figure 4The figure shows the relative concentration change curve of sulfamethoxazole during the photothermal catalytic degradation process in this embodiment. After stirring in the dark for 30 min, the relative concentration of SMX only decreased from 1 to about 0.99, indicating that the adsorption effect of CsCuCl3 on SMX is weak, and the system has no significant removal effect on sulfamethoxazole in the water sample under dark conditions. After the light is turned on, the relative concentration of SMX decreases rapidly. At 15 min, the C / C0 ratio drops to about 0.56, at 45 min it further drops to about 0.125, and after 90 min it is only about 0.009, indicating that CsCuCl3 exhibits a highly efficient photo-driven degradation ability for SMX under these reaction conditions. This result, combined with the absorption spectrum, XRD and photothermal tests confirmed that CsCuCl3 has a stable crystal structure, broad-spectrum photoresponse and photothermal conversion ability, suggests that CsCuCl3 microwires can serve as a pollutant degradation material with potential photothermal synergistic effects.

[0036] Example 3: Photothermal catalytic degradation of PFOA

[0037] 100 mL of a 5 mg / L PFOA aqueous solution was placed in a beaker, and 20 mg of CsCuCl3 micron-wire catalyst was added. Before the degradation reaction began, the mixture was sonicated for 5 minutes to uniformly disperse the catalyst. Then, under stirring conditions, the light was turned on. The light apparatus and conditions were the same as in Example 2, and the degradation experiment lasted for 90 minutes. During the degradation process, 5 mL samples were taken approximately every 15 minutes. After enrichment by solid-phase extraction, the PFOA concentration change was determined by high-performance liquid chromatography-mass spectrometry (LC-MS). Figure 5 As shown, after 30 min of pre-equilibration in the dark, the degradation rate of PFOA remained almost unchanged, indicating that the simple adsorption effect of CsCuCl3 on PFOA is weak, and significant removal is difficult to achieve under dark conditions. After the light was turned on, the PFOA removal rate continued to increase over time, reaching approximately 8% at 10 min, approximately 20% at 20 min, approximately 32% at 30 min, and further increasing to approximately 70% at 60 min. Considering that PFOA, as a typical perfluorocarboxylic acid pollutant, has extremely high chemical stability, the above results indicate that CsCuCl3 also has a significant treatment capacity for highly stable PFAS pollutants. Combining the aforementioned absorption spectroscopy, XRD, and photothermal test results, it can be concluded that CsCuCl3 possesses a stable crystal structure, broad-spectrum photoresponse, and photothermal conversion characteristics, and shows application potential in the treatment of recalcitrant new pollutants.

[0038] In summary, the CsCuCl3 micron-line photothermal catalytic degradation method for antibiotics and new pollutants provided by this invention fully utilizes the broad-spectrum absorption characteristics and photothermal conversion capabilities of copper-based halide perovskite materials, achieving highly efficient removal of recalcitrant organic pollutants under simulated sunlight conditions. Its innovation lies in the organic combination of photocatalysis and photothermal effects, overcoming the shortcomings of traditional photocatalytic materials such as narrow spectral response and poor thermal stability, achieving excellent degradation performance without the use of precious metal additives. The method of this invention is simple in procedure, mild in conditions, requires no chemical reagents, and does not generate secondary pollutants, possessing good practicality and environmental benefits, and is suitable for future treatment of new water pollutants and water purification.

[0039] To facilitate the separation, recovery, and continuous application of the catalyst in actual water treatment systems, the CsCuCl3 micron wires can be loaded onto the surface of an inert support to form an immobilized catalyst layer and filled into a reactor to constitute a fixed-bed photothermal catalytic reactor; or they can be combined with an inert support to form a recyclable particulate catalyst.

[0040] Example 4: Inorganic cesium copper halide perovskite microwire catalyst

[0041] When the CsCuCl3 microwires are composited with an inert support to form a recyclable particulate catalyst, the inert support is selected from one or more of the following: quartz sheets, quartz beads, glass beads, quartz sand, alumina spheres, alumina rings, alumina foam, honeycomb ceramics, cordierite honeycomb, glass fiber mat, and quartz fiber mat. The CsCuCl3 microwires are loaded onto the surface of the inert support by one or more of the following methods: dip coating, spray coating, drop coating, vacuum impregnation, spin coating, and brush coating. An intermediate adhesion layer may be introduced during the loading process to improve the bonding strength between the CsCuCl3 microwires and the support. The intermediate adhesion layer is selected from one or more of the following: silica sol, alumina sol, boehmite sol, polyvinylidene fluoride, polytetrafluoroethylene, and polyvinylpyrrolidone.

[0042] Example 5: Recyclable Particulate Catalyst

[0043] The recyclable particulate catalyst comprises an inert particle core and a CsCuCl3 micron-sized active layer coated on its surface; the inert particle core is selected from one or more of alumina particles, quartz particles, glass particles, and ceramic particles. The recyclable particulate catalyst can be prepared by one or more of the following methods: roller coating, disc granulation, spray coating, impregnation coating, and extrusion granulation. In practical applications, the obtained particulate catalyst can be rapidly recovered from the reaction solution through sieving, sedimentation, filtration, or basket separation, and can be reused in subsequent pollutant degradation processes, thus balancing catalytic activity with recyclability and stability in engineering applications.

[0044] Example 6: Fixed-bed photothermal catalytic reactor

[0045] The fixed-bed photothermal catalytic reactor includes a reactor shell and an immobilized catalyst carrier filled inside the shell; the reactor shell can be made of quartz, glass or other light-transmitting materials; the water to be treated passes through the fixed bed in an intermittent, circulating or continuous flow manner to achieve photothermal catalytic degradation of pollutants under light conditions.

[0046] The fixed-bed photothermal catalytic reactor or recyclable granular catalyst is used for the photothermal catalytic degradation of sulfamethoxazole, perfluorooctanoic acid, and other antibiotic pollutants, as well as new pollutants. This invention, by immobilizing or granulating CsCuCl3 micrometer wires, significantly reduces the loss of powdered catalyst during water treatment while maintaining its light absorption, photothermal conversion, and catalytic activity. This improves the catalyst's mechanical stability, recovery efficiency, and recyclability, making it suitable for continuous, large-scale water treatment applications.

[0047] The embodiments described above are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. The use of inorganic cesium copper halide perovskite microwires in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids, characterized in that, The inorganic cesium copper halide perovskite CsCuX3 microwires are used as photothermal catalysts to degrade antibiotics and / or perfluorinated organics in water, wherein X is one of Cl, Br, and I.

2. The use of the inorganic cesium copper halide perovskite microwires according to claim 1 in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids, characterized in that, The CsCuX3 micron-wire catalyst is supported on an inert support to form a fixed-bed photothermal catalytic reactor, or it is combined with an inert particulate support to form a recyclable particulate catalyst for the photothermal catalytic degradation of antibiotics and / or perfluorinated organic compounds in water.

3. The use of the inorganic cesium copper halide perovskite microwires according to claim 1 in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids, characterized in that, The diameter of the micron wire is 100-300 micrometers and the length is 3-10 millimeters.

4. The use of the inorganic cesium copper halide perovskite microwires according to claim 1 in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids, characterized in that, The water undergoing degradation treatment is domestic sewage, aquaculture wastewater, surface water, or groundwater contaminated with antibiotics and / or perfluorocarboxylic acid organic compounds; the antibiotics are one or more of sulfamethoxazole, sulfadiazine, sulfamethazine, and sulfadiazine; and the perfluorocarboxylic acid organic compounds are one or more of perfluorooctanoic acid, perfluorobutyric acid, perfluorohexanoic acid, perfluorononanoic acid, and perfluorodecanoic acid.

5. An inorganic cesium copper halide perovskite microwire catalyst for use in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids as described in claim 1, characterized in that, It is composed of CsCuX3 micron wires and an inert carrier. The inert carrier is selected from one or more of the following: quartz sheet, quartz bead, glass bead, quartz sand, alumina ball, alumina ring, alumina foam, honeycomb ceramic, cordierite honeycomb, glass fiber mat, and quartz fiber mat. The CsCuX3 micron wires are loaded onto the surface of the inert carrier by one or more of the following methods: dip coating, spray coating, drop coating, vacuum impregnation, spin coating, and brush coating.

6. The inorganic cesium copper halide perovskite microwire catalyst according to claim 5, characterized in that, The catalyst is a recyclable granular catalyst, consisting of an inert particle core and a CsCuCl3 micron-sized active layer coated on its surface. The inert particle core is selected from one or more of alumina particles, quartz particles, glass particles, or ceramic particles. The granular catalyst is prepared by one or more of the following methods: roller coating, disc granulation, spray coating, impregnation coating, or extrusion granulation.

7. The inorganic cesium copper halide perovskite microwire catalyst according to claim 5, characterized in that, An intermediate adhesion layer is introduced during the loading process. The intermediate adhesion layer is selected from one or more of silica sol, alumina sol, boehmite sol, polyvinylidene fluoride, polytetrafluoroethylene, and polyvinylpyrrolidone.

8. A fixed-bed photothermal catalytic reactor for use in the photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids as described in claim 1, characterized in that: It includes a reactor shell and an immobilized catalyst carrier filled inside the shell; the reactor shell is made of a light-transmitting material; the water to be treated passes through the fixed bed in an intermittent, circulating or continuous flow manner, and the pollutants are photothermal catalytically degraded under light conditions.

9. A method for photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids using inorganic cesium copper halide perovskite microwires, characterized in that, Includes the following steps: S1. Add the CsCuX3 micron-sized catalyst to the water sample to be degraded; S2. Photothermal catalytic degradation under illumination for 30-90 minutes; during this process, the CsCuX3 micron-wire catalyst is photoexcited to generate photogenerated electron-hole pairs, and part of the invisible light is converted into heat energy, causing the solution temperature to rise. On the one hand, the photogenerated charge carriers drive the photocatalytic oxidation / reduction reaction of antibiotics and / or perfluorocarboxylic acids; on the other hand, the temperature rise accelerates the reaction kinetics and increases the decomposition rate of pollutants.

10. The method for photothermal catalytic degradation of antibiotics / perfluorocarboxylic acids using inorganic cesium copper halide perovskite microwires according to claim 9, characterized in that, The dosage of the CsCuX3 micron-wire catalyst is 5-50 mg per 100 mL water sample; preferably, the light intensity of the illumination is 1 solar constant, and the spectral range covers UV to visible light.

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