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CN-122010228-A - CsCuX3Application of microwires in degradation of antibiotics/perfluorocarboxylic acid organic matters, method and catalyst and immobilized reactor

CN122010228ACN 122010228 ACN122010228 ACN 122010228ACN-122010228-A

Abstract

The invention provides an application of CsCuX 3 micrometer wires in degrading antibiotics/perfluorocarboxylic acid organic matters, a method, a catalyst and an immobilization reactor, wherein inorganic cesium copper halide perovskite CsCuX 3 micrometer wires are used as a photo-thermal catalytic material, and the antibiotics and/or perfluoroorganic matters in water can be degraded under the illumination condition, so that the remarkable degradation of the antibiotics and PFOA can be realized in a short time. And CsCuX 3 microwires can be supported on inert carriers to prepare recyclable granular catalysts or to prepare fixed bed reactors for separation and recovery from the treated water. The CsCuX 3 micro-wire does not contain noble metal, has low material cost and high stability, and is suitable for degradation treatment of various water body types.

Inventors

  • XUE JUNPENG
  • YANG YONGGE

Assignees

  • 江苏科技大学

Dates

Publication Date
20260512
Application Date
20260407

Claims (10)

  1. 1. The application of the inorganic cesium-copper halide perovskite micro wire in photocatalytic degradation of antibiotics/perfluorocarboxylic acid organic matters is characterized in that the inorganic cesium-copper halide perovskite CsCuX 3 micro wire is used as a photocatalytic material for degradation of antibiotics and/or perfluoroorganic matters in water, wherein X is one of Cl, br and I.
  2. 2. The use of inorganic cesium copper halide perovskite micro wire according to claim 1 in photo-thermal catalytic degradation of antibiotics/perfluorocarboxylic acids organic matters, wherein CsCuX 3 micrometer wire catalyst is loaded on an inert carrier to prepare a fixed bed photo-thermal catalytic reactor, or is compounded with an inert particle carrier to prepare a recyclable particle catalyst, and the photo-thermal catalytic material is used for degrading antibiotics and/or perfluoroorganic matters in water.
  3. 3. Use of inorganic cesium copper halide perovskite micro wire according to claim 1, in photocatalytic degradation of antibiotics/perfluorocarboxylic acids organic matter, characterized in that said micro wire has a diameter of 100-300 microns and a length of 3-10 mm.
  4. 4. The use of the inorganic cesium copper halide perovskite microwires according to claim 1 in photocatalytic degradation of antibiotics/perfluorocarboxylic acid organic matters, wherein the degradation treated water is domestic sewage, cultivation wastewater, surface water or groundwater polluted by antibiotics and/or perfluorocarboxylic acid organic matters, the antibiotics are one or more of sulfamethoxazole, sulfadiazine, sulfadimidine, and the perfluorocarboxylic acid organic matters are one or more of perfluorooctanoic acid, perfluorobutyric acid, perfluorohexanoic acid, perfluorononanoic acid and perfluorodecanoic acid.
  5. 5. The inorganic cesium copper halide perovskite micro-wire catalyst for the application in photocatalytic degradation of antibiotics/perfluorocarboxylic acid organic matters according to claim 1 is characterized by being formed by compounding CsCuX 3 micro-wires with an inert carrier, wherein the inert carrier is selected from one or more of quartz plates, quartz beads, glass beads, quartz sand, alumina balls, alumina rings, alumina foam, honeycomb ceramics, cordierite honeycomb, glass fiber felt and quartz fiber felt, and the mode of loading the CsCuX 3 micro-wires on the surface of the inert carrier comprises one or more of dip coating, spray coating, drop coating, vacuum dipping, spin coating and brush coating.
  6. 6. The inorganic cesium copper halide perovskite micro-wire catalyst according to claim 5, wherein the catalyst is a recyclable particle type catalyst, and consists of an inert particle core and a CsCuCl 3 micro-wire active layer coated on the surface of the inert particle core, wherein the inert particle core is one or more selected from alumina particles, quartz particles, glass particles or ceramic particles, and the particle catalyst is prepared by one or more of a roll coating method, a disc granulation method, a spray coating method, an impregnation coating method or an extrusion granulation method.
  7. 7. The inorganic cesium copper halide perovskite microwire catalyst according to claim 5, wherein an intermediate adhesion layer is introduced during said loading process, said intermediate adhesion layer being selected from one or more of silica sol, alumina sol, boehmite sol, polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone.
  8. 8. The fixed bed photo-thermal catalytic reactor for the photo-thermal catalytic degradation of antibiotics/perfluorocarboxylic acids organic matters is characterized by comprising a reactor shell and an immobilized catalyst carrier filled in the shell, wherein the reactor shell is prepared by adopting a light-transmitting material, and a water body to be treated passes through the fixed bed in an intermittent, circulating or continuous flow mode to realize the photo-thermal catalytic degradation of pollutants under the illumination condition.
  9. 9. The method for degrading the antibiotics/perfluorocarboxylic acid organic matters by utilizing the inorganic cesium copper halide perovskite micron line photocatalysis is characterized by comprising the following steps of: S1, adding CsCuX 3 micrometer line catalyst into a water sample to be degraded; s2, photo-thermal catalytic degradation is carried out for 30-90 minutes under the illumination condition, in the process, csCuX 3 micrometer line catalyst is photo-excited to generate photo-generated electron-hole pairs, and invisible light is partially converted into heat energy, so that the temperature of the solution is increased, on one hand, photo-generated carriers drive photo-catalytic oxidation/reduction reaction of antibiotics and/or perfluorocarboxylic acid organic matters, on the other hand, the temperature rise accelerates the reaction dynamics, and the decomposition rate of pollutants is improved.
  10. 10. The method for degrading antibiotic/perfluorocarboxylic acid organic matter by inorganic cesium copper halide perovskite micro-wire photo-thermal catalysis according to claim 9, wherein the dosage of CsCuX 3 micro-wire catalyst is 5-50 mg per 100 mL water samples, preferably the light intensity of the illumination is 1 solar constant, and the spectrum range covers UV to visible light.

Description

Use of CsCuX 3 micro-wires in degradation of antibiotics/perfluorocarboxylic acid organic matters, method and catalyst and immobilized reactor Technical Field The invention relates to the technical field of environmental catalytic materials and water treatment, in particular to an application method of a copper-based halide perovskite material in the aspect of photo-thermal catalytic purification of water. In particular, the invention provides an application of CsCuX 3 micrometer wires in degrading antibiotics/perfluorocarboxylic acid organic matters, a method, a catalyst and an immobilization reactor. Background Antibiotic contamination has become an environmental concern worldwide. Sulfamethoxazole (Sulfamethoxazole, SMX for short) and other sulfa antibiotics are widely used in medical treatment, human and animal breeding, so that the sulfa antibiotics are difficult to completely degrade and continuously remain in the environment. Research shows that antibiotics are listed as one of the new pollutants which are important to control in China, and the environmental hazard is that drug resistance genes can be transmitted through an environmental medium, so that the problem of bacterial drug resistance is caused. The sulfonamide antibiotics are often detected in surface waters, and although the concentration is mostly at ng/L to mug/L level, the "false persistence" pollution characteristic is not ignored due to continuous discharge. The antibiotics are mainly derived from the ways of livestock and poultry breeding wastewater, domestic sewage, sewage treatment plant discharge and the like, and can form potential threats to the water ecological system and human health for a long time. Perfluorooctanoic acid (PFOA) is a typical new contaminant of perfluorinated compounds, with extremely high chemical inertness and bioaccumulation, and is widely present in environmental media. PFOA has large toxicity and difficult degradation, can stay in the environment for a long time, and brings serious hidden trouble to ecological safety and human immunity, nerve and reproductive health. Because the fluorocarbon bonds of PFOA are extremely stable, the traditional treatment method is difficult to remove efficiently. The existing degradation technology comprises advanced oxidation (such as ozone and photocatalysis), electrochemical flocculation, adsorption and the like, but the existing degradation technology has the defects of high cost, low efficiency, incomplete treatment and the like, and is difficult to popularize and apply in a large range. The photocatalysis technology shows the advantages of mild condition, high efficiency and no secondary pollution in PFOA degradation. However, conventional photocatalytic materials (e.g., tiO 2) generally respond only to UV light, have low solar energy utilization, and have poor stability in part, which limits their effectiveness in practical water treatment. In view of this, researchers have recently been working on developing new photocatalytic materials that have high activity, good visible light absorption properties and high stability at the same time, in an effort to achieve efficient degradation of PFOA in water. For example, there have been studies reviewing the characteristics and deficiencies of various PFOA photocatalytic degradation materials over the last 20 years and elucidating the possible degradation pathways of PFOA. Therefore, the method improves the response capability and stability of the photocatalytic material in the visible light region and even the infrared light region, and is a key direction for solving the problem of degradation of new pollutants. Perovskite-based photocatalytic materials are attracting attention due to their excellent photoelectric properties. The traditional lead-based halide perovskite has the problems of poor photostability, lead toxicity and the like although the perovskite has a proper band gap and high carrier mobility. As an emerging lead-free perovskite material, the copper-based halide perovskite (CsCuCl 3) has the advantages of environmental friendliness, high thermal stability and the like, and gradually becomes a research hot spot. In addition, preliminary photocatalysis research shows that the copper-based perovskite has good catalytic activity, namely, zn doping modification CsCuCl 3 shows high yield and selectivity for preparing benzaldehyde by toluene selective oxidation under visible light, and CsCuCl 3 and Cu nanocrystalline in-situ loading construction heterojunction can be used for preparing methane by selective photocatalysis CO 2 reduction. These advances illustrate the considerable potential of copper-based perovskite in the field of photocatalysis. However, the current system research for the photo-thermal synergistic catalysis of water purification by copper-based halide perovskite is still lacking. Traditional photocatalytic research has focused on the pure photo-generated carrier process with less attention to the