All-weather photocatalytic water purification fluorescent beach system and preparation method and application thereof

Abstract

The application relates to the technical field of water treatment, and particularly discloses a fluorescent beach system for all-weather photocatalytic water purification as well as a preparation method and application thereof. The fluorescent beach system comprises a fluorescent beach base body paved by fluorescent sand and a photocatalytic reaction layer loaded on the surface of the fluorescent sand. The system breaks through the dependence of traditional photocatalysis on a continuous strong light source, solves the problem that a powder catalyst is difficult to be applied on a large scale, and has a cumulative removal rate of more than 95% for tetracycline and ofloxacin through 10-day continuous operation in a daily spraying mode. The system does not need an external energy source, has water body repair and landscape functions, and is suitable for antibiotic pollution treatment of open water bodies such as near-shore sea areas, landscape lakes, breeding ponds and the like.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to a fluorescent beach system for all-weather photocatalytic water purification, its preparation method, and its application. Background Technology

[0002] With the increasing intensification of agriculture and the acceleration of industrialization, the problem of antibiotic pollutants, represented by tetracyclines, remaining in the aquatic environment is becoming increasingly prominent. These pollutants have stable chemical structures, strong bioaccumulation, and easily induce drug-resistant bacteria, posing a potential threat to ecosystems and human health. Traditional water treatment processes are unable to effectively remove them.

[0003] For the advanced treatment of antibiotic pollutants in water bodies, photocatalytic advanced oxidation processes, represented by titanium dioxide (TiO2), have attracted much attention due to their high stability and low cost. To overcome the limitation of traditional TiO2 only responding to ultraviolet light (wavelength less than 387 nm, accounting for less than 5% of the solar spectrum), researchers have developed methods involving elemental doping, surface hydrogenation, and self-doping (introducing TiO2 into the water). 3+ Modification strategies such as [missing information] have successfully extended the photoresponse range to the visible light region (400 nm~760 nm). However, the activity evaluation of such visible light-responsive photocatalysts is generally carried out under high-intensity light sources, such as 30 W LED lamps commonly used in laboratories (light intensity of about 65 W·m). -2 or higher power xenon lamps (100 W·m) -2 (Above). In real-world applications, lighting conditions are often much more demanding: indoor lighting, smog, or natural light intensity at dusk can be as low as 20 W·m. -2 The following describes the characteristics of long-afterglow materials (phosphorescent materials) with "optical storage-re-release" properties, noting that their afterglow intensity in the dark is typically below 5 W·m. -2 Under such extremely weak light intensity, the photogenerated carrier yield of existing modified TiO2 is extremely low, making it almost impossible to drive effective pollutant degradation reactions. In addition, most existing photocatalysts exist in the form of nanoparticles, which are easily lost in open water bodies and difficult to recover. There is a lack of an integrated system that can be scaled up and operate continuously under extremely weak light conditions. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an all-weather photocatalytic water purification fluorescent beach system, its preparation method, and its application.

[0005] This invention provides a fluorescent beach system for all-weather photocatalytic water purification, comprising: Fluorescent beach substrate, wherein the fluorescent beach substrate is made of long afterglow material; Photocatalyst, wherein the photocatalyst is supported on the surface of the long afterglow material, and the photocatalyst is C and Ti.3+ Co-doped chiral mesoporous TiO2.

[0006] This invention designs C, Ti materials with extremely weak visible light response. 3+ Co-doped chiral mesoporous TiO2 photocatalysts reduce the weak afterglow light emitted by long-afterglow materials (fluorescent sand) (<5 W·m). -2 It can be effectively excited under light, achieving for the first time a dark-state high-efficiency photocatalytic degradation driven by afterglow light as the sole light source; at the same time, fluorescent sand is used as a light-storage-luminescence light source and catalyst carrier to construct a fluorescent beach water treatment system that can operate 24 / 7 without external energy and can store energy naturally. Large particle carriers are used to solve the problems of recycling and secondary pollution, and to achieve in-situ continuous remediation of pollutants in open water bodies.

[0007] Furthermore, the C and Ti 3+ Co-doped chiral mesoporous TiO2 has a helical stacked chiral mesoporous structure.

[0008] Furthermore, the long afterglow material is fluorescent sand; the afterglow intensity emitted by the fluorescent sand in the dark is less than 5 W·m. -2 .

[0009] Furthermore, the fluorescent sand is yellow-green fluorescent sand or blue fluorescent sand; the yellow-green fluorescent sand is SrAl2O4:Eu 2+ ,Dy 3+ The blue fluorescent sand is Sr2MgSi2O7:Eu 2+ ,Dy 3+ .

[0010] Furthermore, the particle size of the fluorescent sand is 1 cm to 3 cm.

[0011] Furthermore, the afterglow emission peak of the fluorescent sand is located at 500 nm to 540 nm.

[0012] The present invention also provides a method for preparing the aforementioned fluorescent beach system, comprising the following steps: L-type chiral surfactant was dissolved in a mixture of deionized water and sodium hydroxide solution to form a sol; hydrobromic acid was added to the sol and stirred; then trimethylammonium chloride and tetrabutyl titanate were added in sequence, stirred and aged, and after washing and drying, a chiral mesoporous TiO2 precursor was obtained. Chiral mesoporous TiO2 precursor was mixed with ascorbic acid and CO2-free distilled water, ultrasonically dispersed, and then subjected to hydrothermal reduction treatment. After the reaction was completed, the mixture was cooled, centrifuged, washed, and dried to obtain C and Ti. 3+ Co-doped chiral mesoporous TiO2; Fluorescent sand is laid to form a fluorescent beach substrate, and C and Ti are added. 3+A co-doped chiral mesoporous TiO2 photocatalyst is dispersed in water to form a loading liquid, which is then uniformly sprayed onto the surface of fluorescent sand and naturally dried to obtain the fluorescent sand system.

[0013] Furthermore, the L-type chiral surfactant is C 14 -L-AlaA is prepared by an amidation reaction of L-glutamic acid and myristoyl chloride.

[0014] Furthermore, the hydrothermal reduction treatment is performed at a temperature of 160℃~180℃ for a time of 5 h~7 h.

[0015] The present invention also provides an application of the aforementioned fluorescent beach system, wherein the application is to degrade tetracycline and / or ofloxacin in water.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention achieves, for the first time, the afterglow of long-afterglow materials (<5 W·m). -2 This invention directly drives efficient photocatalytic degradation as the sole light source: In existing technologies, long-afterglow materials are only used as auxiliary light sources under strong light irradiation, or even after being combined with photocatalysts, they still require a relatively strong light source to start. This invention designs C and Ti materials with extremely weak visible light response... 3+ Co-doped chiral mesoporous TiO2, enabling it to operate at temperatures below 5 W·m -2 It can still be effectively excited under high light intensity, and for the first time, the afterglow of fluorescent sand is used as the sole excitation source in the dark state. It also achieved significant pollutant degradation effect, breaking through the dependence of photocatalysis technology on continuous strong light source.

[0017] This invention employs an L-shaped chiral surfactant template to construct a helical stacked mesoporous structure, increasing the specific surface area and reducing surface defects (Ti). 3+ (Oxygen vacancies) promote pollutant adsorption and photogenerated carrier separation; simultaneously, hydrothermal reduction treatment is performed using VC as a reducing agent and carbon source to introduce C doping and Ti. 3+ Self-doping synergistically narrows the TiO2 band gap, significantly enhancing its response under extremely weak visible light. This catalyst, under conditions where the afterglow light emitted by fluorescent sand is the sole light source (light intensity < 5 W·m⁻¹), exhibits improved performance. -2 The photocatalytic degradation reaction of pollutants in water is effectively excited and driven, perfectly matching the afterglow characteristics of fluorescent sand.

[0018] This invention utilizes fluorescent sand as both a "light source" (a phosphorescent-luminescent carrier) and a "catalyst carrier" to construct a water treatment system in the form of a fluorescent beach. The large-particle fluorescent sand (0.5 cm to 5 cm) facilitates its deployment and recycling in natural water bodies, completely solving the problems of the difficulty in large-scale application of nanoparticle catalysts and their tendency to cause secondary pollution.

[0019] This invention relies entirely on natural light (or simulated 30 W LED visible light, 65 W·m). -2 It operates based on the light-storing and light-releasing properties of fluorescent sand, requiring no external energy source. Experiments show that it can operate continuously for 10 days (daytime illumination with a 30W LED lamp and a light intensity of 65W·m). -2 Even in complete darkness at night, relying solely on the afterglow of fluorescent sand, the system achieves a tetracycline removal rate of over 95%. This system exhibits excellent degradation performance in freshwater, simulated seawater, and complex water bodies containing humic acid. Particularly in seawater, it demonstrates superior resistance to salt ion interference due to the strong adsorption capacity of the catalyst surface, making it particularly suitable for in-situ remediation of open water bodies such as nearshore seas, landscape lakes, and aquaculture ponds. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art 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.

[0021] Figure 1 C and Ti prepared in Example 1 of this invention 3+ Scanning electron microscope (SEM) image of co-doped chiral mesoporous TiO2 photocatalyst.

[0022] Figure 2 C and Ti prepared in Example 1 of this invention 3+ X-ray photoelectron spectroscopy (XPS) of co-doped chiral mesoporous TiO2 photocatalyst.

[0023] Figure 3 C and Ti prepared in Example 1 of this invention 3+ Comparison of UV-Vis DRS spectra of co-doped chiral mesoporous TiO2 photocatalysts.

[0024] Figure 4 C and Ti prepared in Example 1 of this invention 3+ Comparison of calculated band gaps between co-doped chiral mesoporous TiO2 photocatalysts and Comparative Example 3 chiral mesoporous TiO2 without VC hydrothermal reduction treatment.

[0025] Figure 5 C and Ti prepared in Example 1 of this invention 3+ Co-doped chiral mesoporous TiO2 photocatalysts at light intensities as low as 5 W·m -2 Electron paramagnetic resonance (EPR) spectrum under extremely weak visible light illumination.

[0026] Figure 6 The experiment in this invention simulated weak visible light during the day (30 W LED lamp, luminous intensity 65 W·m). -2 A schematic diagram of the lighting pattern under completely dark conditions at night (relying solely on the afterglow of fluorescent sand).

[0027] Figure 7 This is a comparison chart showing the cumulative removal rates of tetracycline (TC) and ofloxacin (OFX) by the fluorescent beach systems prepared in Examples 1, 2 and Comparative Examples 1-4 of Experiment 1 of the present invention during 10 days of continuous operation.

[0028] Figure 8 This is a comparison chart showing the cumulative removal rate of tetracycline by the fluorescent beach system prepared in Example 1 of Experiment 2 of the present invention after operating for 10 days in fresh water, simulated seawater, and complex water environments containing humic acid.

[0029] Figure 9 The graph shows the cumulative removal rate of tetracycline (TC) and ofloxacin (OFX) of the fluorescent beach system prepared in Example 1 of Experiment 3 of this invention during 20 days of continuous operation, in order to verify the long-term stability of the system. Detailed Implementation

[0030] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods described in the embodiments of the present invention are conventional methods, and the materials and reagents used in the following embodiments are commercially available unless otherwise specified.

[0031] Example 1: A method for preparing a fluorescent beach system for all-weather photocatalytic water purification.

[0032] Weigh 5.0 g of L-glutamic acid and dissolve it in a mixture of 50 mL of deionized water and 10 mL of 2 mol / L NaOH solution. Adjust the pH to (10.5±0.5) and cool in an ice-water bath to (3±2℃). Slowly add 6.8 g of myristoyl chloride dropwise while simultaneously adding 2 mol / L NaOH solution to maintain the pH of the reaction solution between (10.5±0.5). After the addition is complete, continue stirring for 2 h. After the reaction is complete, adjust the pH to (2.5±0.5) with 6 mol / L HCl, precipitating a white solid. Filter the solid, wash it with deionized water until neutral, then wash it three times with petroleum ether, and dry it under vacuum at 40℃ for 24 h to obtain C. 14 -L-AlaA. Weigh 0.3 g of L-type chiral surfactant C. 14-L-AlaA was dissolved in a mixture of 10.0 mL deionized water and 10.0 mL 0.1 mol / L sodium hydroxide solution, and stirred for 10 min to form a homogeneous sol. 10.0 mL 0.1 mol / L hydrobromic acid was added to the sol, and the mixture was stirred for 1 h. Then, 0.25 mL trimethylammonium chloride (TMAPS) and 2.92 mL tetrabutyl titanate were added sequentially, and the mixture was stirred for another 2 h before being aged at 0 °C for 24 h. After aging, the resulting precipitate was washed three times each with deionized water and anhydrous ethanol, and then dried in a vacuum drying oven at 60 °C for 12 h to obtain a chiral mesoporous TiO2 precursor.

[0033] 1.0 g of chiral mesoporous TiO2 precursor was mixed with 0.5 g of ascorbic acid (VC) and 120 mL of CO2-free distilled water. The mixture was ultrasonically dispersed for 30 min at 300 W (40 kHz) and then transferred to a polytetrafluoroethylene-lined high-pressure reactor. Hydrothermal reduction was performed at 170 °C for 6 h. After the reaction, the mixture was allowed to cool naturally to room temperature (25 ± 2 °C). The reaction solution was then centrifuged (10000 r / min, 10 min) and washed three times each with deionized water and anhydrous ethanol. The washed product was then dried in a vacuum drying oven at 60 °C for 12 h to obtain C and Ti. 3+ Co-doped chiral mesoporous TiO2 photocatalyst. Characterization showed that this catalyst maintains a helical stacked chiral mesoporous structure. Figure 1 Its specific surface area was determined to be 77.3 m² using the nitrogen adsorption-desorption (BET) method. 2 / g, the average pore size calculated using the Barrett-Joyner-Halenda (BJH) model is 6.4 nm. XPS analysis shows ( Figure 2 ), Ti 3+ The content reaches 7.5%, and C doping is also present. UV-vis DRS shows a significant redshift of the absorption band edge to approximately 500 nm. Figure 3 The band gap width is narrowed to below 2.55 eV. Figure 4 This catalyst can operate under light intensities as low as 5 W·m⁻¹. -2 Even under extremely weak visible light irradiation, it can still produce obvious ·OH and ·O2. - Signal( Figure 5 This indicates that it has excellent response capability to extremely weak visible light.

[0034] Commercially available yellow-green fluorescent sand (SrAl2O4:Eu) with a particle size of 2±1 cm was selected. 2+ ,Dy 3+(Purchased from Chengxin Technology Luminescent Materials Development Co., Ltd.) was used as a long afterglow material. A fluorescent sand substrate approximately 10 cm thick was laid in a sandbox measuring 60 cm × 40 cm × 12 cm to simulate a coastal beach environment. C and Ti were then used... 3+ Co-doped chiral mesoporous TiO2 photocatalyst was dispersed in deionized water to form a loading solution with a concentration of 2 g / L. The loading solution was uniformly sprayed onto the surface of fluorescent sand, with 1 L of loading solution applied per square meter of fluorescent sand. After natural drying, a fluorescent sand system was obtained. The afterglow intensity of the fluorescent sand after daytime excitation by a light source was measured to be approximately 4.8 ± 0.2 W·m⁻¹. -2 The emission peak is located near 520 nm, which matches the absorption band of the catalyst well.

[0035] Example 2: A method for preparing a fluorescent beach system for all-weather photocatalytic water purification.

[0036] The yellow-green fluorescent sand in Example 1 was replaced with blue fluorescent sand (Sr2MgSi2O7:Eu). 2+ ,Dy 3+ (Purchased from Chengxin Technology Luminescent Materials Development Co., Ltd.), with the other conditions the same as in Example 1.

[0037] Comparative Example 1: Without laying fluorescent sand, only 0.48 g of C and Ti were used. 3+ The co-doped chiral mesoporous TiO2 photocatalyst was placed directly in the reactor in powder form, with the remaining conditions the same as in Example 1.

[0038] Comparative Example 2: Unloaded C and Ti 3+ The co-doped chiral mesoporous TiO2 photocatalyst was prepared by laying fluorescent sand, with all other conditions the same as in Example 1.

[0039] Comparative Example 3: Chiral mesoporous TiO2 that has not undergone VC hydrothermal reduction treatment (i.e., a sample prepared alone as a chiral mesoporous TiO2 precursor, calcined at 500°C for 2 h to remove the template agent, but without VC hydrothermal reduction) was used as the photocatalyst, with the other conditions being the same as in Example 1.

[0040] Comparative Example 4: The C and Ti prepared in Example 1 3+ The co-doped chiral mesoporous TiO2 photocatalyst was simply physically mixed with fluorescent sand at a mass ratio of 1:10 and then laid out as a beach. No spraying or loading was performed, and the other conditions were the same as in Example 1.

[0041] The fluorescent beach systems prepared in Examples 1 and 2 and Comparative Examples 1-4 were used to conduct antibiotic pollutant degradation tests under simulated natural weak visible light conditions.

[0042] Experiment 1: Degradation performance of different fluorescent beach systems Each group of fluorescent beach systems was placed in a photocatalytic reactor, using 30 W LED lamps as the light source to simulate weak natural visible light, with a light intensity adjustment of 65 W·m. -2 The wavelength range was 400 nm to 760 nm. The experiment lasted for 10 days, with the LED lights on during the day (8 hours) and off at night (16 hours), relying entirely on the afterglow of the fluorescent sand (<5 W·m). -2 Provide an excitation light source, such as Figure 6 As shown.

[0043] Continuous water intake was simulated using a spray method: 100 mL of simulated wastewater containing tetracycline (TC, 1 mg / L) and ofloxacin (OFX, 1 mg / L) was uniformly sprayed onto the surface of each group of fluorescent beach systems daily for 10 consecutive days, totaling 1000 mL of wastewater. After spraying, the wastewater flowed naturally across the fluorescent beach surface and seeped out, without being recycled. The antibiotic concentration in the seepage was monitored daily.

[0044] The results show that ( Figure 7 After 10 days of operation, the fluorescent beach system in Example 1 (hereinafter referred to as Example 1) achieved a cumulative removal rate of 96.8% for tetracycline and 95.1% for ofloxacin. This system operated without any added oxidant or external energy supply, relying solely on simulated weak daytime visible light (65 W·m²). -2 ) and nighttime fluorescent sand afterglow (<5 W·m -2 Under the conditions of dynamic spraying, the system achieved efficient and continuous degradation of two typical antibiotics day and night, demonstrating its practicality and stability.

[0045] The fluorescent beach system in Example 2 (hereinafter referred to as Example 2) achieved a cumulative removal rate of 93.8% for tetracycline and 91.5% for ofloxacin. Although silicate-based fluorescent sand has better chemical stability, its afterglow intensity is slightly lower, so its removal rate is slightly lower than that of the aluminate system (Example 1).

[0046] The fluorescent beach system in Comparative Example 1 (hereinafter referred to as Comparative Example 1) showed a cumulative removal rate of only 30% for tetracycline and only 28% for ofloxacin. During the LED light-on period (daytime simulation), the degradation efficiency was similar to that of Example 1. However, during the LED light-off period (nighttime simulation), the catalyst showed almost no degradation activity due to the lack of afterglow light provided by the fluorescent sand. This confirms that the continuous excitation of the photocatalyst by the afterglow light at night is the key to achieving all-weather degradation.

[0047] Comparative Example 2 (the fluorescent beach system) showed a cumulative removal rate of less than 8% for tetracycline and less than 7% for ofloxacin, confirming that the photocatalyst was the sole source of activity for the degradation reaction. Comparative Example 3 (the fluorescent beach system) showed a cumulative removal rate of only 45.2% for tetracycline and only 42.8% for ofloxacin, significantly lower than in Example 1. The photocatalyst in Comparative Example 3 was not subjected to hydrothermal reduction with VC and contained no C or Ti. 3+ Co-doped, with a wider band gap (3.1 eV, Figure 4 ), in the afterglow of fluorescent sand at night (<5 W·m) -2 Under these conditions, there is almost no light response, which proves that the C and Ti introduced by the hydrothermal reduction of VC... 3+ Co-doping is key to achieving extremely weak visible light response. In Comparative Example 4, the cumulative removal rate of tetracycline was only 58.6%, and the cumulative removal rate of ofloxacin was only 55.3%. Figure 7 Physical mixing causes the photocatalyst to be easily washed away by the water flow during the spraying process, and the photocatalyst does not have sufficient contact with the surface of the fluorescent sand, resulting in low photon transfer efficiency from the fluorescent sand to the catalyst.

[0048] Experiment 2: Degradation performance in different aquatic environments The fluorescent beach system of Example 1 was placed in complex aquatic environments including freshwater, simulated seawater (NaCl 25 g / L), and humic acid (10 mg / L), and operated for 10 days under the same light and spraying conditions as in Experiment 1 (100 mL of 1 mg / L tetracycline sprayed daily). The results showed that the cumulative removal rates of tetracycline in the fluorescent beach system of Example 1 were 96.8%, 92.1%, and 87.3% in freshwater, simulated seawater, and humic acid-containing water, respectively. Figure 8 The fluorescent beach system maintains high activity in seawater, thanks to the strong adsorption capacity of chiral mesoporous TiO2 for organic matter, which effectively resists the interference of salt ions.

[0049] Experiment 3: Degradation performance stability test The fluorescent beach system of Example 1 was placed in a photocatalytic reactor under the same lighting conditions as in Experiment 1. A continuous water inflow was simulated by spraying; 100 mL of simulated wastewater containing tetracycline (TC, 1 mg / L) and ofloxacin (OFX, 1 mg / L) was uniformly sprayed onto the surface of the fluorescent beach system daily for 20 consecutive days, totaling 2000 mL of wastewater. After spraying, the wastewater flowed naturally across the surface of the fluorescent beach and seeped out, without being recycled. The antibiotic concentration in the seepage was monitored daily.

[0050] The results show that ( Figure 9After 20 days of operation, the cumulative removal rate of tetracycline by the fluorescent beach system in Example 1 remained at 94.9%, and the cumulative removal rate of ofloxacin was 93.8%, which proves the high efficiency, practicality and stability of the fluorescent beach system.

[0051] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments.

[0052] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A fluorescent beach system for all-weather photocatalytic water purification, characterized in that, include: Fluorescent beach substrate, wherein the fluorescent beach substrate is made of long afterglow material; Photocatalyst, wherein the photocatalyst is supported on the surface of the long afterglow material, and the photocatalyst is C and Ti. 3+ Co-doped chiral mesoporous TiO2.

2. The fluorescent beach system according to claim 1, characterized in that, The C and Ti 3+ Co-doped chiral mesoporous TiO2 has a helical stacked chiral mesoporous structure.

3. The fluorescent beach system according to claim 1, characterized in that, The long afterglow material is fluorescent sand; the afterglow intensity emitted by the fluorescent sand in the dark is less than 5 W·m. -2 .

4. The fluorescent beach system according to claim 3, characterized in that, The fluorescent sand is yellow-green or blue fluorescent sand; the yellow-green fluorescent sand is SrAl2O4:Eu 2+ ,Dy 3+ The blue fluorescent sand is Sr2MgSi2O7:Eu 2+ ,Dy 3 + .

5. The fluorescent beach system according to claim 3, characterized in that, The particle size of the fluorescent sand is 1 cm to 3 cm.

6. The fluorescent beach system according to claim 3, characterized in that, The afterglow emission peak of the fluorescent sand is located at 500 nm to 540 nm.

7. A method for preparing a fluorescent beach system as described in any one of claims 1-6, characterized in that, Includes the following steps: L-type chiral surfactant was dissolved in a mixture of deionized water and sodium hydroxide solution to form a sol; hydrobromic acid was added to the sol and stirred; then trimethylammonium chloride and tetrabutyl titanate were added in sequence, stirred and aged, and after washing and drying, a chiral mesoporous TiO2 precursor was obtained. Chiral mesoporous TiO2 precursor was mixed with ascorbic acid and CO2-free distilled water, ultrasonically dispersed, and then subjected to hydrothermal reduction treatment. After the reaction was completed, the mixture was cooled, centrifuged, washed, and dried to obtain C and Ti. 3+ Co-doped chiral mesoporous TiO2; Fluorescent sand is laid to form a fluorescent beach substrate, and C and Ti are added. 3+ A co-doped chiral mesoporous TiO2 photocatalyst is dispersed in water to form a loading liquid, which is then uniformly sprayed onto the surface of fluorescent sand and naturally dried to obtain the fluorescent sand system.

8. The preparation method according to claim 7, characterized in that, The L-type chiral surfactant is C. 14 -L-AlaA is prepared by an amidation reaction of L-glutamic acid and myristoyl chloride.

9. The preparation method according to claim 7, characterized in that, The hydrothermal reduction treatment is performed at a temperature of 160℃~180℃ for a time of 5 h~7 h.

10. An application of the fluorescent beach system as described in any one of claims 1-6, characterized in that, The application is to degrade tetracycline and / or ofloxacin in water.

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