Method for preparing highly-dispersed metal particle anchored catalyst on the basis of photothermal-coupled subcritical technology, and use

Abstract

Disclosed in the present application are a method for preparing a highly-dispersed metal particle anchored catalyst on the basis of a photothermal-coupled subcritical technology, and the use. The preparation method for a catalyst of the present invention comprises: uniformly dispersing a metal salt and a support material in ultrapure water, and then transferring same to a photothermal-coupled reactor and sealing the reactor; and, under conditions of heating, pressurization and visible light irradiation, a subcritical fluid is formed. The high-temperature environment significantly improves the dispersion of metal particles, and the combined action of high pressure and light irradiation enhances the interaction between the support and the nanoparticles, thereby improving the anchoring stability of the catalyst. Compared with conventional photodeposition chemical methods, the method of the present invention enables the prepared catalyst to have significant advantages in terms of dispersibility and stability and to exhibit excellent catalytic performance in fields such as biomass catalytic oxidation and sterilization reactions.

Description

A method for preparing highly dispersed and anchored metal particle catalysts based on photothermal coupling subcritical technology and its application Technical Field

[0001] This invention relates to the field of metal-supported catalyst preparation technology, and in particular to a method and application for preparing highly dispersed and anchored metal particles based on photothermal coupling subcritical technology. Background Technology

[0002] In the field of catalysis, the dispersibility and anchoring properties of catalysts are among the key factors affecting catalytic performance. Traditional catalyst preparation methods suffer from problems such as catalyst particle agglomeration, uneven dispersion, and weak anchoring, leading to reduced catalytic efficiency and poor reusability. Therefore, developing a new method for preparing catalysts with highly dispersed and anchored metal particles is of great significance.

[0003] Currently, there are various methods for preparing metal-supported catalysts, including physical mixing, chemical precipitation, sol-gel methods, and impregnation methods. However, these methods have limitations to varying degrees when preparing highly dispersed, anchored metal particles. For example, while physical mixing and impregnation methods are simple, they struggle to ensure uniform dispersion of catalyst particles; chemical precipitation methods can produce relatively uniform catalyst particles, but often suffer from weak anchoring; and while sol-gel methods can produce highly dispersed catalysts, the preparation process often requires high-temperature calcination.

[0004] High-temperature, high-pressure fluids under subcritical conditions possess excellent dissolving power and mass transfer properties. Utilizing these characteristics, highly dispersed and effectively anchored metal particles can be achieved during catalyst preparation. Photothermal coupling technology is a novel technique combining light and heat energy. Through the photothermal effect, it can significantly increase the temperature and energy density of the reaction system, thereby accelerating the chemical reaction. Introducing photothermal coupling technology into subcritical water systems can further enhance the dispersion effect and anchoring strength during catalyst preparation. Photothermal coupling subcritical technology not only utilizes the non-contact heating characteristics of light energy, avoiding the thermal stress concentration and localized overheating problems that may arise from traditional heating methods, but also enhances the anchoring effect of metal particles on the catalyst support through the promoting effect of photochemical reactions. Summary of the Invention

[0005] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a method and application for preparing highly dispersed and anchored metal particles based on photothermal coupling subcritical technology.

[0006] The technical solution adopted in this invention is as follows:

[0007] A method for preparing highly dispersed, anchored metal particle catalysts based on photothermal coupling subcritical technology includes the following steps:

[0008] Step 1: Disperse the metal salt and carrier material in ultrapure water, mix them evenly by ultrasonication, and then transfer them to a photothermal coupling reactor. The photothermal coupling reactor is equipped with a quartz window, and a light source is provided on the outside of the quartz window.

[0009] The metal salt is at least one of the nitrates and chlorides corresponding to copper, nickel, and ruthenium;

[0010] The carrier material is at least one of the following: monometallic sulfide MoS2, polymetallic oxide CoFe2O4, and polymetallic sulfide Znln2S4;

[0011] Step 2: Introduce H2 or N2 into the mixture in the photothermal coupling reactor to replace the air in the reactor. Then stop introducing gas, seal the reactor, stir the mixture, and heat it to a temperature of 150-220℃ and a pressure of 1.5-2.5MPa. Turn on the light source to irradiate the mixture, controlling the visible light wavelength at 420-630nm, and maintain the load under stirring for 30-90 minutes.

[0012] Step 3: After the mixture obtained in Step 2 is cooled, it is centrifuged and separated. The resulting solid is washed with ultrapure water and anhydrous ethanol and then vacuum dried to obtain a highly dispersed metal particle anchoring catalyst.

[0013] Furthermore, in step 1, the dispersion concentration of the carrier material in ultrapure water is 0.5-5 g / L, and the mass of the metal element in the metal salt is 0.5-4% of the mass of the carrier material.

[0014] Furthermore, the light source mentioned in step 2 is a 200W-400W xenon lamp with a wavelength range of 420-630nm.

[0015] Furthermore, in step 2, the temperature inside the reactor is 160-200℃ and the pressure is 1.5-2.0MPa, and the stirring loading time in step 2 is 60-80min.

[0016] The metal particle highly dispersed anchored catalyst prepared by the method of the present invention is copper, nickel or ruthenium, and the mass of the metal is 0.5 to 4% of the mass of the support material.

[0017] This invention also provides the application of the highly dispersed anchored metal particle catalyst in photocatalytic disinfection of harmful bacteria. The metal in the catalyst is copper, and the support material is a monometallic sulfide MoS2 or a polymetallic sulfide Znln2S4. The mass of the metal element is 1-4% of the mass of the support material. The photocatalytic application method is as follows: the catalyst is added to a harmful bacteria solution, stirred at room temperature, and irradiated by a 100-300W xenon lamp light source. The visible light wavelength is controlled at 420-630nm by optical elements to carry out a multiphase catalytic water disinfection reaction.

[0018] This invention also provides the application of the highly dispersed metal particle anchored catalyst in the photocatalytic degradation of organic pollutants in water. The metal in the catalyst is nickel, and the support material is a polymetallic sulfide Znln2S4. The mass of the metal element is 3-4% of the mass of the support material. The photocatalytic application method is as follows: the catalyst is added to an aqueous solution of organic pollutants, stirred, and the pH value is adjusted to 1 ± 0.2. The mixture is stirred at room temperature, and first stirred in the dark for 20-60 minutes to reach adsorption-desorption equilibrium. Then, the photocatalytic degradation reaction is carried out under irradiation by a 200-400W Xe lamp with a cutoff filter of 420 nm.

[0019] This invention also provides the application of the highly dispersed metal particle anchored catalyst in photocatalytic oxidation reactions. The metal in the catalyst is ruthenium, and the support material is a polymetallic oxide CoFe2O4. The mass of the metal element is 3-4% of the mass of the support material. This catalyst is used to catalyze the oxidation of HMF to prepare FDCA. The reaction process is as follows: HMF, base, catalyst, and oxidant are dispersed in water, ultrasonically mixed, and then the mixture is transferred to a high-pressure reactor and sealed. The reactor is heated to 100-130℃ and stirred for 8-12 hours. The mass of the catalyst is 70-80% of the mass of HMF, and the molar ratio of base to HMF is 1.5-2:1. The oxidant is tert-butyl hydroperoxide, and the molar amount of the oxidant is 15-20 times the molar amount of HMF.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0021] 1) This invention utilizes the synergistic effect of photothermal coupling and subcritical environment to effectively promote the high dispersion of metal particles on the catalyst support, greatly increasing the number of active sites, thereby significantly improving the catalytic efficiency and reaction rate of the catalyst, and is applicable to a variety of chemical reaction processes.

[0022] 2) Under subcritical conditions, the interaction between metal particles and the support is optimized, forming stable chemical bonds, which effectively prevents the metal particles from falling off and agglomerating during the reaction process, extends the service life of the catalyst, and reduces the replacement frequency and cost.

[0023] 3) The preparation technology of the catalyst of the present invention is simple to operate, the reaction conditions are easy to control, and it is suitable for large-scale industrial production. It is beneficial to the batch preparation and cost control of catalyst products, and provides strong support for industrial applications. Attached Figure Description

[0024] Figure 1 is a schematic diagram of the photothermal coupling reactor in this invention; in Figure 1, 1-reactor, 2-gas cylinder, 3-light source, 4-quartz window, 5-magnetic stirrer.

[0025] Figure 2 is the EDS spectrum of the 1.0 wt% Cu / MoS2 catalyst prepared in Example 1;

[0026] Figure 3 is the EDS spectrum of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Example 2;

[0027] Figure 4. EDS spectrum of the 4.0 wt% Ni / ZnIn2S4 catalyst prepared in Example 3;

[0028] Figure 5 shows the catalytic degradation effect of the catalyst prepared in Example 3 on sulfamethoxazole;

[0029] Figure 6 shows the reusability of the catalyst prepared in Example 3;

[0030] Figure 7. EDS spectrum of the 4.0 wt% Ru / FeCo2O4 catalyst prepared in Example 4;

[0031] Figure 8 shows the catalytic oxidation effect of the catalyst prepared in Example 4;

[0032] Figure 9 shows the reusability of the catalyst prepared in Example 4;

[0033] Figure 10. EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 1;

[0034] Figure 11 EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 2;

[0035] Figure 12. EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 3;

[0036] Figure 13 EDS chromatogram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 4;

[0037] Figure 14. EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 5;

[0038] Figure 15 shows the EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 6. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0040] The structural schematic diagram of the photothermal coupling reactor used in this embodiment of the invention is shown in Figure 1. The photothermal coupling reactor includes a reactor 1 with a heating device. The reactor 1 is made of stainless steel. A quartz window 4 is provided on the top of the reactor 1, and a light source 3 is provided on the outside of the quartz window 4. A stirring magnet is added inside the reactor 1. The reactor 1 is placed on a magnetic stirrer 5. The top of the reactor 1 is provided with a gas inlet and a gas outlet. The gas inlet is connected to a gas cylinder 2 through an inlet pipe with an inlet valve, and the gas outlet is connected to an exhaust pipe with an outlet valve.

[0041] Example 1: Preparation of 1.0 wt% Cu / MoS2 catalyst using photothermal coupled subcritical technology, the steps are as follows:

[0042] 1) Dissolve 2.47 g (NH4)2MoO4 and 2.284 g NH2CSNH2 sequentially in 70 mL of water and stir for 30 min to ensure complete mixing to form mixed solution A; then adjust the pH of solution A to 7.0 with 1 M NaOH solution to obtain solution B, and transfer it to a 100 mL hydrothermal reactor with a polytetrafluoroethylene liner; after sealing the hydrothermal reactor, transfer it to an oven, heat it to 200 °C and maintain it for 24 h, and after cooling to room temperature, take it out to obtain mixed solution C containing precipitate; centrifuge solution C at 8000 rpm for 5 min to obtain a black solid precipitate; wash it three times each with ultrapure water and anhydrous ethanol to obtain a black solid material, and finally dry it in a vacuum oven at 60 °C for 8 h to obtain MoS2 material with a three-dimensional nanoflower-like structure.

[0043] 2) Disperse 2.1 mg CuCl2 and 100 mg MoS2 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. After opening the inlet and outlet valves and purging the system with hydrogen to remove air and dissolved oxygen, maintain atmospheric pressure, then close the inlet valve and maintain magnetic stirring. Heat the reaction solution in the photothermal coupling reactor to 200 °C and maintain a pressure of 1.5 MPa. Turn on the xenon lamp source with a power of 300 W and control the visible light wavelength in the range of 420-630 nm. After the reaction continues for 60 min, centrifuge to separate the solids. Wash the solids three times with water and anhydrous ethanol, and dry them under vacuum at 60 °C to obtain the 1.0 wt% Cu / MoS2 catalyst with a three-dimensional structure.

[0044] Figure 2 shows the EDX curve of the 1.0 wt% Cu / MoS2 catalyst prepared in Example 1. As can be seen from Figure 2, Cu atoms are highly dispersed on the surface of the MoS2 material in the 1.0 wt% Cu / MoS2 catalyst of Example 1.

[0045] The 1.0 wt% Cu / MoS2 catalyst prepared in Example 1 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0046] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension was prepared by adding 20 mL of PBS buffer solution and 0.02 g of the 1.0 wt% Cu / MoS2 catalyst. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Then, under magnetic stirring and at room temperature (25°C), 0.2 mL of the prepared *Pseudomonas aeruginosa* suspension was added. A 150 W xenon lamp was turned on to simulate sunlight, and the visible light wavelength was controlled at 420-630 nm using optical elements to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 15 min, and the total disinfection reaction time was 80 min.

[0047] The efficacy of 1.0 wt% Cu / MoS2 against Pseudomonas aeruginosa in this case is shown in Table 1. As can be seen from Table 1, Pseudomonas aeruginosa in the water was completely inactivated after 80 minutes.

[0048] S2: After 80 min of sterilization reaction in step S1, 1.0 wt% Cu / MoS2 in the residue was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and finally vacuum dried at 60°C to regenerate the catalyst. The recovered catalyst was then used for the next batch of sterilization experiments following the same procedure as in step S1, achieving the recycling of the sterilizing agent. This process was repeated, and sterilization experiment data for five cycles of catalyst recycling were obtained. The experimental results are shown in Table 1.

[0049] Table 1. Sterilization and recycling effects of 1.0wt% Cu / MoS2

[0050]

[0051] As can be seen from Table 1, the 1.0wt% Cu / MoS2 in Example 1 is effective in disinfecting harmful bacteria and has good reusability against Pseudomonas aeruginosa. After the 1.0wt% Cu / MoS2 is used 5 times, the sterilization effect does not change significantly.

[0052] Example 2: Preparation of 1.0 wt% Cu / ZnIn2S4 catalyst using photothermal coupled subcritical technology, the steps are as follows:

[0053] 1) Dissolve 0.068g ZnCl2, 0.239g InCl2·4H2O and 0.15g CH3CSNH2 in 40mL of water and mix thoroughly to prepare a 40mL mixed metal salt solution A. Then adjust the pH to 1.0 with 5M HCl solution to obtain solution B. Transfer B to a hydrothermal reactor with a polytetrafluoroethylene liner. After sealing the hydrothermal reactor, transfer it to an oven and heat it to 160℃ for 16h. After cooling to room temperature, remove it. At this time, mixed solution C contains precipitate. Then, wash it three times with ultrapure water and three times with anhydrous ethanol to obtain a yellow solid. Finally, dry it in a vacuum oven at 60℃ for 12h to successfully prepare the three-dimensional flower-like structure material ZnIn2S4.

[0054] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with hydrogen. Then, close the outlet valve and introduce pressurized H2 until the pressure inside the photothermal coupling reactor reaches 1 MPa. Close the inlet valve and maintain magnetic stirring. After heating to 160 °C and the pressure is 2 MPa, turn on the xenon lamp source (300 W power) and control the visible light wavelength in the range of 420-630 nm. After the reaction continues for 60 min, centrifuge to separate the solids. Wash the solids three times with water and anhydrous ethanol, and dry them under vacuum at 60 °C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0055] Figure 3 shows the EDX curve of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Example 2. As can be seen from Figure 3, Cu atoms are highly dispersed on the surface of ZnIn2S4 material in the 1.0 wt% Cu / ZnIn2S4 catalyst of Example 2.

[0056] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Example 2 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0057] S1: First, prepare a concentration of 10... 8The *Pseudomonas aeruginosa* suspension at CFU / mL was prepared, followed by 20 mL of PBS buffer solution and the addition of 0.02 g of catalyst. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Then, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight. The visible light wavelength was controlled at 420-630 nm using optical elements to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, for a total disinfection reaction time of 80 min.

[0058] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 2. As can be seen from Table 2, Pseudomonas aeruginosa in the water was completely inactivated after 80 minutes.

[0059] S2: After 80 min of sterilization reaction in step S1, 1.0 wt% Cu / ZnIn2S4 in the residue was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and finally vacuum dried at 60°C to regenerate the catalyst. The recovered catalyst was then used for the next batch of sterilization experiments following the same procedure as in step S1, achieving the recycling of the sterilizing agent. This process was repeated, and sterilization experiment data for five cycles of catalyst recycling were obtained. The experimental results are shown in Table 2.

[0060] In Example 2, 1.0wt% Cu / ZnIn2S4 was used for the disinfection of harmful bacteria. The reusability of 1.0wt% Cu / ZnIn2S4 is shown in Table 2. After 5 cycles of 1.0wt% Cu / ZnIn2S4, the sterilization effect did not change significantly.

[0061] Example 3: Preparation of 4.0 wt% Ni / ZnIn2S4 using photothermal coupling subcritical technology, the steps are as follows:

[0062] 1) The preparation method of ZnIn2S4 is the same as that in Example 2.

[0063] 2) 19.6 mg Ni(NO3)2·6H2O and 100 mg ZnIn2S4 were dispersed in 50 mL of ultrapure water and ultrasonically dispersed until uniform. The mixture was placed in a stainless steel photothermal coupling reactor and sealed. Referring to Figure 1, the gas inlet of the photothermal coupling reactor was connected to a hydrogen cylinder through an inlet pipe with an inlet valve. The inlet and outlet valves were opened to purge air and dissolved oxygen from the system with hydrogen. Then, the outlet valve was closed, and pressurized H2 was introduced until the pressure inside the photothermal coupling reactor reached 1 MPa. The inlet valve was then closed, and magnetic stirring was maintained. After heating to 160 °C and the pressure to 2 MPa, a xenon lamp light source was turned on. The xenon lamp power was 300 W, and the visible light wavelength was controlled at 420-630 nm. After the reaction continued for 60 min, the mixture was centrifuged. The obtained solid was washed three times with water and anhydrous ethanol, and then vacuum dried at 60 °C to obtain the 4.0 wt% Ni / ZnIn2S4 catalyst with a three-dimensional structure.

[0064] The EDX curve of the 4.0 wt% Ni / ZnIn2S4 catalyst prepared in Example 3 is shown in Figure 4. As can be seen from Figure 4, in the 4.0 wt% Ni / ZnIn2S4 catalyst of Example 3, Ni atoms are highly dispersed on the surface of ZnIn2S4 material.

[0065] The 4.0% Ni / ZnIn2S4 or ZnIn2S4 catalyst prepared in Example 3 was used for the degradation of sulfamethoxazole (SMX). The operation steps are as follows:

[0066] S1: 10 mg of catalyst was added to 50 mL of an aqueous solution containing SMX (1.5 mg / L). The reaction mixture was sonicated for 1 min, and the initial pH was adjusted to within a deviation range of 1 ± 0.2. The reaction mixture was then transferred to a quartz reactor, and a magnetic stir bar was added. The quartz reactor was placed on a magnetic stirrer and stirred in the dark for 30 min to allow SMX and the photocatalyst to reach adsorption-desorption equilibrium. Immediately afterward, the reactor was illuminated for reaction using a 300W Xe lamp with a cutoff filter of 420 nm. Samples were taken every 15 min under illumination for a total of 60 min.

[0067] Following the experimental procedure described above, the 4.0% Ni / ZnIn2S4 or ZnIn2S4 catalyst prepared in Example 3 was used for the degradation of sulfamethoxazole. The degradation effect of sulfamethoxazole is shown in Figure 5. As can be seen from Figure 5, the catalytic activity of 4.0% Ni / ZnIn2S4 is significantly higher than that of ZnIn2S4. After 60 min of catalytic degradation with 4.0% Ni / ZnIn2S4, 93.1% of sulfamethoxazole in the water has been degraded.

[0068] S2: The 4.0wt% Ni / ZnIn2S4 in the residue after 60 min of photocatalytic reaction under 4.0% Ni / ZnIn2S4 catalysis in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and vacuum dried at 60℃ before being subjected to degradation experiments again, thus achieving catalyst recycling. The reusability of 4.0wt% Ni / ZnIn2S4 is shown in Figure 6. After 5 cycles of 4.0wt% Ni / ZnIn2S4, the catalytic degradation effect did not change significantly. In Figure 6, the 80 min cycle time for each catalyst reuse was divided into two stages: a 30 min dark treatment stage and a 60 min photocatalytic reaction stage.

[0069] Example 4: Preparation of 4.0 wt% Ru / FeCo2O4 using photothermal coupling subcritical technology, the steps are as follows:

[0070] 1) Dissolve 1 mmol Fe(NO3)3·9H2O, 2 mmol Fe(NO3)3·9H2O, and 3 mmol citric acid monohydrate in 60 mL of deionized water and mix thoroughly. Next, pour the mixture into a preheated flask with a stopper and heat it in a 65°C water bath. Then, slowly add sodium hydroxide to the solution, maintaining a molar ratio of sodium hydroxide to Fe metal salt of 1:6 (i.e., 0.5 mmol of sodium hydroxide), while stirring in the water bath for 60 min. Adjust the pH of the solution to 13 by adding ammonia, stir again, and transfer the solution to a 200°C polytetrafluoroethylene hydrothermal reactor and seal it for 5 h of hydrothermal treatment. After hydrothermal treatment, allow the reactor to cool naturally to room temperature. Wash the resulting precipitate with deionized water and anhydrous ethanol until the washing solution is neutral, then dry it to obtain the iron-cobalt spinel nanocatalyst FeCo2O4.

[0071] 2) Dissolve 8.2 mg RuCl3 and 100 mg FeCo2O4 in 50 mL of ultrapure water and disperse evenly by ultrasonication. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a nitrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with nitrogen. Then, close the outlet valve, maintain atmospheric pressure, and close the inlet valve while maintaining magnetic stirring. After heating to 200 °C and reaching a pressure of 1.5 MPa, turn on the xenon lamp source (300 W), control the visible light wavelength to 420-630 nm, and react for 60 min. After centrifugation, wash the obtained solid three times with water and anhydrous ethanol, and dry it under vacuum at 60 °C to obtain the 4.0 wt% Ru / FeCo2O4 catalyst with a three-dimensional structure.

[0072] The EDX of the 4.0wt% Ru / FeCo2O4 catalyst prepared in Example 4 is shown in Figure 7. As can be seen from Figure 7, in the 4.0wt% Ru / FeCo2O4 catalyst prepared in Example 4, Ru atoms are highly dispersed on the surface of the FeCo2O4 material.

[0073] The 4.0 wt% Ru / FeCo2O4 ruthenium-based spinel catalyst material prepared in Example 4 was used for biomass oxidation. The operation steps are as follows:

[0074] S1: 0.5 mmol of 5-hydroxymethylfurfural (HMF), 1 mmol of NaOH, and 50 mg of 4.0 wt% FeCo2O4 catalyst were added to the reactor. 9 mmol of tert-butyl hydroperoxide (t-BuOOH) was added as an oxidant, and ultrapure water was used as the solvent to maintain the liquid phase volume at 20 mL. After ultrasonic mixing, the mixture was transferred to a micro high-pressure reactor and sealed. The temperature was raised to 120 °C, and magnetic stirring was started at 500 rpm. Samples were taken for analysis at regular intervals, filtered through a 0.22 μm filter membrane, and quantitatively analyzed by high-performance liquid chromatography (HPLC).

[0075] Following the experimental procedure described above, the 4.0 wt% Ru / FeCo2O4 catalyst from Example 4 was used for biomass oxidation, and the oxidation effect on HMF is shown in Figure 8. As can be seen from Figure 8, 99% of the HMF in the water was converted after 8 hours.

[0076] S2: After reacting for 20 hours under the catalysis of 4.0% Ru / FeCo2O4 in step S1, the 4.0% Ru / FeCo2O4 in the residue was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and dried under vacuum at 60℃ before being used for catalytic oxidation experiments again, thus achieving catalyst recycling. The recovered catalyst was used for the next batch of catalytic experiments following the steps in step S1, achieving catalyst recycling. This process was repeated, and the catalytic experimental data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Figure 9. The reusability of 4.0wt% Ru / FeCo2O4 is shown in Figure 9. After 5 cycles of 4.0wt% Ru / FeCo2O4, the oxidation effect did not change significantly.

[0077] Comparative Example 1: Preparation of 1.0 wt% Cu / ZnIn2S4 catalyst using photothermal coupled subcritical technology (room temperature and pressure), the steps are as follows:

[0078] 1) The preparation method of ZnIn2S4 is the same as that in Example 2.

[0079] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture in a quartz photoreactor, introduce hydrogen gas to remove dissolved oxygen from the system, maintain normal pressure, control the temperature in a constant temperature water bath, and maintain magnetic stirring. Turn on the xenon lamp with a power of 300 W and control the visible light band to 420-630 nm. After the photodeposition reaction continues for 1 hour, centrifuge the solid. Wash the obtained solid three times with water and anhydrous ethanol, and vacuum dry at 60 °C to obtain the 1.0 wt% Cu / ZnIn2S4 composite functional material with a three-dimensional structure.

[0080] The EDS diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 1 is shown in Figure 10. As can be seen from Figure 10, the Cu atoms in the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 1 are not uniformly distributed.

[0081] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 1 was used for the elimination of harmful Pseudomonas aeruginosa bacteria. The operation steps are as follows:

[0082] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension at CFU / mL was prepared, followed by 20 mL of PBS buffer solution and the addition of 0.02 g of catalyst. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Then, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight. The visible light wavelength was controlled at 420-630 nm using optical elements to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, for a total disinfection reaction time of 80 min.

[0083] Comparative Example 1, using 1.0 wt% Cu / ZnIn2S4, was used for highly effective elimination of harmful bacteria. The elimination effect on *Pseudomonas aeruginosa* is shown in Table 2. Table 2 shows that *Pseudomonas aeruginosa* in the water was completely inactivated after 80 minutes.

[0084] S2: The 1.0 wt% Cu / ZnIn2S4 in the residue after 80 min of sterilization reaction in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and finally vacuum dried at 60℃ to regenerate the catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, realizing the recycling of the sterilizing agent. This process was repeated, and the sterilization experiment data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Table 2. As shown in Table 2, the sterilization effect of 1.0 wt% Cu / ZnIn2S4 in Comparative Example 1 decreased significantly after 5 cycles, indicating that the anchoring effect of Cu nanoparticles on the ZnIn2S4 surface was poor.

[0085] Table 2. Effects of ambient temperature and pressure on the sterilization and recycling efficiency of catalyst materials.

[0086]

[0087] Comparative Example 2: Preparation of 1.0 wt% Cu / ZnIn2S4 using photothermal coupled subcritical technology (heating without pressure)

[0088] 1) The preparation process of ZnIn2S4 is as described in Example 2.

[0089] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse them evenly; place the mixture into a stainless steel photothermal coupling reactor and seal the photothermal coupling reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder via an inlet pipe with an inlet valve. The inlet and outlet valves are opened to purge air and dissolved oxygen from the system with hydrogen. Then, the outlet and inlet valves are closed, meaning no additional pressurized H2 is introduced into the photothermal coupling reactor to achieve internal H2 pressure. The H2 pressure inside the reactor is 0.1 MPa (at atmospheric pressure), and magnetic stirring is maintained. After heating to 160°C, the pressure reaches 0.5 MPa. A xenon lamp with a power of 300W is turned on, controlling the visible light wavelength to 420-630 nm. After the reaction continues for 60 minutes, centrifugation is performed. The resulting solid is washed three times with water and anhydrous ethanol, and then vacuum dried at 60°C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0090] The EDX diagram of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 2 is shown in Figure 11. As can be seen from Figure 11, in the 1.0 wt% Cu / ZnIn2S4 catalyst of Comparative Example 2, Cu atoms are highly dispersed on the surface of ZnIn2S4 material.

[0091] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 2 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0092] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension at CFU / mL was prepared, followed by 20 mL of PBS buffer solution and the addition of 0.02 g of catalyst. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Then, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight. The visible light wavelength was controlled at 420-630 nm using optical elements to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, for a total disinfection reaction time of 80 min.

[0093] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 3. As can be seen from Table 3, Pseudomonas aeruginosa in the water was completely inactivated after 80 minutes.

[0094] S2: The 1.0 wt% Cu / ZnIn2S4 in the residue after 80 min of sterilization reaction in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and finally vacuum dried at 60℃ to regenerate the catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, realizing the recycling of the sterilizing agent. This process was repeated, and the sterilization experiment data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Table 3. In Comparative Example 2, the sterilization effect decreased after 5 cycles of 1.0 wt% Cu / ZnIn2S4 recycling, indicating that low pressure is not conducive to the anchoring of Cu nanoparticles on the ZnIn2S4 surface.

[0095] Table 3. Effects of initial pressure on the sterilization and recycling efficiency of catalyst materials.

[0096]

[0097] Comparative Example 3: Preparation of 1.0 wt% Cu / ZnIn2S4 using photothermal coupling subcritical technology (room temperature and pressure), the steps are as follows:

[0098] 1) The preparation process of ZnIn2S4 is as described in Example 2.

[0099] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with hydrogen. Then close the outlet and inlet valves, i.e., do not additionally introduce pressurized H2 into the photothermal coupling reactor to achieve a pressurized state. The H2 pressure inside the photothermal coupling reactor is 2 MPa (at atmospheric pressure). Maintain 25°C, turn on the xenon lamp source (300 W), control the visible light wavelength to 420-630 nm, and react for 60 min. Centrifuge and separate the solids. Wash the obtained solids three times with water and anhydrous ethanol, and dry them under vacuum at 60°C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0100] Figure 12 shows the EDX curve of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 3. As can be seen from Figure 12, the dispersion of Cu atoms on the surface of ZnIn2S4 material in the 1.0 wt% Cu / ZnIn2S4 catalyst of Comparative Example 3 is worse than that in Example 2.

[0101] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 3 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0102] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension was prepared at CFU / mL. Then, 20 mL of PBS buffer solution was added and 0.02 g of catalyst was added. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Subsequently, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight (the visible light wavelength was controlled at 420-630 nm by optical elements) to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, and the total disinfection reaction time was 80 min.

[0103] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 4. As can be seen from Table 4, after 80 minutes, 92% of Pseudomonas aeruginosa in the water was inactivated, showing a decreasing trend compared to the effect in Example 2.

[0104] S2: The 1.0 wt% Cu / ZnIn2S4 in the residual liquid after 80 min of sterilization reaction in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and vacuum dried at 60℃ before being subjected to sterilization experiments again, thus realizing the recovery and regeneration of the sterilizing agent and catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, realizing the recycling of the sterilizing agent. In this way, the sterilization experiment data of the catalyst was tested after 5 cycles of recycling, and the experimental results are shown in Table 4. As shown in Table 4, the sterilization effect of 1.0 wt% Cu / ZnIn2S4 did not change much after 5 cycles of recycling. However, the catalyst prepared at room temperature in Comparative Example 3 was not conducive to the dispersion of metallic Cu on the support material, so its catalytic sterilization activity was not as good as that in Example 2.

[0105] Table 4. Effect of preparation temperature on the sterilization and recycling efficiency of catalyst materials.

[0106]

[0107] Comparative Example 4: Preparation of 1.0 wt% Cu / ZnIn2S4 catalyst using photothermal coupled subcritical technology (ultraviolet region), the steps are as follows:

[0108] 1) The preparation process of ZnIn2S4 is as described in Example 2.

[0109] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with hydrogen. Then close the outlet and inlet valves, i.e., do not additionally introduce pressurized H2 into the photothermal coupling reactor to achieve a pressurized state. The H2 pressure inside the photothermal coupling reactor is 1 MPa at atmospheric pressure. Raise the temperature to 160 °C and the pressure to 2 MPa. Turn on the xenon lamp source with a power of 300 W and control the wavelength range at 315-400 nm. After the reaction continues for 60 min, centrifuge the solid. Wash the obtained solid three times with water and anhydrous ethanol, and dry it under vacuum at 60 °C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0110] Figure 13 shows the EDX curve of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 4. As can be seen from Figure 13, the Cu atoms in the 1.0 wt% Cu / ZnIn2S4 catalyst of Comparative Example 4 are highly dispersed on the surface of ZnIn2S4 material compared with those in Example 2.

[0111] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 4 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0112] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension was prepared at CFU / mL. Then, 20 mL of PBS buffer solution was added and 0.02 g of catalyst was added. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Subsequently, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight (the visible light wavelength was controlled at 420-630 nm by optical elements) to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, and the total disinfection reaction time was 80 min.

[0113] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 5. As can be seen from Table 5, after 80 minutes, 100% of Pseudomonas aeruginosa in the water was inactivated, consistent with the effect in Example 2.

[0114] S2: After 80 minutes of sterilization reaction in step S1, 1.0 wt% Cu / ZnIn2S4 in the residual liquid was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and vacuum dried at 60℃ before being subjected to sterilization experiments again, achieving the recovery and regeneration of the sterilizing agent and catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, achieving the recycling of the sterilizing agent. This process was repeated, and the sterilization experiment data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Table 5. As shown in Table 5, after 5 cycles of 1.0 wt% Cu / ZnIn2S4 in Comparative Example 4, the sterilization effect remained at 100%. This is because Cu ions have stronger absorption in the ultraviolet region, which is beneficial to enhancing the interaction between Cu ions and the carrier, and strengthening the anchoring degree. However, due to the energy consumption and harm to the human body of ultraviolet light, visible light in the 420-630nm band is more advantageous when the application effect is similar.

[0115] Table 5. Effects of wavelength range on the sterilization and recycling efficiency of catalyst materials.

[0116]

[0117] Comparative Example 5: Preparation of 1.0 wt% Cu / ZnIn2S4 catalyst using photothermal coupled subcritical technology (infrared region), the steps are as follows:

[0118] 1) The preparation process of ZnIn2S4 is as described in Example 2.

[0119] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with hydrogen. Then close the outlet and inlet valves, i.e., do not additionally introduce pressurized H2 into the photothermal coupling reactor to achieve a pressurized state. The H2 pressure inside the photothermal coupling reactor is 1 MPa at atmospheric pressure. Raise the temperature to 160 °C and the pressure to 2 MPa. Turn on the xenon lamp source with a power of 300 W and control the wavelength range at 780-920 nm. After the reaction continues for 60 min, centrifuge and separate the solids. Wash the obtained solids three times with water and anhydrous ethanol, and dry them under vacuum at 60 °C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0120] Figure 14 shows the EDX curve of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 5. As can be seen from Figure 14, the Cu atoms in the 1.0 wt% Cu / ZnIn2S4 catalyst of Comparative Example 5 are also highly dispersed on the surface of ZnIn2S4 material compared with Example 2.

[0121] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 5 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0122] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension was prepared at CFU / mL. Then, 20 mL of PBS buffer solution was added and 0.02 g of catalyst was added. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Subsequently, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight (the visible light wavelength was controlled at 420-630 nm by optical elements) to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, and the total disinfection reaction time was 80 min.

[0123] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 5. As can be seen from Table 5, after 80 minutes, 100% of Pseudomonas aeruginosa in the water was inactivated, consistent with the effect in Example 2.

[0124] S2: The 1.0 wt% Cu / ZnIn2S4 in the residue after 80 min of sterilization reaction in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and vacuum dried at 60℃ before being subjected to sterilization experiments again, thus realizing the recovery and regeneration of the sterilizing agent and catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, realizing the recycling of the sterilizing agent. This process was repeated, and the sterilization experiment data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Table 5. As shown in Table 5, the sterilization effect of 1.0 wt% Cu / ZnIn2S4 in Comparative Example 5 decreased by 5% after 5 cycles. This is because Cu ions have weak absorption in the infrared region, which to some extent weakens the interaction between Cu ions and the support, making it easier for the loaded Cu ions to fall off after multiple uses.

[0125] Comparative Example 6: Preparation of 1.0 wt% Cu / ZnIn2S4 catalyst using photothermal coupled subcritical technology (other visible light regions), the steps are as follows:

[0126] 1) The preparation process of ZnIn2S4 is as described in Example 2.

[0127] 2) Disperse 2.1 mg CuCl2 and 100 mg ZnIn2S4 in 50 mL of ultrapure water and ultrasonically disperse until uniform. Place the mixture into a stainless steel photothermal coupling reactor and seal the reactor. Referring to Figure 1, the gas inlet of the photothermal coupling reactor is connected to a hydrogen cylinder through an inlet pipe with an inlet valve. Open the inlet and outlet valves to purge air and dissolved oxygen from the system with hydrogen. Then close the outlet and inlet valves, i.e., do not additionally introduce pressurized H2 into the photothermal coupling reactor to achieve a pressurized state. The H2 pressure inside the photothermal coupling reactor is 1 MPa at atmospheric pressure. Raise the temperature to 160 °C and the pressure to 2 MPa. Turn on the xenon lamp source with a power of 300 W and control the wavelength range at 650-780 nm. After the reaction continues for 60 min, centrifuge and separate the solids. Wash the obtained solids three times with water and anhydrous ethanol, and dry them under vacuum at 60 °C to obtain the 1.0 wt% Cu / ZnIn2S4 catalyst with a three-dimensional structure.

[0128] Figure 15 shows the EDX curve of the 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 6. As can be seen from Figure 15, the Cu atoms in the 1.0 wt% Cu / ZnIn2S4 catalyst of Comparative Example 6 are also highly dispersed on the surface of ZnIn2S4 material compared with Example 2.

[0129] The 1.0 wt% Cu / ZnIn2S4 catalyst prepared in Comparative Example 6 was used for the elimination of harmful bacteria. The operation steps are as follows:

[0130] S1: First, prepare a concentration of 10... 8 The *Pseudomonas aeruginosa* suspension was prepared at CFU / mL. Then, 20 mL of PBS buffer solution was added and 0.02 g of catalyst was added. The mixture was sonicated for 2 min to ensure uniform dispersion of the catalyst in the solution. Subsequently, under magnetic stirring and at room temperature (25°C), 0.2 mL of *Pseudomonas aeruginosa* suspension was added, and a 150 W xenon lamp was turned on to simulate sunlight (the visible light wavelength was controlled at 420-630 nm by optical elements) to carry out a multiphase catalytic water disinfection reaction. Samples were taken every 20 min, and the total disinfection reaction time was 80 min.

[0131] In this case, 1.0 wt% Cu / ZnIn2S4 was used for highly effective disinfection of harmful bacteria. The disinfection effect on Pseudomonas aeruginosa is shown in Table 5. As can be seen from Table 5, after 80 minutes, 100% of Pseudomonas aeruginosa in the water was inactivated, consistent with the effect in Example 2.

[0132] S2: The 1.0 wt% Cu / ZnIn2S4 in the residual liquid after 80 min of sterilization reaction in step S1 was separated by centrifugation, then washed repeatedly with ultrapure water and anhydrous ethanol, and vacuum dried at 60℃ before being subjected to sterilization experiments again, achieving the recovery and regeneration of the sterilizing agent and catalyst. The recovered catalyst was used for the next batch of sterilization experiments according to the method and steps in step S1, achieving the recycling of the sterilizing agent. This process was repeated, and the sterilization experiment data for 5 cycles of catalyst recycling were tested. The experimental results are shown in Table 5. As shown in Table 5, the sterilization effect of 1.0 wt% Cu / ZnIn2S4 in Comparative Example 6 decreased by 2% after 5 cycles. This is because the wavelength is close to the infrared region, which has a slight impact on the anchoring effect of Cu ions, and a small amount of the loaded Cu ions detached after multiple uses. After 20 cycles, the sterilization effect was significantly lower than that in Example 2. Therefore, 420-630 nm is the most suitable wavelength range for photothermal coupling technology.

[0133] Table 6. Comparison of sterilization effects of catalyst materials after 20 cycles of use.

[0134] .

Claims

1. A method for preparing highly dispersed, anchored metal particle catalysts based on photothermal coupling subcritical technology, characterized in that... Includes the following steps: Step 1: Disperse the metal salt and carrier material in ultrapure water, mix them evenly by ultrasonication, and then transfer them to a photothermal coupling reactor. The photothermal coupling reactor is equipped with a quartz window, and a light source is provided on the outside of the quartz window. The metal salt is at least one of the nitrates and chlorides corresponding to copper, nickel, and ruthenium; The carrier material is at least one of the following: monometallic sulfide MoS2, polymetallic oxide CoFe2O4, and polymetallic sulfide Znln2S4; Step 2: Introduce H2 or N2 into the mixture in the photothermal coupling reactor to replace the air in the reactor. Then stop introducing gas, seal the reactor, stir the mixture, and heat it to a temperature of 150-220℃ and a pressure of 1.5-2.5MPa. Turn on the light source to irradiate the mixture, controlling the visible light wavelength at 420-630nm, and maintain the load under stirring for 30-90 minutes. Step 3: After the mixture obtained in Step 2 is cooled, it is centrifuged and separated. The resulting solid is washed with ultrapure water and anhydrous ethanol and then vacuum dried to obtain a highly dispersed metal particle anchoring catalyst.

2. The method for preparing a highly dispersed, anchored metal particle catalyst based on photothermal coupling subcritical technology as described in claim 1, characterized in that... In step 1, the dispersion concentration of the carrier material in ultrapure water is 0.5-5 g / L, and the mass of the metal element in the metal salt is 0.5-4% of the mass of the carrier material.

3. The method for preparing a highly dispersed, anchored metal particle catalyst based on photothermal coupling subcritical technology as described in claim 1, characterized in that... The light source mentioned in step 2 is a 200W-400W xenon lamp with a wavelength range of 420-630nm.

4. The method for preparing a highly dispersed, anchored metal particle catalyst based on photothermal coupling subcritical technology as described in claim 1, characterized in that... In step 2, the temperature inside the reactor is 160-200℃ and the pressure is 1.5-2.0MPa. The stirring loading time in step 2 is 60-80min.

5. The highly dispersed, anchored metal particle catalyst prepared by any one of claims 1-4, characterized in that... The metal is copper, nickel, or ruthenium, and the mass of the metal is 0.5 to 4% of the mass of the carrier material.

6. The application of the highly dispersed metal particle anchoring catalyst as described in claim 5 in photocatalytic elimination of harmful bacteria, characterized in that... The metal is copper, and the support material is a monometallic sulfide MoS2 or a polymetallic sulfide Znln2S4. The mass of the metal element is 1-4% of the mass of the support material. The application of the highly dispersed anchored metal particle catalyst in photocatalytic disinfection of harmful bacteria is as follows: the catalyst is added to the harmful bacteria solution, stirred at room temperature, and irradiated by a 100-300W xenon lamp light source. The visible light wavelength is controlled at 420-630nm by optical elements to carry out a multiphase catalytic water disinfection reaction.

7. The application of the highly dispersed metal particle anchoring catalyst as described in claim 5 in the photocatalytic degradation of organic pollutants in water, characterized in that... The metal is nickel, and the support material is a polymetallic sulfide Znln2S4. The mass of the metal element is 3-4% of the mass of the support material. The application of the highly dispersed metal particle anchored catalyst in the photocatalytic degradation of organic pollutants in water is as follows: the catalyst is added to an aqueous solution of organic pollutants, stirred, and the pH value is adjusted to 1 ± 0.

2. The mixture is stirred at room temperature and first stirred in the dark for 20-60 minutes to reach adsorption-desorption equilibrium. Then, under the illumination of a 200-400W Xe lamp source with a cutoff filter of 420 nm, the photocatalytic degradation reaction is carried out.

8. The application of the highly dispersed metal particle anchored catalyst as described in claim 5 in photocatalytic oxidation reactions.

9. The application as described in claim 8, characterized in that... The metal is ruthenium, and the support material is a polymetallic oxide CoFe2O4. The mass of the metal element is 3-4% of the mass of the support material. This catalyst is used to catalyze the oxidation of HMF to prepare FDCA. The reaction process is as follows: HMF, base, catalyst and oxidant are dispersed in water, ultrasonically mixed evenly, the mixture is transferred to a high-pressure reactor and sealed, and the mixture is heated to 100-130℃ and stirred for 8-12 hours. The mass of the catalyst is 70-80% of the mass of HMF, and the molar ratio of base to HMF is 1.5-2:

1.

10. The application as described in claim 9, characterized in that... The oxidant is tert-butyl hydrogen peroxide, and the molar amount of the oxidant is 15-20 times the molar amount of HMF.

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