A composite nano-zinc oxide material for the degradation of organic pollutants in water and its preparation method

Abstract

This invention discloses a composite nano-zinc oxide material for the degradation of organic pollutants in water and its preparation method, belonging to the field of wastewater treatment agent preparation technology. A dispersion is obtained by mixing p-phenylenediamine, terephthalic acid, deionized water, and a mesoporous conditioner. An aqueous solution of zinc chloride is added to the dispersion, and the mixture reacts to obtain a porous polymer material. The porous polymer material is then impregnated in an alkaline solution to obtain zinc hydroxide@porous material. A mixed solution is obtained by mixing and dissolving ammonium molybdate, thiourea, and deionized water. The zinc hydroxide@porous material and the mixed solution are then subjected to a co-heating reaction and calcination to obtain the composite nano-zinc oxide material. This invention prepares a zinc hydroxide@porous material with a porous structure, and then reacts it with a molybdenum disulfide precursor solution to obtain a composite nano-zinc oxide material with good degradation effect on organic pollutants.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment agent preparation technology, specifically relating to a composite nano zinc oxide material for the degradation of organic pollutants in water and its preparation method. Background Technology

[0002] Water is the source of life and a fundamental natural resource for maintaining ecosystem balance and supporting human socio-economic development. With the acceleration of industrialization, the increase in urbanization, and the large-scale development of agricultural production, large amounts of wastewater containing organic pollutants are being discharged indiscriminately, leading to severe pollution of global aquatic environments. Water pollution refers to the phenomenon where, due to human activities or natural processes, a large amount of pollutants enter water bodies, exceeding the water body's self-purification capacity, thereby causing water quality deterioration, damage to aquatic ecosystems, and a reduction in the value of water resources. Organic pollutants, as one of the most significant types of water pollution, cause harm that is insidious, long-term, and cumulative. This harm manifests primarily in three aspects: the ecological environment (persistent organic pollutants such as polychlorinated biphenyls and organophosphorus pesticides accumulate in fish and algae, leading to deformities and decreased reproductive capacity in fish, and excessive algal growth, disrupting the food chain structure of aquatic bodies), human health (organic pollutants can also damage organs such as the liver, kidneys, and nervous system, causing chronic poisoning symptoms such as dizziness, fatigue, nausea, and vomiting; long-term exposure can lead to organ failure), and socio-economic factors (polluted water cannot be directly used for drinking, irrigation, or industrial production; it requires complex treatment to meet standards, increasing water treatment costs and the economic burden on businesses and governments). Based on the nature and source of pollutants, water pollution can be mainly divided into three categories: physical pollution, chemical pollution, and biological pollution. Chemical pollution is the most prevalent type, and organic pollutants are the most complex and harmful type of chemical pollution. Major organic pollutants originate from industrial production, including benzene compounds, halogenated hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), dyes, pesticides, and antibiotics. These pollutants are mostly highly toxic, difficult to degrade, and remain in water bodies for extended periods, posing serious threats to aquatic ecosystems and human health. For example, azo dyes in textile dyeing wastewater are not only toxic but also cause water discoloration and affect water transparency; antibiotics and hormones in pharmaceutical wastewater can affect the growth and reproduction of aquatic organisms and lead to antibiotic resistance in humans. Petroleum pollutants, including alkanes, cycloalkanes, and aromatic hydrocarbons, especially PAHs, are carcinogenic and can accumulate through the food chain, harming human health. Various treatment methods have been developed for organic pollutants in water bodies, which can be categorized into four main types based on their treatment principles: physical treatment, chemical treatment, biological treatment, and advanced oxidation treatment. Advanced oxidation processes are a new type of water treatment technology developed in recent years. The core of this technology is to generate highly oxidizing hydroxyl radicals through light, electricity, catalysts, and other means, which decompose large organic molecules into small organic acids, titanium dioxide, and water. It mainly includes photocatalytic oxidation, electrocatalytic oxidation, and Fenton oxidation. It has the characteristics of high treatment efficiency, wide applicability, and the ability to degrade recalcitrant organic pollutants, making it an effective method for treating recalcitrant organic pollutants.The core of photocatalytic degradation is to utilize the strong oxidizing free radicals generated by nanomaterials under light conditions to decompose organic pollutants into harmless substances. Although nanomaterials have significant advantages and broad application prospects in the degradation of organic pollutants in water, there are still many defects and shortcomings in their practical applications. These mainly focus on the problems of nanomaterial aggregation, poor performance when used alone, and poor application stability. These problems seriously limit the large-scale application of nanomaterials.

[0003] Zinc oxide and molybdenum disulfide are both common photocatalytic degradation materials. When used alone, their effects on degrading organic matter are limited. However, when used in combination, they can complement each other, effectively broadening the photoresponse range, promoting charge separation, inhibiting photocorrosion, and increasing active sites, thus significantly improving photocatalytic performance. However, when prepared in combination, poor bonding between materials and shielding of active sites can easily lead to poor photocatalytic degradation of organic matter.

[0004] Dye wastewater is a major contributor to industrial wastewater pollution. Developing a novel photocatalytic degradation material that combines zinc oxide and molybdenum disulfide to effectively degrade dye wastewater is of significant value in broadening the application methods of photocatalytic materials and improving degradation efficiency. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention prepares a zinc hydroxide@porous material with a porous structure, and then reacts it with a molybdenum disulfide precursor solution to obtain a composite nano-zinc oxide material with good degradation effect on organic pollutants, thereby solving the technical problems mentioned in the background art. Specifically, the technical solution of this invention includes the following: One objective of this invention is to provide a method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, the preparation method comprising the following steps: p-phenylenediamine, terephthalic acid, deionized water and mesoporous regulator are mixed to obtain a dispersion. Zinc chloride aqueous solution is added to the dispersion and mixed. The mixture is then heated to 160℃~170℃ and reacted for 24h~25h to obtain a porous polymer material. Zinc hydroxide@porous material is obtained by impregnating porous polymeric material in alkaline solution; Ammonium molybdate, thiourea, and deionized water were mixed and dissolved to obtain a mixed solution; The composite nano-zinc oxide material is obtained by mixing zinc hydroxide, porous material, and a mixture in a weight ratio of 1:50~60, followed by co-heating reaction and calcination.

[0006] Furthermore, the mesoporous regulator includes poloxamer 407.

[0007] Furthermore, the mass concentration of the zinc chloride aqueous solution is 13 g / L to 14 g / L.

[0008] Furthermore, the ratio of p-phenylenediamine, terephthalic acid, deionized water, mesoporous conditioner, and zinc chloride aqueous solution is 4.5g~7g:5g~8g:400mL~560mL:23g~38g:4mL~7mL.

[0009] Furthermore, the alkaline solution includes a sodium hydroxide solution with a pH of 9.5 to 10, or a potassium hydroxide solution with a pH of 9.5 to 10.

[0010] Furthermore, the conditions for the impregnation treatment include an impregnation temperature of 25°C and an impregnation time of 1 hour.

[0011] Furthermore, the weight ratio of ammonium molybdate, thiourea, and deionized water is 0.3894~0.3944:0.4575~0.7591:65~70.

[0012] Furthermore, the conditions for the co-heating reaction include a reaction temperature of 200℃~220℃ and a reaction time of 24h~26h.

[0013] Furthermore, the calcination conditions include a calcination temperature of 400℃~450℃ and a calcination time of 40min~50min.

[0014] A second objective of this invention is to provide a composite nano-zinc oxide material for the degradation of organic pollutants in water.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: The composite nano-zinc oxide material prepared by the technical method of this invention can achieve a higher removal effect under lower dose radiation conditions when photocatalytically degrading organic pollutants in water, and has a significant light energy utilization rate. Attached Figure Description

[0016] Figure 1 The figures are XRD patterns of the composite nano zinc oxide materials obtained in Examples 1-4 of the present invention. In the figures, a is the XRD pattern of the composite nano zinc oxide material obtained in Example 1, b is the XRD pattern of the composite nano zinc oxide material obtained in Example 2, c is the XRD pattern of the composite nano zinc oxide material obtained in Example 3, and d is the XRD pattern of the composite nano zinc oxide material obtained in Example 4. Figure 2 This is a SEM image of the composite nano-zinc oxide material obtained in Example 1 of the present invention. The icon size is 200 nm. Figure 3 This is a SEM image of the composite nano-zinc oxide material obtained in Example 2 of the present invention. The icon size is 200 nm. Figure 4This is a SEM image of the composite nano-zinc oxide material obtained in Example 3 of the present invention. The icon size is 200 nm. Figure 5 This is a SEM image of the composite nano-zinc oxide material obtained in Example 4 of the present invention. The icon size is 200 nm. Figure 6 This is a SEM image of the composite nano-zinc oxide material obtained in Comparative Example 1 of the present invention. The icon size is 200 nm. Figure 7 This is a SEM image of the composite nano-zinc oxide material obtained in Comparative Example 2 of the present invention. The icon size is 200 nm. Figure 8 This is a SEM image of the composite nano-zinc oxide material obtained in Comparative Example 3 of the present invention. The icon size is 200 nm. Figure 9 This is a SEM image of the composite nano-zinc oxide material obtained in Comparative Example 4 of the present invention. The icon size is 200 nm. Figure 10 The image shows a SEM image of the composite nano-zinc oxide material obtained in Comparative Example 5 of this invention. The image size is 200 nm. Detailed Implementation

[0017] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments and accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

[0018] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods. Example 1

[0019] A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: 4.5 g of p-phenylenediamine, 5 g of terephthalic acid, 400 mL of deionized water, and 23 g of poloxamer 407 were mixed and then placed in a 25°C environment. The mixture was stirred at 600 rpm for 40 min to obtain a dispersion. Next, 4 mL of a pre-prepared 13 g / L zinc chloride aqueous solution was added to the dispersion, and the stirring speed was reduced to 300 rpm. The mixture was stirred for another 1 h. The entire mixture was then poured into a reaction vessel and heated to 160°C in a sealed environment. The reaction was carried out for 24 h. After the reaction, the solid particles were removed and immersed in a sodium hydroxide solution at 25°C and pH 9.5 for 1 h. After impregnation, the solid particles were filtered out. They were first rinsed with deionized water until the rinsing wastewater was neutral, then rinsed three times with anhydrous ethanol, followed by three more rinses with deionized water. Finally, they were dried in a 50℃ drying oven for 10 hours to obtain zinc hydroxide@porous material. 0.3894 g of ammonium molybdate and 0.4575 g of thiourea were weighed and added to 65 mL of deionized water, mixed and stirred until dissolved and evenly dispersed to obtain a mixed solution. 1 g of zinc hydroxide@porous material and 50 mL of the mixed solution were weighed and poured into a reaction vessel, then heated to 200℃ in a sealed environment and reacted for 24 hours. After the reaction, the precipitate was collected by centrifugation, washed three times with deionized water, filtered using a vacuum pump, and finally dried in an 80℃ drying oven for 5 hours to obtain a solid dried product. The solid dried product was calcined at 400℃ in air for 40 minutes. Finally, it was naturally cooled to room temperature and removed to obtain the composite nano-zinc oxide material. Example 2

[0020] A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: 5g of p-phenylenediamine, 6g of terephthalic acid, 440mL of deionized water, and 27g of poloxamer 407 were mixed and then placed in a 25°C environment. The mixture was stirred at 600 rpm for 40 minutes to obtain a dispersion. Next, 5mL of a pre-prepared 13g / L zinc chloride aqueous solution was added to the dispersion, and the stirring speed was reduced to 300 rpm. The mixture was stirred for another 1 hour. The entire mixture was then poured into a reaction vessel and heated to 160°C in a sealed environment. The reaction was carried out for 25 hours. After the reaction, the solid particles were removed and immersed in a sodium hydroxide solution at 25°C and pH 9.5 for 1 hour. After impregnation, the solid particles were filtered out. They were first rinsed with deionized water until the rinsing wastewater was neutral, then rinsed three times with anhydrous ethanol, followed by three more rinses with deionized water. Finally, they were dried in a 50℃ drying oven for 10 hours to obtain zinc hydroxide@porous material. 0.3930 g of ammonium molybdate and 0.6060 g of thiourea were weighed and added to 65 mL of deionized water, mixed and stirred until dissolved and evenly dispersed to obtain a mixed solution. 1 g of zinc hydroxide@porous material and 50 mL of the mixed solution were weighed and poured into a reaction vessel, then heated to 200℃ in a sealed environment and reacted for 25 hours. After the reaction, the precipitate was collected by centrifugation, washed three times with deionized water, filtered using a vacuum pump, and finally dried in an 80℃ drying oven for 5 hours to obtain a solid dried product. The solid dried product was calcined at 420℃ in air for 40 minutes. Finally, it was naturally cooled to room temperature and removed to obtain the composite nano-zinc oxide material. Example 3

[0021] A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: 6g of p-phenylenediamine, 7g of terephthalic acid, 500mL of deionized water, and 33g of poloxamer 407 were mixed and then placed in a 30°C environment. The mixture was stirred at 700 rpm for 45 min to obtain a dispersion. Next, 6mL of a pre-prepared 14g / L zinc chloride aqueous solution was added to the dispersion, and the stirring speed was reduced to 300 rpm. The mixture was stirred for 1 h. The entire mixture was then poured into a reaction vessel and heated to 170°C in a sealed environment. The reaction was carried out at this temperature for 25 h. After the reaction, the solid particles were removed and immersed in a sodium hydroxide solution at 25°C and pH 10 for 1 h. After impregnation, the solid particles were filtered out. They were first rinsed with deionized water until the rinsing wastewater was neutral, then rinsed three times with anhydrous ethanol, followed by three more rinses with deionized water. Finally, they were dried in a 50℃ drying oven for 10 hours to obtain zinc hydroxide@porous material. 0.3931g of ammonium molybdate and 0.6065g of thiourea were weighed and added to 70mL of deionized water, mixed and stirred until dissolved and evenly dispersed to obtain a mixed solution. 1g of zinc hydroxide@porous material and 60mL of the mixed solution were weighed and poured into a reaction vessel, then heated to 210℃ in a sealed environment and reacted for 26 hours. After the reaction, the precipitate was collected by centrifugation, washed three times with deionized water, filtered using a vacuum pump, and finally dried in an 80℃ drying oven for 5 hours to obtain a solid dried product. The solid dried product was calcined at 440℃ in air for 50 minutes. Finally, it was naturally cooled to room temperature and removed to obtain the composite nano-zinc oxide material. Example 4

[0022] A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: 7g of p-phenylenediamine, 8g of terephthalic acid, 560mL of deionized water, and 38g of poloxamer 407 were mixed and then placed in a 30°C environment with stirring at 800 rpm for 50 min to obtain a dispersion. Next, 7mL of a pre-prepared 14g / L zinc chloride aqueous solution was added to the dispersion, and the stirring speed was reduced to 300 rpm, with stirring continued for 1 h. The mixture was then poured into a reaction vessel, heated to 170°C in a sealed environment, and reacted for 25 h. After the reaction, the solid particles were removed and immersed in a sodium hydroxide solution at 25°C and pH 10 for 1 h. After impregnation, the solid particles were filtered out. They were first rinsed with deionized water until the rinsing wastewater was neutral, then rinsed three times with anhydrous ethanol, followed by three more rinses with deionized water. Finally, they were dried in a 50℃ drying oven for 10 hours to obtain zinc hydroxide@porous material. 0.3944g of ammonium molybdate and 0.7591g of thiourea were weighed and added to 70mL of deionized water, mixed and stirred until dissolved and evenly dispersed to obtain a mixed solution. 1g of zinc hydroxide@porous material and 60mL of the mixed solution were weighed and poured into a reaction vessel, then heated to 220℃ in a sealed environment and reacted for 26 hours. After the reaction, the precipitate was collected by centrifugation, washed three times with deionized water, filtered using a vacuum pump, and finally dried in an 80℃ drying oven for 5 hours to obtain a solid dried product. The solid dried product was calcined at 450℃ in air for 50 minutes. Finally, it was naturally cooled to room temperature and removed to obtain the composite nano-zinc oxide material.

[0023] Comparative Example 1 A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: In Example 4, poloxamer 407 was replaced with poloxamer 188, and the rest of the preparation process remained the same as in Example 4.

[0024] Comparative Example 2 A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: Weigh 0.8g of ammonium molybdate and 1.5g of thiourea and add them to 70mL of deionized water. Mix and stir until dissolved and evenly dispersed to obtain a mixed solution. The rest of the preparation process is the same as in Example 4.

[0025] Comparative Example 3 A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: The amount of poloxamer 407 in Example 4 was increased to 50g, while the rest of the preparation process remained the same as in Example 4.

[0026] Comparative Example 4 A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: The calcination temperature in the example was increased to 500°C, the processing time was extended to 60 min, and the rest of the preparation process remained the same as in Example 4.

[0027] Comparative Example 5 A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, specifically including the following steps: The zinc hydroxide@porous material obtained in Example 4 was calcined at 450°C in air for 50 min to obtain nano-zinc oxide. 0.3944 g of ammonium molybdate and 0.7591 g of thiourea were weighed and added to 70 mL of deionized water. The mixture was stirred until dissolved and evenly dispersed to obtain a mixed solution. The mixed solution was poured into a reaction vessel and heated to 220°C in a sealed environment for 26 h. After the reaction, the precipitate was collected by centrifugation. The precipitate was washed three times with deionized water, filtered by vacuum pump, and finally dried in an 80°C drying oven for 5 h to obtain molybdenum disulfide. Nano-zinc oxide and molybdenum disulfide were added together in an agate mortar at a 1:1 mass ratio and ground continuously for 5 minutes. The gray powder on the mortar was scraped off to obtain the composite nano-zinc oxide material.

[0028] (a) Material characterization: (1) The composite nano-zinc oxide materials obtained in Examples 1-4 were characterized by X-ray powder diffraction (XRD), with molybdenum disulfide and zinc oxide as references. The test parameters used were as follows: tube voltage 40 kV, tube current 40 mA, continuous scanning mode, diffraction angle range (2θ) of 20°~75°, and scanning speed 0.02° / s. The results are shown in […]. Figure 1 As can be seen from the figure, the characteristic diffraction peaks of the prepared composite nano zinc oxide material are similar to those of ZnO and MoS2. (2) The microstructure of the composite nano-zinc oxide materials obtained in Examples 1-4 and Comparative Examples 1-5 was characterized by field emission scanning electron microscopy (SEM), and the results are shown in the figure. Figures 2-10 ,in Figures 2-5 The composite nano zinc oxide materials corresponding to Examples 1-4 are respectively. Figures 6-10 Comparing the composite nano zinc oxide materials of Examples 1 to 5 in turn, as can be seen from the SEM images, the composite nano zinc oxide materials of Examples 1 to 4 have complete structures and uniform distribution, but the composite nano zinc oxide materials of Examples 1 to 5 exist in a completely irregular fragmented form, and the structure of the material is severely damaged, which has a negative impact on the photocatalytic activity of the material.

[0029] (II) Photocatalytic performance The concentration is 5×10-5 A mol / L methylene blue solution was prepared. 50 mL of the methylene blue solution was added to a beaker. 0.1 g of the composite nano-zinc oxide materials obtained in Examples 1-4 and Comparative Examples 1-5 were added to the beaker respectively. Under low-dose ultraviolet radiation of 7 W, samples were taken every 60 min, and the absorbance in the wavelength range of 400-800 nm was measured using a UV-Vis spectrophotometer. A methylene blue solution without any reagents was used as a blank reference, and other conditions remained unchanged.

[0030] The degradation rates of methylene blue at 60 min and 120 min were calculated using the formula (A1-A) / A1, where A1 and A are the initial absorbance and absorbance after degradation, respectively. The results are shown in Table 1 below.

[0031] Table 1 Degradation rate The following conclusions can be drawn from Table 1 above: (1) As can be seen from Examples 1 to 4, the composite nano zinc oxide prepared by the present invention can achieve a higher removal effect under low-radiation ultraviolet light and is effective for the removal of organic dye wastewater.

[0032] (2) Comparative Example 1 shows that the photocatalytic degradation activity of the prepared composite nano zinc oxide material is poor. This may be because poloxamer 188 has a smaller molecular weight, shorter hydrophilic and hydrophobic chains, and poorer steric hindrance compared to poloxamer 407. The micelles may stick together to form aggregates during the condensation process due to molecular chain movement and cross-linking reaction, which is not conducive to the deposition of zinc hydroxide. Moreover, the aggregates may easily lead to poor and uneven molybdenum disulfide loading when mixed with the molybdenum disulfide precursor solution in the subsequent reaction, which is not conducive to the formation of the composite structure and thus affects the photocatalytic degradation performance.

[0033] (3) Comparative Example 2 shows that the photocatalytic degradation activity of the prepared composite nano zinc oxide material is poor. This may be because although adding ammonium molybdate and thiourea can ensure that molybdenum is maximized to be converted into molybdenum disulfide, the excessive amount of thiourea may cause excessive hydrogen sulfide to be generated at high temperature, which will react with zinc oxide to form impurities such as zinc sulfide, affecting the formation of zinc oxide, destroying the composite structure of the two, and resulting in poor photocatalytic efficiency.

[0034] (4) Comparative Example 3 shows that the photocatalytic degradation activity of the prepared composite nano zinc oxide material is poor. This may be because poloxamer can form micelles through self-assembly to create pores and thus increase the loading. However, excessive poloxamer may increase the viscosity of the system, which is not conducive to pore formation and thus affects the loading. On the other hand, excessive poloxamer may over-encapsulate the particles, causing the particles to aggregate and become larger. Oversized particles may lose the photocatalytic activity at the nanoscale, destroy the composite structure, and thus be not conducive to the photocatalytic degradation of organic matter.

[0035] (5) Comparative Example 4 shows that the photocatalytic degradation activity of the prepared composite nano zinc oxide material is poor. This may be because, on the one hand, high temperature will drive the crystal nuclei to continue to merge and grow, resulting in excessively large particle size and loss of nano-size effect; on the other hand, excessive calcination treatment may make the powder more compact and caking, the specific surface area will drop sharply, the structure will collapse, and thus the photocatalytic degradation activity will become poor.

[0036] (6) Comparative Example 5 shows that the photocatalytic degradation activity of the prepared composite nano zinc oxide material is poor. It can be seen that the composite method of the two has a great influence on the photocatalytic activity. Simple mixing and grinding will destroy its structure, which is not conducive to exerting photocatalytic activity.

[0037] The embodiments and accompanying drawings described above have provided a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water, characterized in that, The preparation method includes the following steps: p-phenylenediamine, terephthalic acid, deionized water and mesoporous regulator are mixed to obtain a dispersion. Zinc chloride aqueous solution is added to the dispersion and mixed. The mixture is then heated to 160℃~170℃ and reacted for 24h~25h to obtain a porous polymer material. Zinc hydroxide@porous material is obtained by impregnating porous polymeric material in alkaline solution; Ammonium molybdate, thiourea, and deionized water were mixed and dissolved to obtain a mixed solution; The composite nano-zinc oxide material is obtained by mixing zinc hydroxide, porous material, and a mixture in a weight ratio of 1:50~60, followed by co-heating reaction and calcination.

2. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The mesoporous regulator includes poloxamer 407.

3. The preparation method of the composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The zinc chloride aqueous solution has a mass concentration of 13 g / L to 14 g / L.

4. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The ratio of p-phenylenediamine, terephthalic acid, deionized water, mesoporous conditioner, and zinc chloride aqueous solution is 4.5g~7g:5g~8g:400mL~560mL:23g~38g:4mL~7mL.

5. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The alkaline solution includes a sodium hydroxide solution with a pH of 9.5 to 10.

6. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The conditions for the immersion treatment include an immersion temperature of 25°C and an immersion time of 1 hour.

7. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The weight ratio of ammonium molybdate, thiourea, and deionized water is 0.3894~0.3944:0.4575~0.7591:65~70.

8. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The conditions for the co-heating reaction include a reaction temperature of 200℃~220℃ and a reaction time of 24h~26h.

9. The method for preparing a composite nano-zinc oxide material for the degradation of organic pollutants in water according to claim 1, characterized in that, The calcination conditions include a calcination temperature of 400℃~450℃ and a calcination time of 40min~50min.

10. A composite nano-zinc oxide material for the degradation of organic pollutants in water, characterized in that, The composite nano zinc oxide material is prepared by any one of the preparation methods for composite nano zinc oxide material for the degradation of organic pollutants in water as described in claims 1 to 9.

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