A defective HKUST-1 photocatalytic material, its preparation method and application

Abstract

This invention discloses a defective HKUST-1 photocatalytic material, its preparation method, and its application, relating to the technical field of HKUST-1 photocatalytic materials. Based on HKUST-1, this invention introduces a defective ligand to obtain the defective HKUST-1 photocatalytic material. The defective ligand is 3-carboxybenzaldehyde. The preparation process of the defective HKUST-1 photocatalytic material is as follows: copper nitrate and 1,3,5-benzenetricarboxylic acid are mixed and dissolved in a solvent, then a 3-carboxybenzaldehyde solution is added and stirred again until homogeneous. The mixture is then reacted overnight at 80–100°C. After the reaction is complete, the mixture is cooled to room temperature, filtered, and the resulting filter cake is washed and dried to obtain the defective HKUST-1 photocatalytic material. The defective HKUST-1 photocatalytic material of this invention exhibits a significantly increased specific surface area, a further reduced band gap, and a 2.93-fold increase in photocatalytic activity, further enhancing the material's adsorption performance and photocatalytic activity.

Description

Technical Field

[0001] This invention relates to the field of HKUST-1 photocatalytic materials technology, specifically to a defective HKUST-1 photocatalytic material, its preparation method, and its application. Background Technology

[0002] Pollutants generated by industrial development have caused enormous harm to ecosystems and human society, and the presence of various pollutants in water sources has become a major problem. Water pollutants include heavy metals, antibiotics, organic dyes, and nitrates. For example, tetracycline (TC), a broad-spectrum antibiotic that is either natural or semi-synthetic, has become prominent in the treatment of bacterial infections. However, it is not completely absorbed during use, and therefore TC has been detected in aquatic environments, especially drinking water, posing a serious threat to the natural environment and human health. Another example is Cr(VI), a mutagenic and carcinogenic pollutant in surface water and groundwater, and one of the toxic heavy metals. Therefore, the effective removal of Cr(VI) from the aquatic environment is of great significance. There are many methods for removing water pollutants, including adsorption, coagulation, ozone oxidation, electrochemical methods, and photocatalytic degradation. Among these, compared with traditional purification methods, photocatalytic degradation utilizes direct sunlight to directly convert pollutants into carbon dioxide and water, thus photocatalysis is considered the most promising method.

[0003] Currently, metal-organic frameworks (MOFs) are commonly used photocatalysts in the photocatalytic removal of water pollutants. HKUST-1, a typical MOF, is frequently used as a photocatalyst in this process. The preparation of HKUST-1 involves dissolving copper nitrate and 1,3,5-benzenetricarboxylic acid (H3BTC) in a solvent and reacting overnight at 80–100°C. After the reaction, the mixture is cooled to room temperature, filtered, and the resulting filter cake is washed and dried to obtain HKUST-1. Compared to other MOFs, HKUST-1 has advantages such as ease of modification, large specific surface area, and strong stability in water. The metal active sites in the HKUST-1 structure are saturated with easily leaving guest small molecules or ligand ions. High-temperature activation removes these small molecules, exposing the active sites and enabling catalytic reactions at these metal active sites. Furthermore, through high temperature and acid site modulation, Cu can be generated. + / Cu 2+ Mixed metal ions, photoexcitation generates e - Migration to Cu + / Cu 2+ Accelerated Cu + and Cu 2+The valence state changes between these states promote the separation of photogenerated carriers and are also beneficial to improving photocatalytic efficiency. However, with the increasing severity of water pollution, the catalytic activity of the existing HKUST-1 material needs to be further improved. Summary of the Invention

[0004] This invention provides a defective HKUST-1 photocatalytic material, which introduces different defective ligands into the HKUST-1 structure by mixing components and using a solvothermal method to further enhance the photocatalytic activity of the material.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A defective HKUST-1 photocatalytic material is obtained by introducing a defective ligand into HKUST-1. The defective ligand is 3-carboxybenzaldehyde. The preparation process of the defective HKUST-1 photocatalytic material is as follows: copper nitrate and 1,3,5-benzenetricarboxylic acid are mixed in a solvent, then a 3-carboxybenzaldehyde solution is added and stirred again until homogeneous. The mixture is then reacted overnight at 80-100°C. After the reaction is completed, the mixture is cooled to room temperature, filtered, and the resulting filter cake is washed and dried to obtain the defective HKUST-1 photocatalytic material.

[0007] Preferably, the solvent for dissolving copper nitrate, 1,3,5-benzenetricarboxylic acid, and 3-carboxybenzaldehyde is a DMF / EtOH / H2O mixed solution with a volume ratio of 1:1:1.

[0008] Preferably, the molar ratio of copper nitrate, 1,3,5-benzenetricarboxylic acid, and 3-carboxybenzaldehyde is 6:3:7.

[0009] The preparation method of the defective HKUST-1 photocatalytic material includes the following steps:

[0010] (1) Dissolve copper nitrate, 1,3,5-benzenetricarboxylic acid and 3-carboxybenzaldehyde in solvents for later use;

[0011] (2) Mix copper nitrate solution and 1,3,5-benzenetricarboxylic acid solution and stir until a homogeneous blue mixed solution is obtained;

[0012] (3) Add the 3-carboxybenzaldehyde solution to the system and continue stirring until the mixture is homogeneous;

[0013] (4) Place the system at 80-100℃ and react overnight;

[0014] (5) After the reaction is complete, cool to room temperature and filter. Wash and dry the filter cake obtained by filtration to obtain the defective HKUST-1 photocatalytic material.

[0015] Furthermore, the filter cake obtained from filtration in step (5) is washed with ethanol 3 to 5 times.

[0016] Furthermore, the drying temperature in step (5) is 60–80°C.

[0017] Furthermore, the defective HKUST-1 photocatalytic material obtained after drying in step (5) is ground before use, and then activated as a photocatalyst in a vacuum oven at 120°C.

[0018] The aforementioned defective HKUST-1 photocatalytic material is used as a photocatalyst in the photocatalytic removal of water pollutants.

[0019] Furthermore, the water pollutant is one or more of tetracycline, hexavalent Cr, and dyes.

[0020] The aforementioned defective HKUST-1 photocatalytic material is used as a photocatalyst in the fuel denitrification reaction.

[0021] In summary, compared with the prior art, the present invention has the following advantages and beneficial effects:

[0022] 1. This invention utilizes a defective HKUST-1 photocatalytic material prepared by introducing a specific defective ligand, 3-carboxybenzaldehyde. Activity experiments were conducted using tetracycline degradation and Cr(VI) reduction as reaction models. The results show that the defective HKUST-1 photocatalytic material DE-CHO, prepared by introducing the specific defective ligand 3-carboxybenzaldehyde, exhibits the best photocatalytic performance. After visible light irradiation for a certain period, the removal rates of both tetracycline and Cr(VI) reached over 93%. DE-HKUST-1 also demonstrated good catalytic activity in the degradation of other pollutants, such as the removal of methylene blue and pyridine. Compared with pure HKUST-1, the photocatalytic performance is significantly improved, providing possibilities for future practical applications of the material.

[0023] 2. Data characterization based on this invention shows that defect engineering by introducing a specific defective ligand, 3-carboxybenzaldehyde, leads to changes in the microenvironment of Cu ions, generating more mixed-valence unsaturated coordination sites (Cu). + / Cu 2+ On the one hand, Cu can expose more active sites by lacking linker ligands, thereby accelerating the reaction efficiency of guest molecules. On the other hand, Cu... + / Cu 2+ The introduction of [a specific ingredient] can reduce the band gap, effectively improve the light absorption performance of the material, and enhance the transfer and separation efficiency of charge carriers, thus jointly promoting the improvement of photocatalytic ability.

[0024] 3. The DE-CHO photocatalyst provided by this invention did not exhibit significant changes in photocatalytic performance after four cycles, and its crystal structure remained intact, indicating that the DE-CHO photocatalyst possesses excellent stability and reusability. This invention confirms the presence of mixed-valence unsaturated coordination sites (Cu). + / Cu 2+ The study explored the mechanism of action and investigated the potential impact of the number of defects generated by defect engineering, providing insights into the control of defect concentration on the photocatalytic performance of materials.

[0025] 4. The defects of this invention are that the preparation process of HKUST-1 photocatalytic material does not add too many reaction steps compared to the preparation process of HKUST-1 photocatalytic material. The preparation process is relatively simple and easy to promote and apply. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the process for preparing HKUST-1 and DE-HKUST-1 series composite materials in Example 1 of this invention;

[0027] Figure 2 (a) XRD pattern and (b) magnified XRD pattern at 5-15° for HKUST-1 and DE-HKUST-1 series composite materials;

[0028] Figure 3 SEM images of HKUST-1 and DE-HKUST-1 series composite materials, where (a) HKUST-1, (b) DE-CHO, (c) DE-OH, (d) DE-COOH, and (ef) DE-N;

[0029] Figure 4 FTIR spectra of HKUST-1 and DE-HKUST-1 series composite materials;

[0030] Figure 5 (a) Nitrogen adsorption-desorption isotherm, (b) pore size distribution, (c) UV diffuse reflectance spectrum, and (d) Tauc plot of HKUST-1 and DE-HKUST-1 series composite materials.

[0031] Figure 6 Photocatalytic activity diagrams of HKUST-1 and DE-HKUST-1 series composite materials are shown, including (a) photocatalytic tetracycline (TC) degradation rate, (b) tetracycline degradation kinetic curve, (c) photocatalytic methylene blue (MB) degradation rate, (d) photocatalytic Cr(VI) reduction rate, (e) photocatalytic pyridine degradation rate, and (f) summary of pollutant degradation rates.

[0032] Figure 7(a) Cyclic test results of DE-CHO for HKUST-1 and DE-HKUST-1 series composite materials and (b) XRD patterns before and after 4 reaction cycles. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to various embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments.

[0034] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in these embodiments, unless otherwise specified, employs conventional testing methods in the art. The terminology used in this invention is merely for describing particular implementations and is not intended to limit the scope of the disclosure.

[0035] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains; other raw materials, reagents, test methods and techniques not specifically mentioned herein refer to raw materials and reagents commonly used by one of ordinary skill in the art, as well as commonly employed test methods and techniques.

[0036] Example 1

[0037] 1. Preparation of HKUST-1 and DE-HKUST-1 series composite materials

[0038] like Figure 1 As shown, this embodiment prepared HKUST-1 photocatalytic material and defective HKUST-1 photocatalytic materials with different defective ligands according to the following steps.

[0039] (1) HKUST-1 photocatalyst: The HKUST-1 photocatalyst was prepared by a solvothermal method. First, 2.00 g of Cu(NO3)2·3H2O (8.29 mmol) and 0.96 g of 1,3,5-benzenetricarboxylic acid (4.57 mmol) were weighed and dissolved in 30 mL of a 1:1:1 (volume ratio) deionized water / DMF / ethanol mixed solvent, and stirred until all solutes were dissolved. Then, the above solutions were mixed and stirred until a homogeneous blue mixed solution was obtained. The above mixed solution was transferred to a 100 mL hydrothermal reactor with a polytetrafluoroethylene liner and reacted at 85 °C for 20 h. After the reaction was completed, it was naturally cooled to room temperature and filtered. Finally, the product was washed with ethanol 3-5 times and then dried in a vacuum drying oven at 65 °C for 24 h to obtain the HKUST-1 catalyst.

[0040] (2) Defective HKUST-1 photocatalytic materials with different defective ligands (DE-HKUST-1 series composite materials): 0.72 g Cu(NO3)2·H2O (3 mmol), 0.31 g H3BTC (1.5 mmol), and different masses of defective ligands (3.5 mmol) were dissolved in 24 mL of DMF:EtOH:H2O (1:1:1, v / v / v). The mixture was stirred until the solutes were fully dissolved. Then, the Cu(NO3)2·H2O and H3BTC solutions were mixed and stirred until a homogeneous blue mixture was obtained. At this point, the solution containing the defective ligands was added and stirred again for 30 min. The mixture was then transferred to a 100 mL hydrothermal reactor with a polytetrafluoroethylene liner and reacted at 85 °C for 20 h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The product was centrifuged and washed 3-5 times, then dried completely in a vacuum drying oven at 65 °C. Finally, the powder was ground and collected, and then placed in a vacuum oven at 120 °C for photocatalyst activation. The DE-HKUST-1 samples formed based on four different defective ligands (3-carboxybenzaldehyde, m-hydroxybenzoic acid, isophthalic acid, and pyridine-3,5-dicarboxylic acid) are named as follows: DE-CHO (3-carboxybenzaldehyde); DE-OH (m-hydroxybenzoic acid); DE-COOH (isophthalic acid); DE-N (pyridine-3,5-dicarboxylic acid).

[0041] 2. Microstructure analysis of HKUST-1 and DE-HKUST-1 series composite materials

[0042] like Figure 2 The image shows the XRD patterns of HKUST-1 and DE-HKUST-1 series composite materials. DE-CHO, DE-OH, and DE-COOH exhibit XRD patterns that are essentially identical to those of HKUST-1. Figure 2 (a) demonstrates that the topological structures of the three materials were preserved, and the overall framework remained intact. However, the XRD pattern of DE-N exhibits characteristic peaks that are distinctly different from those of HKUST-1, indicating that the structure has been altered. This may be related to the excessive connection of defective ligands due to excessively high concentrations of defective ligands. (XRD magnification) Figure 2 (b) Subtle characteristic peak changes can be seen at the low-angle peak positions of DE-CHO, DE-OH, and DE-COOH, which may be related to the defects of ordered missing clusters. The appearance of new crystal planes changes the microenvironment around the active sites and regulates the adsorption and transport of guest molecules.

[0043] like Figure 3 The image shown is a SEM image of the HKUST-1 and DE-HKUST-1 series composite materials. Figure 3 (a) It can be seen that pure HKUST-1 has a complete octahedral structure with a smooth and flat surface, and an overall size of about 5 μm. However, with the addition of different defect ligands, the morphology of DE-HKUST-1 gradually changes, and its size becomes smaller. The morphology of DE-CHO (…) Figure 3 (b) The morphology of DE-OH and DE-COOH clearly transforms from octahedral to irregular shape, exhibiting truncated octahedral or other irregular shapes. Figure 3 (c) and (d) are more pronounced on the surface and edges, while retaining the octahedral morphology of the parent Cu-BTC structure. The surface becomes rougher, and small portions of the edges are missing. The morphology of DE-N ( Figure 3 (e) and (f) tend to be spherical, and their porous structure is clearly visible under high magnification. These morphological changes are inseparable from the defective structures generated by ligand substitution. The defects caused by different defective ligands lead to surface roughness and changes in the overall structure. This structural regulation changes the microenvironment of the active sites, achieves better interfacial contact between the catalyst and reactants, and promotes the transfer of photogenerated carriers at the interface, thereby improving the material properties.

[0044] like Figure 4 The image shows the FT-IR spectra of HKUST-1 and DE-HKUST-1 series composite materials. The samples of HKUST-1 and DE-CHO, DE-OH, and DE-COOH all have wavelengths at 1645, 1445, 1368, 721, and 488 cm⁻¹. -1 The position shows a distinct infrared peak. Located at 1645cm... -1 and 1445cm -1 The peak at 1368 cm⁻¹ represents an -OCO- bond. Simultaneously, at 1368 cm⁻¹... -1 The absorption peak at 940 cm⁻¹ is related to the stretching mechanism of CO. -1 The peak values ​​at 721 and 488 cm⁻¹ are attributed to the bending vibrations of CH. -1 The peak values ​​are related to the bending and stretching modes of Cu-O. These confirm that these defects in HKUST-1 still maintain its typical band structure, indicating that introducing defects by adding these three ligands does not significantly disrupt the topology of HKUST-1. However, the infrared peaks of DE-N show a partial shift compared to HKUST-1, which may be due to the preferential binding of PyDC ligands to Cu. 2+ The interaction prevents the H3BTC ligand from binding with Cu. 2+Effective binding occurs, leading to changes in the overall structure. This confirms the conclusions drawn from XRD, and subsequent studies will only focus on DE-N as a reference (auxiliary ligand). Simultaneously, the infrared spectra of the missing linker ligands and the corresponding defective HKUST-1 were compared. As shown in the infrared spectra in the figure, different characteristic absorption peaks appeared in the FT-IR spectrum of DE-HKUST-1, and new absorption peaks and band shifts were observed due to the doping of these defective linkers. These are related to the introduction of new functional groups in the defective ligands, and the hydrogen atoms on the -OH group may be removed due to deprotonation when coordinated with copper ions. The results indicate that the three defective ligands in the DE-CHO, DE-OH, and DE-COOH samples can be effectively integrated into the structure of the corresponding defective MOFs without disrupting the parent HKUST-1 matrix structure.

[0045] like Figure 5 The figure shows the N2 adsorption-desorption isotherms and pore size distribution of HKUST-1 and DE-HKUST-1 series composite materials. The N2 adsorption-desorption experiments yielded the specific surface area and pore volume of the photocatalysts. Compared to pure HKUST-1, the specific surface area and total pore volume of DE-CHO and DE-OH were increased, with DE-CHO showing the greatest increase. The specific surface area of ​​both DE-CHO and DE-OH increased to 1522.5 m². 2 / g and 1397.2m 2 / g (Table 1) is due to the formation of defects introducing vacancies and mesopores, and the pore size distribution also shows the presence of mesoporous structures. A large specific surface area is beneficial for the exposure of active sites and the transport and adsorption of guest molecules. Meanwhile, a decrease in specific surface area can be observed in DE-COOH and DE-N. The significant change in specific surface area of ​​DE-N may be due to structural changes. The isothermal hysteresis loop observed in DE-HKUST-1 can also be attributed to the mesoporous structure.

[0046] The effect of defect structure formation on carrier light absorption capability was then investigated using UV-vis-DRS. Figure 3-5 As shown in (c), compared to HKUST-1, DE-CHO and DE-OH materials exhibit higher absorption intensity and a wider light absorption range. This demonstrates that the defect structure improves the light absorption value of the materials, which can be verified in subsequent photocatalytic activity tests. Furthermore, the presence of defects can lead to new energy levels to modulate the band gap. The band gaps (Eg) of HKUST-1, DE-CHO, and DE-COOH were calculated. g The values ​​are 2.55, 2.45, and 2.64 eV, respectively. Figure 3-5 (d) Narrow band gaps are generally more advantageous in photocatalysis, which suggests that DE-CHO may have optimal activity and the most suitable defect structure.

[0047] Table 1. Specific surface area and pore size of HKUST-1 and DE-HKUST-1 series composite materials

[0048]

[0049] 3. Comparison of photocatalytic performance of HKUST-1 and DE-HKUST-1 series composite materials

[0050] like Figure 6 As shown, based on the excellent properties exhibited by DE-HKUST-1 prepared through defect engineering, this embodiment investigates the photocatalytic performance of HKUST-1 and DE-HKUST-1 series composite materials using photocatalytic degradation of tetracycline as a reaction model. Figure 6 As shown in (a), under visible light irradiation, the material reached the adsorption-desorption equilibrium point after 30 min of dark reaction. After 60 min of light irradiation, HKUST-1 showed a 57% degradation rate of tetracycline. The DE-HKUST-1 sample exhibited higher photocatalytic activity, with DE-CHO showing the best degradation effect on tetracycline (~91%). The kinetic curves of the samples all followed a first-order kinetic model (…). Figure 6 (b) The calculated reaction rate constants for DE-CHO, DE-OH, DE-COOH, and HKUST-1 were 1.99, 1.03, 0.87, and 0.68 h⁻¹, respectively. -1 Quantitative analysis data showed that the photocatalytic activity of DE-CHO was approximately 2.93 times higher than that of HKUST-1 before structural regulation. Its activity order was basically the same as that of Cu. + / Cu 2+ The content order of CUS remains consistent because of the mixed valence Cu + / Cu 2+ CUS (Cu) alters the metal atomic environment, reducing the band gap and increasing charge transfer. It can also act as a catalytic active center, accelerating the reaction rate and thus improving photocatalytic activity. This experiment preliminarily verifies that defect engineering improves the photocatalytic activity of HKUST-1. It is worth noting that although Cu... + / Cu 2+ The content of is higher in DE-COOH than in DE-OH, but the activity of DE-OH is slightly higher than that of DE-COOH. The main reason may be that an excessively high defect ratio will cause photogenerated carriers to move to deeper layers and have difficulty returning to the surface, resulting in severe recombination and affecting photocatalytic activity.

[0051] Subsequently, Cr(VI) reduction, dye degradation, and fuel denitrification experiments were conducted on the HKUST-1 and DE-HKUST-1 series materials to verify the activity of the photocatalysts. Figure 6As shown in (c), DE-HKUST-1 was tested for photoactivity using methylene blue (MB), a typical representative of dye degradation, as the experimental subject. Compared to MB, DE-HKUST-1 showed improved activity as a photocatalyst. DE-CHO still exhibited the best photocatalytic activity within the same timeframe, achieving a degradation rate of 91%, essentially reaching complete degradation. However, DE-N showed fluctuations in degradation rate, possibly due to the instability of its synthesized flower-like structure. Similarly, in fuel denitrification and Cr(VI) reduction... Figure 6 In the photocatalytic activity experiments (d) and (e), DE-HKUST-1 still exhibited good photocatalytic activity. In Cr(VI) reduction, the reduction activity was improved by introducing a hole sacrificial agent to reduce electron-hole recombination. Using ammonium oxalate as the hole sacrificial agent, after 60 minutes of visible light irradiation, DE-CHO showed the best photocatalytic performance, with a reduction rate increasing to nearly 100%, which confirms the previous results. All photocatalytic degradation activities were summarized in a unified manner, as follows: Figure 6 (f) and Table 2 are shown.

[0052] Table 2. Pollutant degradation rates of HKUST-1 and DE-HKUST-1 series composite materials under a 300W visible light (λ>420nm) xenon lamp.

[0053]

[0054] Stability is a crucial factor affecting catalyst performance and is essential for practical applications. The introduction of these defects should not compromise the overall integrity of the catalyst framework. To investigate the stability of the defective HKUST-1 photocatalyst, a cyclic recovery experiment was conducted using the optimal photocatalyst (DE-CHO). Under identical conditions, one complete tetracycline degradation cycle was defined as one cycle. After the reaction, the solid catalyst was collected, dried, and then reintroduced into the next cycle, repeating this process four times. The results are as follows: Figure 7 As shown in (a) and (b), the photocatalytic performance of DE-CHO did not decrease significantly, indicating that DE-CHO has good stability. Furthermore, the final XRD test showed that the crystal structure of the photocatalyst after participating in the reaction did not change compared with the unused photocatalyst.

[0055] The embodiments described above merely illustrate specific implementation methods of this application, and while the descriptions are detailed and specific, they should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the technical solution of this application, and these modifications and improvements all fall within the scope of protection of this application.

Claims

1. The application of a defective HKUST-1 photocatalytic material as a photocatalyst in fuel denitrification reaction, characterized in that, The defective HKUST-1 photocatalytic material is obtained by introducing a defective ligand into HKUST-1. The defective ligand is 3-carboxybenzaldehyde, and its preparation method includes the following steps: (1) Dissolve copper nitrate, 1,3,5-benzenetricarboxylic acid and 3-carboxybenzaldehyde in solvents for later use; (2) Mix the copper nitrate solution and the 1,3,5-benzenetricarboxylic acid solution and stir until a homogeneous blue mixed solution is obtained; (3) Add the 3-carboxybenzaldehyde solution to the system and continue stirring until the mixture is homogeneous; (4) Place the system in a hydrothermal reactor at 80~100℃ and react overnight; (5) After the reaction is complete, cool to room temperature and filter. Wash and dry the filter cake obtained by filtration to obtain the defective HKUST-1 photocatalytic material. The solvent for dissolving copper nitrate, 1,3,5-benzenetricarboxylic acid, and 3-carboxybenzaldehyde is a DMF / EtOH / H2O mixed solution with a volume ratio of 1:1:1; the molar ratio of copper nitrate, 1,3,5-benzenetricarboxylic acid, and 3-carboxybenzaldehyde is 6:3:

7.

2. The application as described in claim 1, characterized in that, The filter cake obtained in step (5) is washed with ethanol 3 to 5 times.

3. The application as described in claim 1, characterized in that, Step (5) The drying temperature is 60~80℃.

4. The application as described in claim 1, characterized in that, Before use, the defective HKUST-1 photocatalytic material obtained after drying in step (5) is ground and then activated in a vacuum oven at 120°C.

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