Covalently bonded MOFs@COFs composite material, and preparation method and application thereof

Abstract

The application provides a covalently bonded MOFs@COFs composite material and a preparation method and application thereof, and is the first report of the composite material in the field of photocatalytic hydrogen peroxide production. The catalyst used in the application is a composite material NU-66 formed by covalently bonding metal organic frameworks (MOFs) and covalent organic frameworks (COFs) x @TpTapt( x =0.2~0.5), the material is simple in the photocatalytic hydrogen peroxide production method, green and environment-friendly, and high in safety. Under irradiation, in the absence of a sacrificial agent and a cocatalyst, the material can exhibit high photocatalytic hydrogen peroxide production activity in an air atmosphere. The application not only improves atomic utilization, but also significantly improves the wastewater treatment effect of in-situ generated hydrogen peroxide. The composite material is first reported to be applied in the field, has important research value and significance, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to a MOFs@COFs composite material based on covalent bonding, its preparation method and application, specifically its application in the field of photocatalytic hydrogen peroxide production, belonging to the field of green chemistry. Background Technology

[0002] Hydrogen peroxide, also known as hydrogen peroxide solution in aqueous solution, is a green and efficient oxidant widely used in pulp and textile bleaching, chemical synthesis, medical disinfection, and rocket propellant. Currently, commercial hydrogen peroxide production both domestically and internationally mainly employs two methods: the anthraquinone (AO) method and the thermocatalytic method. While these methods offer advantages such as low cost and high production volume, they also have their drawbacks. The AO method requires a palladium catalyst; leakage into the oxidation or extraction system can lead to the violent decomposition of hydrogen peroxide, with severe consequences. Although the anthraquinone method has undergone several improvements, it remains inherently an energy-intensive synthesis method that can impact equipment lifespan. Thermocatalysis directly produces hydrogen peroxide using a heated H2 / O2 mixture. However, due to the explosiveness of this mixture over a wide concentration range, the safety risks are even greater. Furthermore, most thermocatalysts utilize precious metal co-catalysts such as gold, palladium, or platinum, resulting in high production costs and further increasing the risk by using a mixed gas as a raw material. Therefore, safe, efficient, energy-saving, and environmentally friendly hydrogen peroxide production presents a significant challenge.

[0003] Emerging photocatalytic technologies, using H2O and O2 as raw materials and inexhaustible sunlight as an energy source, avoid the mixing of H2 and O2, making them safe and environmentally friendly, and have received widespread attention in recent years. Both metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been preliminarily reported in the photocatalytic production of hydrogen peroxide directly using H2O and O2 as raw materials. However, current common problems include the weak light absorption capacity and low photogenerated charge separation efficiency of MOFs, and the need for sacrificial agents, poor crystallinity, and difficulty in reusing COFs, as well as their relatively small specific surface area which hinders substrate transport, resulting in low efficiency in the photocatalytic production of hydrogen peroxide. Summary of the Invention

[0004] This invention uses covalently bonded MOFs@COFs composite materials as photocatalysts to promote the efficient photocatalytic preparation of hydrogen peroxide from H2O and O2. This meets the current needs of the chemical industry for compatibility with the ecological environment and sustainable development, and therefore has important industrial application value and social significance.

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

[0006] A covalently bonded MOFs@COFs composite material is a covalently bonded material of a metal-organic framework and a covalent organic framework. Preferably, the metal-organic framework is a Zr-based metal-organic framework; the covalent organic framework is a phenyltriazine covalent organic framework.

[0007] This invention discloses a method for preparing the above-mentioned covalently bonded MOFs@COFs composite material, comprising the following steps: preparing a metal-organic framework using 2-amino-terephthalic acid and a metal salt; and then preparing a covalently bonded MOFs@COFs composite material using the metal-organic framework, phloroglucinol compound, and phenyltriazine compound as raw materials.

[0008] In this invention, the mass of MOFs in the MOFs@COFs composite material is 10-60% of the mass of COFs, preferably 20-50%.

[0009] This invention discloses the application of the above-mentioned covalently bonded MOFs@COFs composite material in the preparation of hydrogen peroxide. Preferably, this invention discloses the application of the above-mentioned covalently bonded MOFs@COFs composite material as a catalyst in the preparation of hydrogen peroxide. More preferably, this invention discloses the application of the above-mentioned covalently bonded MOFs@COFs composite material as a photocatalyst in the preparation of hydrogen peroxide.

[0010] This invention discloses a method for photocatalytic production of hydrogen peroxide, comprising the following steps: irradiating an aqueous solution containing the above-mentioned covalently bonded MOFs@COFs composite material to obtain hydrogen peroxide.

[0011] This invention discloses a method for treating wastewater by in-situ generation of hydrogen peroxide, comprising the following steps: irradiating a wastewater solution containing the above-mentioned covalently bonded MOFs@COFs composite material to complete the in-situ generation of hydrogen peroxide for wastewater treatment.

[0012] In this invention, the illumination is carried out at room temperature and in air.

[0013] In this invention, after light exposure, the solution is filtered, and the filtrate is an aqueous solution containing hydrogen peroxide.

[0014] In this invention, no sacrificial agent or co-catalyst is required for photocatalytic hydrogen peroxide production.

[0015] Preferably, the illumination time is 0.1 to 10 hours.

[0016] In this invention, the illumination is visible light, such as sunlight, or visible light from a xenon lamp with an external 420 nm cutoff filter (λ≥420 nm).

[0017] In this invention, the wastewater is water containing organic pollutants, including phenolic compounds.

[0018] The beneficial effects of this invention are mainly reflected in:

[0019] (1) This invention provides a method for photocatalytic hydrogen peroxide production using MOFs@COFs composite materials based on covalent bonding, which does not use organic solvents (ethanol, isopropanol, benzyl alcohol, etc.) as sacrificial agents, and is green, environmentally friendly and pollution-free;

[0020] (2) This invention provides a method for photocatalytic hydrogen peroxide production based on covalently bonded MOFs@COFs composite materials. The reaction system does not require the introduction of saturated oxygen as an oxygen source, and can use sunlight (visible light) as an energy source. Compared with the industrial indirect synthesis of hydrogen peroxide by anthraquinone, the method of this invention has low energy consumption and high safety.

[0021] (3) This invention provides a method for photocatalytic hydrogen peroxide production using MOFs@COFs composite materials based on covalent bonding. Compared with the direct preparation of hydrogen peroxide by mixing oxygen and hydrogen, this method is safer and has no precious metal pollution.

[0022] (4) This invention provides a method for photocatalytic hydrogen peroxide production based on covalently bonded MOFs@COFs composite materials, and the hydrogen peroxide produced in situ can be used for wastewater treatment at the same time.

[0023] (5) Compared with the traditional photocatalytic preparation of hydrogen peroxide, this method eliminates the problem of difficult separation of organic sacrificial agents and their oxidation products from the source;

[0024] (6) This invention proposes for the first time a method for photocatalytic production of hydrogen peroxide using covalently bonded MOFs@COFs composite materials. Compared with the photocatalytic production of hydrogen peroxide using individual MOFs or COFs, the yield of hydrogen peroxide per unit time is significantly improved.

[0025] (7) The method for preparing hydrogen peroxide according to the present invention has mild reaction conditions and simple operation. It only requires uniformly dispersing the composite material with ultrapure water, stirring at room temperature in an air atmosphere without sacrificial agents or co-catalysts, and then irradiating it with visible light for a period of time. After that, the reaction solution is taken and filtered to obtain a high concentration of hydrogen peroxide solution. The method of the present invention for preparing hydrogen peroxide has the advantages of high yield, high efficiency and stable catalytic performance, and has good application prospects. Attached Figure Description

[0026] Figure 1 For NU-66 xSchematic diagram and characterization of @TpTapt preparation: (a) Synthetic route of NU-66x@TpTapt; (b) Experimental PXRD patterns of NU-66, TpTapt, and NU-66x@TpTapt; and (c) Fourier transform infrared spectra; (dg) NU-66, (eh) TpTapt, and (fi) NU-66. 0.4 SEM and TEM images of @TpTapt; (j) NU-66 0.4 EDX plot of @TpTapt (C, N, O and Zr elements).

[0027] Figure 2 This is a schematic diagram of a photocatalytic reaction device.

[0028] Figure 3 For NU-66, TpTapt and a series of gradient composite materials NU-66 x @TpTapt( x =0.2~0.5) Relationship between photocatalytic hydrogen peroxide production rate and time (a), and the yield of different catalysts (b); Conditions: 300 W xenon lamp (λ>420 nm), water (50 mL), catalyst (10 mg).

[0029] Figure 4 For NU-66 0.4 Performance graph of five catalytic recycle cycles for @TpTapt.

[0030] Figure 5 The diagram shows the application of in-situ generated hydrogen peroxide in wastewater treatment. Detailed Implementation

[0031] This invention aims to provide a covalently bonded MOFs@COFs composite material and its method for efficient photocatalytic hydrogen peroxide production, and to provide its application in hydrogen peroxide preparation. The novel photocatalytic method for hydrogen peroxide preparation involved in this invention does not use sacrificial agents or co-catalysts, making it green, environmentally friendly, and pollution-free; it does not require a pure oxygen environment, achieving high yields in air; it uses visible light as an energy source, resulting in low energy consumption, high safety, simple and convenient operation, mild reaction conditions, and a novel reaction mechanism; and the hydrogen peroxide yield per unit time is higher than that of similar prototype materials.

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described below with reference to specific embodiments; however, the scope of protection of this invention is not limited thereto. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined as long as they do not conflict with each other.

[0033] The method for producing hydrogen peroxide using the above-mentioned covalently bonded MOFs@COFs composite material is as follows:

[0034] (1) The synthesized covalently bonded MOFs@COFs composite material was ultrasonically dispersed in pure water to obtain a dispersion with a catalyst concentration of 0.01 to 1 g / L. The dispersion was then irradiated with light at room temperature to achieve photocatalytic production of hydrogen peroxide.

[0035] (2) Filter the reaction product obtained in step (1) and take the filtrate to obtain hydrogen peroxide aqueous solution (hydrogen peroxide).

[0036] Methods for testing hydrogen peroxide concentration:

[0037] The amount of hydrogen peroxide was analyzed by iodometric titration. 1 mL of 0.1 mol∙L⁻¹ hydrogen peroxide was added. -1 C8H5KO4 aqueous solution and 1 mL 0.4 mol∙L -1 Add KI aqueous solution to the resulting solution, then let stand for 30 min. Hydrogen peroxide molecules react under acidic conditions (H₂O₂ + 3I⁻). - +2H + →I3 - + 2H2O) and iodide anion (I - The reaction produces triiodide anion (I3) with strong absorption around 350 nm. - I3 - The amount of hydrogen peroxide was determined by UV-Vis spectrophotometry based on the absorbance at 350 nm, and the amount of hydrogen peroxide produced in each reaction was estimated accordingly.

[0038] This invention synthesizes a dual-channel nanocatalyst NU-66x@TpTapt (Figure 1a) for photocatalytic H2O2 production by combining MOFs and CTFs through a covalent bonding integration strategy. NU-66x@TpTapt is a nanocatalyst for photocatalytic H2O2 production. 0.4 @TpTapt efficiently converts H2O and O2 into H2O2 via photocatalysis, without the need for any sacrificial agents in an air environment, achieving an H2O2 conversion rate of up to 5464 μmol / h. -1 g -1 Furthermore, AQY and SCC reached 19.1% and 1.01% respectively at a wavelength of 420 nm, far exceeding other reported photocatalysts. More importantly, NU-66 0.4 @TpTapt also exhibits excellent performance under sunlight, and the in-situ generated H2O2 shows outstanding performance in wastewater treatment and antibacterial experiments.

[0039] Preferably, the covalently bonded MOFs@COFs composite material of this invention is prepared from 2-aminoterephthalic acid, zirconium chloride, trialdehyde phloroglucinol, and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine as raw materials. First, a metal-organic framework is prepared using 2-aminoterephthalic acid and zirconium chloride; then, the covalently bonded MOFs@COFs composite material is prepared using the metal-organic framework, trialdehyde phloroglucinol, and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine as raw materials.

[0040] The pharmaceutical ingredients used in this invention—2-aminoterephthalic acid, zirconium chloride, trialdehyde phloroglucinol, and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine—were all purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., with a purity of 98%. All raw materials used in this invention are existing products, and the specific preparation operations and performance testing follow conventional techniques.

[0041] Preparation Examples

[0042] (1) Synthesis of NU-66: 2-Amino-terephthalic acid (0.543 g, 3.0 mmol) and zirconium chloride (0.5 g, 2.16 mmol) were added to DMF (50 mL) and ultrasonically dispersed until the solution became transparent. The solution was then transferred to a round-bottom flask and glacial acetic acid (8.3 mL) was added and ultrasonically dispersed. The reactants were then heated at 120 °C for 24 hours. After the reaction was complete, the solid powder was collected by centrifugation using methanol as solvent and dried overnight at 80 °C to obtain product A, NU-66.

[0043] (2) Synthesis of TpTapt: Trialdehyde phloroglucinol (Tp, 0.2 mmol, 42 mg) and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (Tapt, 0.2 mmol, 71 mg) were mixed and placed in an ampoule. A mixed solvent consisting of glacial acetic acid (1 mL), mesitylene (3 mL), and 1,4-dioxane (3 mL) was added. The ampoule was frozen in liquid nitrogen, then evacuated to remove air, then thawed, and finally purged with nitrogen. This freeze-thaw cycle was repeated three times. The ampoule was then sealed and allowed to cool to room temperature. The reactants were then sonicated to ensure uniform dispersion. Finally, the ampoule was placed in an oven and reacted at 120 °C for 72 h. After the reaction was completed, the product was washed sequentially with solvents such as ethanol, DMF, and acetone, and further purified by Soxhlet extraction. After the above operations were completed, the product was placed in an oven at 100 °C and dried overnight to obtain a yellow solid powder B, which is TpTapt.

[0044] (3) Synthesis of composite material NU-66x@TpTapt (x=0.2~0.5): The composite material was synthesized using the same method as product B, with product A added before the solvent. The amount of product A added was calculated based on the theoretical yield of TpTapt and the mass ratio of the two. Product A and product B were covalently combined during the co-synthesis process. After the reaction, the solid was washed, Soxhlet extracted, and dried to collect composite materials in different proportions.

[0045] In NU-66x@TpTapt, x is the mass ratio of m(NU-66) / m(TpTapt), where m(TpTapt) is the theoretical value calculated based on the feed ratio of TpTapt.

[0046] The molecular structure of NU-66@TpTapt in this invention is shown below:

[0047]

[0048] The combination of powder X-ray diffraction (PXRD) and theoretical simulation confirmed the crystal structure of the prepared sample. Figure 1 b) Fourier transform infrared spectroscopy (FT-IR) further characterized the structure of the prepared sample (Figure 1c). Furthermore, the -NH2 peak at 399.90 eV in NU-66... 0.4 The disappearance of @TpTapt further reveals the presence of imine bonds. These results indicate that a dual-channel nanocatalyst was successfully synthesized through covalent bonds acting as a "bridge". The morphology and microstructure of the prepared samples were studied using SEM and TEM, as shown in Figures 1d~i. After NU-66 was combined with TpTapt, the TpTapt layer encapsulating the surface of NU-66 could be clearly observed in TEM. To more clearly confirm the elemental distribution characteristics of NU-66 and TpTapt, NU-660.4@TpTapt was characterized by HRTEM and EDX elemental spectra. Figure 1j shows the spatial distribution of C, N, O, and Zr, confirming the presence of imine bonds in NU-66. 0.4The uniform distribution of all elements in @TpTapt was observed. The porous structure and specific surface area of ​​the prepared samples were obtained through N2 adsorption-desorption analysis. The combination of the two materials exhibited a type I isotherm of an H4-type hysteresis loop, indicating the presence of a mixed microporous and mesoporous structure. The thermal stability of the samples was evaluated using TGA. The results show that the excellent thermal stability of TpTapt is due to the abundant heteroatom (N) content in its structure. The thermal stability of NU-66 modified with TpTapt was also significantly improved. Simultaneously, the dual-channel nanoreactor NU-66... 0.4 @TpTapt maintains excellent stability in various solvents.

[0049] Application Examples

[0050] For example Figure 2 The schematic diagram of the reaction apparatus illustrates the photocatalytic reaction. In air, 10 mg of NU-66, TpTapt, and a series of gradient NU-66 composite materials are introduced. x @TpTapt( x =0.2~0.5) were added to 100 mL of quartz reactor, followed by 50 mL of deionized water. The mixture was sonicated for 5 minutes to ensure uniform dispersion of the catalyst. The reactor was then subjected to dark adsorption for 30 minutes to reach adsorption-desorption equilibrium. The reactor was then irradiated with a xenon lamp fitted with a 420 nm filter. Samples were taken at fixed intervals and filtered through a 0.22 μm filter membrane to obtain a filtrate containing hydrogen peroxide. The hydrogen peroxide content in the solution was quantitatively analyzed using the potassium iodide colorimetric method.

[0051] Comparative Example 1

[0052] The method for photocatalyzing hydrogen peroxide growth is described in the application example: the catalyst used is NU-66.

[0053] Comparative Example 2

[0054] The method for photocatalyzing hydrogen peroxide is described in the application example: the catalyst used is TpTapt. Example 1

[0055] A method for growing hydrogen peroxide using covalently bonded MOFs@COFs composite materials as photocatalysts, referring to the application example: the catalyst used is NU-66. 0.2 @TpTapt. Example 2

[0056] A method for growing hydrogen peroxide using covalently bonded MOFs@COFs composite materials as photocatalysts, referring to the application example: the catalyst used is NU-66. 0.3 @TpTapt. Example 3

[0057] A method for growing hydrogen peroxide using covalently bonded MOFs@COFs composite materials as photocatalysts, referring to the application example: the catalyst used is NU-66. 0.4 @TpTapt. Example 4

[0058] A method for growing hydrogen peroxide using covalently bonded MOFs@COFs composite materials as photocatalysts, referring to the application example: the catalyst used is NU-66. 0.5 @TpTapt.

[0059] Figure 3 For NU-66, TpTapt and a series of gradient composite materials NU-66 x @TpTapt( x =0.2~0.5) (Examples 1~4) Relationship between photocatalytic hydrogen peroxide production rate and time. Among them, the composite material NU-66 0.4 @TpTapt exhibits the best photocatalytic hydrogen peroxide production performance, reaching 1092.77 μM / h. Calculations show that NU-66... 0.4 @TpTapt achieved an apparent quantum yield (AQY) of 19.1% and a solar energy conversion efficiency (SCC) of 1.04% at a wavelength of 420 nm, far exceeding most previously reported photocatalysts. Example 5

[0060] NU-66 was recovered by centrifugal washing and drying. 0.4 @TpTapt, further testing its recyclability was conducted, with the experimental process referring to the application example. Figure 4 For NU-66 0.4 @TpTapt's five-catalytic recycle performance, NU-66 0.4 @TpTapt exhibits excellent recyclability. Example 6

[0061] The in-situ generated hydrogen peroxide was used for wastewater treatment, and real wastewater was simulated by preparing a solution of 50 ppm bisphenol A, phenol and 2,4-dichlorophenol.

[0062] Referring to Example 3, the difference is that the reaction solution is the simulated real wastewater solution prepared above (instead of deionized water).

[0063] Comparison Example

[0064] 0.1 mmol of catalase was added to 50 mL of simulated real wastewater solution, and the catalyst was sonicated for 5 minutes to ensure uniform dispersion. The reactor was then subjected to dark adsorption for 30 minutes to reach adsorption-desorption equilibrium. The reactor was then irradiated with a xenon lamp fitted with a 420 nm filter. Samples were taken at fixed intervals and filtered through a 0.22 μm filter membrane to obtain a filtrate containing hydrogen peroxide. The hydrogen peroxide content in the solution was quantitatively analyzed using the potassium iodide colorimetric method.

[0065] Figure 5 For NU-66 0.4 The in-situ generated hydrogen peroxide obtained by @TpTapt is used in wastewater treatment. Currently, there are few reports on the use of in-situ generated hydrogen peroxide solutions to treat pollutants due to the presence of sacrificial or buffering agents in most systems; the in-situ generated hydrogen peroxide of this invention exhibits excellent activity in adsorbing and degrading pollutants, and most organic pollutants, dyes, and antibiotics at 50 ppm can be completely degraded within half an hour without the addition of catalase.

[0066] Furthermore, the morphology and structure of the photocatalyst after use were characterized by XRD, FT-IR, XPS, SEM, and TEM, and the Zr4 content in the aqueous solution before and after the reaction was detected by ICP-AES. + The content of [a specific substance] remained relatively stable. The results indicate that NU-66@TpTapt exhibits good stability during photocatalysis.

[0067] This invention is the first to combine MOFs and COFs materials through covalent bonds. Although such materials have been widely reported in photocatalytic hydrogen production and pollutant degradation, their application in the efficient photocatalytic preparation of hydrogen peroxide using H2O and O2 as raw materials has not been reported. Moreover, the reaction system has high atom utilization and the hydrogen peroxide generated in situ can be used for wastewater treatment.

[0068] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. The application of a covalently bonded MOFs@COFs composite material in the preparation of hydrogen peroxide, characterized in that, The covalently bonded MOFs@COFs composite material is a covalently bonded material of metal-organic framework and covalent organic framework; the metal-organic framework is a Zr-based metal-organic framework; the covalent organic framework is a phenyltriazine covalent organic framework; the covalently bonded MOFs@COFs composite material is prepared by using 2-amino-terephthalic acid and metal salt to prepare metal-organic framework; and then using metal-organic framework, phloroglucinol compound and phenyltriazine compound as raw materials to prepare covalently bonded MOFs@COFs composite material.

2. The application of the covalently bonded MOFs@COFs composite material according to claim 1 in the preparation of hydrogen peroxide, characterized in that, In MOFs@COFs composites, the mass of MOFs is 10 to 60% of the mass of COFs.

3. The application of the covalently bonded MOFs@COFs composite material according to claim 1 in the preparation of hydrogen peroxide, characterized in that, The application does not require a sacrificial agent.

4. The application of a covalently bonded MOFs@COFs composite material in the simultaneous preparation of hydrogen peroxide and wastewater treatment, characterized in that, The covalently bonded MOFs@COFs composite material is a covalently bonded material of metal-organic framework and covalent organic framework; the metal-organic framework is a Zr-based metal-organic framework; the covalent organic framework is a phenyltriazine covalent organic framework; the covalently bonded MOFs@COFs composite material is prepared by using 2-amino-terephthalic acid and metal salt to prepare metal-organic framework; and then using metal-organic framework, phloroglucinol compound and phenyltriazine compound as raw materials to prepare covalently bonded MOFs@COFs composite material.

5. A method for photocatalytic production of hydrogen peroxide, characterized in that, The process includes the following steps: irradiating an aqueous solution containing a covalently bonded MOFs@COFs composite material with light to obtain hydrogen peroxide; the covalently bonded MOFs@COFs composite material is a covalently bonded material of a metal-organic framework and a covalent organic framework; the metal-organic framework is a Zr-based metal-organic framework; the covalent organic framework is a phenyltriazine covalent organic framework; the covalently bonded MOFs@COFs composite material is prepared by using a metal-organic framework prepared from 2-amino-terephthalic acid and a metal salt; and then preparing the covalently bonded MOFs@COFs composite material using the metal-organic framework, phloroglucinol compound, and phenyltriazine compound as raw materials.

6. A method for treating wastewater by in-situ generation of hydrogen peroxide, comprising the following steps: irradiating a wastewater solution containing a covalently bonded MOFs@COFs composite material with light to complete the in-situ generation of hydrogen peroxide for wastewater treatment; wherein the covalently bonded MOFs@COFs composite material is a covalently bonded material of a metal-organic framework and a covalent organic framework; the metal-organic framework is a Zr-based metal-organic framework; the covalent organic framework is a phenyltriazine covalent organic framework; the covalently bonded MOFs@COFs composite material is prepared by using a metal-organic framework prepared from 2-amino-terephthalic acid and a metal salt; and then using the metal-organic framework, a phloroglucinol compound, and a phenyltriazine compound as raw materials to prepare the covalently bonded MOFs@COFs composite material.

7. The method according to claim 6, characterized in that, Wastewater is water containing organic pollutants.

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