Heterogeneous catalyst COFBMTD-PY as well as preparation method and application thereof

Abstract

The invention provides a heterogeneous catalyst COFBMTD-PY as well as a preparation method and application thereof, belongs to the technical field of photocatalysts, and can solve the problems that the current thioether oxidation reaction needs to be operated under a high-temperature condition, the dosage of the catalyst is large, an additional cocatalyst is needed, and in the actual use process, most of the catalysts cannot be recycled and are not easy to recover, so that the cost is low, and the like. The loss of the catalyst is serious, and the reaction waste is increased. The heterogeneous catalyst COFBMTD-PY disclosed by the invention is constructed by taking 1, 3, 6, 8-tetra-(p-aminophenyl)-pyrene and 2 ', 5'-bis ((1H-imidazole-1-yl) methyl)-[1, 1 ': 4', 1 ''-terphenyl]-4, 4''-diformaldehyde as units, and the heterogeneous catalyst COFBMTD-PY has a structural formula shown in the specification. The heterogeneous catalyst COFBMTD-PY disclosed by the invention can be applied to catalysis of oxidation reaction of methyl thioether and derivatives thereof, and has the advantages that efficient conversion of thioether is realized, reaction selectivity is precisely regulated and controlled, sulfone generation caused by excessive oxidation is avoided, a cocatalyst or extra oxygen is not needed, and the catalyst can be repeatedly utilized.

Description

Technical Field

[0001] This invention belongs to the field of photocatalyst technology, and particularly relates to a heterogeneous catalyst COF. BMTD-PY Its preparation methods and applications. Background Technology

[0002] With the deepening of green chemistry and sustainable development concepts, the development of efficient and environmentally friendly organic synthesis methods has become an important research direction in the field of chemistry. Among these, selective oxidation reactions have wide applications in the synthesis of pharmaceuticals, pesticides, and fine chemicals. The oxidation of thioethers is particularly important because the products sulfoxides and sulfones are key structural units in many bioactive molecules. However, traditional thioether oxidation methods often rely on highly toxic oxidants such as m-chloroperoxybenzoic acid and chromates, or harsh reaction conditions, which not only generate large amounts of harmful waste but also face difficulties in controlling reaction selectivity.

[0003] Photocatalytic oxidation technology utilizes clean solar energy to drive chemical reactions, aligning with the development trend of green chemistry. In recent years, photocatalysts (such as TiO2 and CdS) have shown potential in sulfide oxidation, but they still suffer from low visible light utilization and dependence on co-catalysts (such as noble metal Pt, oxidizing agents, etc.) or additional oxidants (such as H2O2, O2, etc.), limiting the industrial-scale application of sulfide oxidation catalysts. Therefore, developing novel, highly efficient photocatalytic materials for sulfide oxidation is a significant challenge currently facing the field of photocatalysis. Summary of the Invention

[0004] This invention addresses the technical problems of current sulfide oxidation catalysts, which require high-temperature operation, large catalyst quantities, and additional co-catalysts. Furthermore, in practical applications, most catalysts are not recyclable and difficult to recover, leading to severe catalyst loss and increased reaction waste. To address these issues, this invention proposes a heterogeneous catalyst, COF. BMTD-PY The present invention relates to its preparation method and application. The catalyst of the present invention is a novel photocatalyst for selective oxidation of sulfides driven by sunlight. It has the advantages of achieving efficient conversion of sulfides, precise control of reaction selectivity, avoiding excessive oxidation to generate sulfones, requiring no co-catalyst or additional oxygen, and the catalyst can be repeatedly recycled, thus reducing production costs.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a heterogeneous catalyst COF BMTD-PY The heterogeneous catalyst COF was constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde as unit cells. BMTD-PY It has the following structure: .

[0006] In another aspect, the present invention also provides the heterogeneous catalyst COF. BMTD-PY The preparation method includes the following steps: 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde are added to a first reaction vessel, followed by the addition of a mixed solvent of mesitylene, n-butanol, and acetic acid. The first reaction vessel is then placed in an oven for complete reaction. After the reaction is completed, the mixture is filtered under reduced pressure and washed to obtain the heterogeneous catalyst COF. BMTD-PY .

[0007] In one embodiment, the molar ratio of 1,3,6,8-tetra-(p-aminophenyl)-pyrene to 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde is 1:2; the volume ratio of mesitylene, n-butanol, and acetic acid is 1~1.3:3~3.3:1~1.3.

[0008] In one embodiment, the reaction conditions in the oven are: constant temperature reaction at 120℃~125℃ for 72 hours.

[0009] In one embodiment, the washing step includes: washing three times with N,N-dimethylformamide, and then washing three times with ethanol.

[0010] In another aspect, the present invention also provides the heterogeneous catalyst COF. BMTD-PY Application of photocatalysts in the oxidation of anisole and its derivatives.

[0011] In one embodiment, the steps include: first, the heterogeneous catalyst COF... BMTD-PY Anisole or its derivatives were added to a second reaction vessel, followed by acetonitrile. The second reaction vessel was then placed on a 660nm red LED photoreactor and stirred to allow for complete reaction. After the reaction was complete, the mixture was filtered to obtain the target compound. The resulting solution was centrifuged to recover the heterogeneous catalyst COF. BMTD-PY .

[0012] In one embodiment, the stirring reaction time is 10h~13h, and the reaction temperature is 24℃~26℃.

[0013] In one embodiment, anisole or a derivative thereof, and a heterogeneous catalyst COF BMTD-PY The molar ratio is 1:0.02.

[0014] In one embodiment, the structural formula of the anisole sulfide derivative is as follows: , , , , Any one of them.

[0015] Compared with the prior art, the advantages and positive effects of the present invention are as follows: The present invention achieves this through the rational design of COF BMTD-PY The electronic structure of COF is applied to the catalytic oxidation reaction of anisole and its derivatives, enabling efficient conversion of sulfides; this invention utilizes COF BMTD-PY The inherent pore confinement effect enables precise control of reaction selectivity and avoids excessive oxidation to generate sulfone. The reaction process of this invention does not require high temperature, and the amount of catalyst used is small and no co-catalyst or additional oxygen is needed to achieve heterogeneous catalysis, truly realizing green catalysis. Moreover, the catalyst can be reused and is easy to recycle, which improves the utilization rate of the catalyst and reduces the production cost. Attached Figure Description

[0016] Figure 1 The heterogeneous catalyst COF provided in the embodiments of the present invention BMTD-PY A schematic diagram of the synthesis; Figure 2 The heterogeneous catalyst COF prepared in Example 1 of this invention BMTD-PY Powder X-ray diffraction pattern; Figure 3 The heterogeneous catalyst COF prepared in Example 1 of this invention BMTD-PY Infrared spectra of the ligands; Figure 4 Example 7 of the present invention describes the recovery of the catalyst COF. BMTD-PY Yield graphs corresponding to cyclic experiments; Figure 5 Example 7 of the present invention describes the recovery of the catalyst COF. BMTD-PY Powder X-ray diffraction pattern after 5 cycles of reaction. Detailed Implementation

[0017] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all 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] Covalent organic frameworks (COFs) are a class of crystalline porous materials formed by light elements (C, H, O, N, etc.) linked by strong covalent bonds. They have high specific surface area, tunable pore size and excellent photoelectric properties. Compared with traditional photocatalysts, COFs have the following advantages: (1) The structure can be precisely designed, and the band structure can be optimized by regulating the building blocks, thereby improving the visible light response capability; (2) The highly ordered pore structure is conducive to substrate mass transfer and exposure of active sites; (3) The abundant functional groups can serve as catalytic active centers, enabling efficient photocatalysis.

[0019] This invention provides a heterogeneous catalyst COF BMTD-PY This invention relates to COF, its preparation method, and its applications. BMTD-PY The electronic structure of COF, when applied to thioether oxidation reactions, enables highly efficient conversion of thioethers; this invention utilizes COF BMTD-PY The inherent pore confinement effect of COF enables precise control of reaction selectivity, avoiding excessive oxidation to sulfone. This invention eliminates the dependence of traditional photocatalytic systems on co-catalysts or additional oxygen, truly achieving green catalysis. Compared with existing technologies, this invention not only expands the application scope of COF in organic photocatalysis but also provides new ideas for developing green oxidation processes, possessing significant theoretical and practical value. Among these, the heterogeneous catalyst COF of this invention... BMTD-PY The reaction process does not require high temperatures, and heterogeneous catalysis can be achieved with a small amount of catalyst and no other additives. At the same time, the catalyst can be reused and is easy to recover, which improves the utilization rate of the catalyst and reduces the production cost.

[0020] The heterogeneous catalyst COF provided in this embodiment of the invention BMTD-PY The heterogeneous catalyst COF was constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde as unit cells. BMTD-PY It has the following structure: .

[0021] The heterogeneous catalyst COF in the embodiments of the present invention BMTD-PY The preparation method and reaction process are shown in the attached figure. Figure 1 As shown, the specific steps include: Pre-weighed 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde were added to a Schlenk tube, followed by the addition of a mixed solvent of mesitylene, n-butanol, and acetic acid. The Schlenk tube was then placed in an oven and reacted at 120°C–125°C for 72 hours. After the reaction, the mixture was filtered under reduced pressure, washed three times with N,N-dimethylformamide (DMF), and then three times with ethanol to obtain the heterogeneous catalyst COF. BMTD-PY .

[0022] In a preferred embodiment of the present invention, the molar ratio of 1,3,6,8-tetra-(p-aminophenyl)-pyrene to 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde is 1:2.

[0023] In a preferred embodiment of the present invention, the volume ratio of mesitylene, n-butanol and acetic acid is 1~1.3:3~3.3:1~1.3, and more preferably, the volume ratio of mesitylene, n-butanol and acetic acid is 1:3:1.

[0024] In a preferred embodiment of the present invention, the volume of mesitylene is 0.5 mL, the volume of n-butanol is 1.5 mL, the volume of acetic acid is 0.5 mL, and the concentration of acetic acid is 6 M.

[0025] In a preferred embodiment of the present invention, the reduced pressure filtration step includes: using a circulating water vacuum pump to generate a negative pressure of 0.1 MPa in the filtration flask for filtration.

[0026] In a preferred embodiment of the present invention, the reaction temperature is 120°C.

[0027] The heterogeneous catalyst COF in the embodiments of the present invention BMTD-PY As a photocatalyst, it is used to catalyze the oxidation reaction of anisole and its derivatives. The structural formula of the anisole derivative is as follows: , , , Any one of them.

[0028] The heterogeneous catalyst COF in the embodiments of the present invention BMTD-PY As a photocatalyst in the catalytic oxidation of sulfides, the reaction process is as follows: .

[0029] The heterogeneous catalyst COF in the embodiments of the present invention BMTD-PY It is applied to the catalytic oxidation of sulfides, specifically including the following steps: Under conditions of 24℃~26℃, the weighed heterogeneous catalyst COF was first... BMTD-PY Anisole or its derivatives were added to a round-bottom flask equipped with a magnetic stir bar, followed by acetonitrile. The flask was then placed on a 660nm red LED photoreactor and stirred for 10-13 hours to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter, the yield was determined by gas chromatography, and the heterogeneous catalyst COF was recovered. BMTD-PY .

[0030] In a preferred embodiment of the present invention, the reaction temperature is 25°C and the stirring reaction time is 12 hours.

[0031] In one embodiment of the present invention, anisole or its derivatives, and a heterogeneous catalyst COF... BMTD-PY The molar ratio is 1:0.02.

[0032] In a preferred embodiment of the present invention, anisole or its derivative is 0.3 mmol, and the heterogeneous catalyst COF... BMTD-PY The concentration is 13 mg, and the amount of acetonitrile added is 2 mL.

[0033] In one embodiment of the present invention, the heterogeneous catalyst COF BMTD-PY The recovery methods include: after the reaction is complete, separating the catalyst from the post-reaction solution by centrifugation, and then naturally drying it to obtain the heterogeneous catalyst COF. BMTD-PY .

[0034] The heterogeneous catalyst COF of this invention BMTD-PY It exhibits good stability and can be efficiently recovered through simple centrifugation or filtration, yielding the recovered heterogeneous catalyst COF. BMTD-PY It was reused to catalyze the oxidation of sulfides, and after being recycled 5 times, the yield of the product was still greater than 91%.

[0035] To more clearly and in detail describe the heterogeneous catalyst COF provided in the embodiments of the present invention... BMTD-PY The preparation method and application of the present invention will be described below with reference to specific embodiments. All raw materials used in all embodiments of the present invention are commercially available. Specifically, the raw materials for 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde are supplied by Jilin Zhongke Science & Technology Co., Ltd., and the other raw materials are supplied by Sinopharm Chemical Reagent Co., Ltd.

[0036] Example 1 Heterogeneous catalyst COF BMTD-PY Preparation This embodiment uses a heterogeneous catalyst COF. BMTD-PY The preparation method includes the following steps: Weigh 11.3 mg (0.02 mmol) of 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 17.8 mg (0.04 mmol) of 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde and add them to a Schlenk tube; then add a mixed solvent of 0.5 mL of mesitylene, 1.5 mL of n-butanol, and 0.5 mL of 6M acetic acid; place the Schlenk tube in an oven and react at 120 °C for 72 h; after the reaction, use a circulating water vacuum pump to create a negative pressure of 0.1 MPa in the filtration flask for reduced pressure filtration; then wash three times with N,N-dimethylformamide and three times with ethanol to obtain the heterogeneous catalyst COF of this example. BMTD-PY .

[0037] The prepared heterogeneous catalyst COF BMTD-PY Characterization was performed using powder X-ray diffraction (PXRD) and infrared absorption spectroscopy (IR), respectively, and the results are as follows: Figure 2 and Figure 3 As shown. Among them, Figure 2 The powder X-ray diffraction pattern is shown below. Figure 2 It can be seen that there is a distinct characteristic peak at 3.8°, indicating that the COF prepared by this invention... BMTD-PY The material has good crystallinity; Figure 3 It is a heterogeneous catalyst COF BMTD-PY Infrared spectra of ligands, from Figure 3 It can be seen that the monomer contains obvious characteristic peaks of primary amine groups and carbonyl groups, resulting in a heterogeneous catalyst COF. BMTD-PY The presence of a distinct imine group characteristic peak indicates that the primary amine condenses with a carbonyl group to form a Schiff base structure.

[0038] Examples 2-6 are the heterogeneous catalysts COF prepared in Example 1. BMTD-PY The specific applications in the catalytic oxidation of thioethers are shown in Table 1, with the specific raw materials and amounts used in Examples 2-6.

[0039] Table 1 Raw materials and dosages for Examples 2-6

[0040] Example 2 Heterogeneous catalyst COF BMTD-PY Application of photocatalysts in the catalytic oxidation of anisole. This embodiment uses a heterogeneous catalyst COF. BMTD-PY The photocatalytic application is used in the oxidation reaction of anisole, and the reaction process is shown below: .

[0041] This embodiment uses a heterogeneous catalyst COF. BMTD-PY The oxidation reaction applied to anisole specifically includes the following steps: According to benzyl sulfide, COF BMTD-PY The molar ratio was 1:0.02. 13 mg of the heterogeneous catalyst COF was weighed out. BMTD-PY And 37.3 mg of anisole; Under conditions of 25℃, the heterogeneous catalyst COF was first... BMTD-PY Add anisole and methyl sulfide to a 10 mL round-bottom flask equipped with a magnetic stir bar, then add 2 mL of acetonitrile. Place the round-bottom flask on a 660 nm red LED photoreactor and stir with a magnetic stir bar for 12 h to allow the reaction to proceed fully. After the reaction is complete, filter the crude product through a membrane filter to obtain the target product, methyl sulfinylbenzene. The yield of methyl sulfinylbenzene was determined by gas chromatography and found to be 99%.

[0042] Example 3 Heterogeneous catalyst COF BMTD-PY Application of photocatalysts in the oxidation of 4-methyl anisole This embodiment uses a heterogeneous catalyst COF. BMTD-PY The photocatalytic application is used in the oxidation reaction of 4-methyl anisole, and the reaction process is shown below: .

[0043] This embodiment uses a heterogeneous catalyst COF. BMTD-PY The oxidation reaction applied to 4-methyl anisole specifically includes the following steps: According to 4-methyl anisole, COF BMTD-PY The molar ratio was 1:0.02. 13 mg of the heterogeneous catalyst COF was weighed out. BMTD-PY And 41.5 mg of 4-methyl anisole; Under conditions of 25℃, the heterogeneous catalyst COF was first... BMTD-PY 4-Methyl anisole sulfide was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, followed by 2 mL of acetonitrile. The flask was then placed on a 660 nm red LED photoreactor and stirred with a magnetic stir bar for 12 h to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter to obtain the target product 1-methyl-4-(methylsulfinyl)benzene. The yield of 1-methyl-4-(methylsulfinyl)benzene was determined by gas chromatography, and the yield was 99%.

[0044] Example 4 Heterogeneous catalyst COF BMTD-PY Application of photocatalysts in the oxidation of 4-methoxyanisole This embodiment uses a heterogeneous catalyst COF. BMTD-PY The photocatalytic application is used in the oxidation reaction of 4-methoxyanisole, and the reaction process is shown below: .

[0045] This embodiment uses a heterogeneous catalyst COF. BMTD-PY The oxidation reaction applied to 4-methoxyanisole specifically includes the following steps: According to 4-methoxyanisole, COF BMTD-PY The molar ratio was 1:0.02. 13 mg of the heterogeneous catalyst COF was weighed out. BMTD-PY And 46.3 mg of 4-methoxyanisole; Under conditions of 25℃, the heterogeneous catalyst COF was first... BMTD-PY 4-Methoxyanisole was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, followed by 2 mL of acetonitrile. The flask was then placed on a 660 nm red LED photoreactor and stirred with a magnetic stir bar for 12 h to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter to obtain the target product 1-methoxy-4-(methylsulfinyl)benzene. The yield of 1-methoxy-4-(methylsulfinyl)benzene was determined by gas chromatography, and the yield was 94%.

[0046] Example 5 Heterogeneous catalyst COF BMTD-PY Application as a photocatalyst in the catalytic oxidation of 4-chlorobenzyl sulfide This embodiment uses a heterogeneous catalyst COF. BMTD-PY The photocatalytic application is used in the oxidation reaction of 4-chlorobenzyl sulfide, and the reaction process is shown below: .

[0047] This embodiment uses a heterogeneous catalyst COF. BMTD-PY The oxidation reaction applied to 4-chlorobenzyl sulfide specifically includes the following steps: According to 4-chlorobenzyl sulfide, COF BMTD-PY The molar ratio was 1:0.02. 13 mg of the heterogeneous catalyst COF was weighed out. BMTD-PY And 47.6 mg of 4-chloroanisole; Under conditions of 25℃, the heterogeneous catalyst COF was first... BMTD-PY4-Chlorophenyl sulfide was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, followed by 2 mL of acetonitrile. The flask was then placed on a 660 nm red LED photoreactor and stirred with a magnetic stir bar for 12 h to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter to obtain the target product 1-chloro-4-(methylsulfinyl)benzene. The yield of 1-chloro-4-(methylsulfinyl)benzene was determined by gas chromatography, and the yield was 96%.

[0048] Example 6 Heterogeneous catalyst COF BMTD-PY Application of photocatalysts in the oxidation of 4-bromophenyl sulfide This embodiment uses a heterogeneous catalyst COF. BMTD-PY The photocatalytic application is used in the oxidation reaction of 4-bromophenyl sulfide, and the reaction process is shown below: .

[0049] This embodiment uses a heterogeneous catalyst COF. BMTD-PY The oxidation reaction applied to 4-bromophenyl sulfide specifically includes the following steps: According to 4-bromophenyl sulfide, COF BMTD-PY The molar ratio was 1:0.02. 13 mg of the heterogeneous catalyst COF was weighed out. BMTD-PY And 60.9 mg of 4-bromobenzyl sulfide; Under conditions of 25℃, the heterogeneous catalyst COF was first... BMTD-PY 4-Bromophenyl sulfide was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, followed by 2 mL of acetonitrile. The flask was then placed on a 660 nm red LED photoreactor and stirred with a magnetic stir bar for 12 h to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter to obtain the target product 1-bromo-4-(methylsulfinyl)benzene. The yield of 1-bromo-4-(methylsulfinyl)benzene was determined by gas chromatography and found to be 92%.

[0050] The products and yields obtained in Examples 2-6 are shown in Table 2.

[0051] Table 2. Products and Yields of Examples 2-6

[0052] As can be seen from the above, Examples 2-6 of the present invention are heterogeneous catalysts COF. BMTD-PY When applied to the oxidation of sulfides, the yield of the product is greater than 90%, and can reach up to 99%, indicating that the heterogeneous catalyst COF of this invention achieves a yield of more than 90%, and can reach up to 99%. BMTD-PY Capable of achieving efficient conversion of sulfides; anisole or its derivatives, heterogeneous catalyst COF BMTD-PYThe molar ratio is 1:0.02, requiring less catalyst and eliminating the need for high temperatures, resulting in high catalytic efficiency and reduced production costs.

[0053] Example 7 Heterogeneous catalyst COF BMTD-PY Recycling and reuse After the reaction in Example 2 was completed, the precipitate obtained by centrifugation was filtered out, air-dried, and recovered to obtain the recovered heterogeneous catalyst COF. BMTD-PY ; At 25°C, 13 mg of the recovered heterogeneous catalyst COF was first used. BMTD-PY 0.3 mmol of anisole sulfide was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, followed by acetonitrile. The reaction vessel was then placed on a 660 nm red LED photoreactor and stirred for 12 h to allow for complete reaction. After the reaction was complete, the crude product was filtered through a membrane filter to obtain methylsulfinylbenzene. The yield of methylsulfinylbenzene was determined by gas chromatography. The heterogeneous catalyst COF was used. BMTD-PY The catalytic cycle effect is as follows Figure 4 As shown. By Figure 4 It can be seen that the heterogeneous catalyst COF of the present invention BMTD-PY After being recycled and reused 5 times, the yield of the product was still greater than 91%, indicating that the catalyst of the present invention can be recycled and reused.

[0054] This invention recycles COF after it has been used 5 times. BMTD-PY The powder X-ray diffraction pattern of the material is as follows: Figure 5 As shown. By Figure 5 It can be seen that the heterogeneous catalyst COF of the present invention BMTD-PY After being recycled and reused 5 times, the heterogeneous catalyst COF BMTD-PY The good preservation of the crystal form indicates that the novel covalent organic framework material provided by this invention has very stable performance as a heterogeneous catalyst for the photocatalytic oxidation of sulfides.

[0055] The above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Any modifications, alterations, evolutions, or improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope of the present invention.

Claims

1. A heterogeneous catalyst COF BMTD-PY Its characteristics are, The heterogeneous catalyst COF was constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde as unit cells. BMTD-PY It has the following structure: 。 2. A heterogeneous catalyst COF as described in claim 1 BMTD-PY The preparation method of the [method] is characterized by, The process includes the following steps: 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde are added to a first reaction vessel, followed by the addition of a mixed solvent of mesitylene, n-butanol, and acetic acid. The first reaction vessel is then placed in an oven for complete reaction. After the reaction is complete, the mixture is filtered under reduced pressure and washed to obtain the heterogeneous catalyst COF. BMTD-PY .

3. The heterogeneous catalyst COF according to claim 2 BMTD-PY The preparation method of the [method] is characterized by, The molar ratio of 1,3,6,8-tetra-(p-aminophenyl)-pyrene to 2',5'-bis((1H-imidazol-1-yl)methyl)-[1,1':4',1''-terphenyl]-4,4''-dicarboxaldehyde is 1:2; the volume ratio of mesitylene, n-butanol, and acetic acid is 1~1.3:3~3.3:1~1.

3.

4. The heterogeneous catalyst COF according to claim 2 BMTD-PY The preparation method of the [method] is characterized by, The reaction conditions in the oven were: constant temperature reaction at 120℃~125℃ for 72 hours.

5. The heterogeneous catalyst COF according to claim 2 BMTD-PY The preparation method of the [method] is characterized by, The washing steps include: first washing three times with N,N-dimethylformamide, then washing three times with ethanol.

6. The heterogeneous catalyst COF according to claim 1 BMTD-PY Application of photocatalysts in the oxidation of anisole and its derivatives.

7. The application according to claim 6, characterized in that, Includes the following steps: First, the heterogeneous catalyst COF BMTD-PY Anisole or its derivatives were added to a second reaction vessel, followed by acetonitrile. The second reaction vessel was then placed on a 660nm red LED photoreactor and stirred to allow for complete reaction. After the reaction was complete, the mixture was filtered to obtain the target compound. The resulting solution was centrifuged to recover the heterogeneous catalyst COF. BMTD-PY .

8. The application according to claim 7, characterized in that, The stirring reaction time is 10~13h, and the reaction temperature is 24℃~26℃.

9. The application according to claim 7, characterized in that, Benzyl sulfide or its derivatives, heterogeneous catalyst COF BMTD-PY The molar ratio is 1:0.

02.

10. The application according to any one of claims 6-9, characterized in that, The structural formula of the benzyl sulfide derivative is , , , , Any one of them.

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