D-A structural heterogeneous catalyst COFBTC-PY as well as preparation method and application thereof

Abstract

The invention provides a D-A structure type heterogeneous catalyst COFBTC-PY as well as a preparation method and application thereof, belongs to the technical field of photocatalysts, and can solve the technical problems that a catalyst system applied to benzylamine oxidative coupling generally has relatively low sunlight utilization efficiency and too high photo-induced electron-hole pair recombination rate at present. The invention relates to a D-A structural type heterogeneous catalyst COFBTC-PY, the D-A structural type heterogeneous catalyst COFBTC-PY is constructed by using 1, 3, 6, 8-tetra-(p-aminophenyl)-pyrene and 5, 5 '-(benzo [C] [1, 2, 5] thiadiazole-4, 7-diyl) bis (thiophene-2-formaldehyde) as units, and the D-A structural type heterogeneous catalyst COFBTC-PY has the following structural formula as shown in the specification. The D-A structure type heterogeneous catalyst COFBTC-PY can be used as a photocatalyst to be applied to catalysis of oxidation reaction of benzylamine or derivatives thereof, and has the advantages of high activity, excellent stability, wide spectral response, recyclability and low cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photocatalysts, and particularly relates to a D-A structure type heterogeneous catalyst COF BTTC-PY and a preparation method and application thereof. BACKGROUND

[0002] In the field of organic chemistry, imines (compounds containing C=N bonds) as a class of key intermediates are the core structural units for constructing many nitrogen-containing molecules with biological activity, high-value fine chemicals and drug molecules. Therefore, the efficient synthesis strategy of imine compounds has attracted widespread attention. The traditional synthesis path of imine compounds mainly relies on the condensation reaction of amines and carbonyl compounds. However, this method is often limited by harsh reaction conditions, unsatisfactory product yield, poor selectivity control, and the use of a large amount of harmful reagents or solvents, resulting in heavy environmental burden.

[0003] In recent years, photocatalytic oxidation coupling of benzylamine is considered as a promising alternative synthesis scheme due to its efficient performance under mild conditions and excellent atomic economy, sustainability and environmental friendliness. However, the current catalyst systems applied to the oxidation coupling of benzylamine, including metal oxides, metal sulfides and organic small molecule photosensitizers, generally have low solar utilization efficiency and high recombination rate of photo-generated electron-hole pairs. These inherent defects seriously restrict the overall conversion efficiency of light energy to chemical energy, and hinder the practical application and popularization of the technology in large-scale and industrial production. Therefore, developing new photocatalysts with low cost, high activity, excellent stability and wide spectral response to efficiently drive the oxidation coupling of benzylamine to generate imines has become a key technical problem to be solved in the field of photocatalytic research. SUMMARY

[0004] The present application is aimed at the technical problem that the current catalyst systems applied to the oxidation coupling of benzylamine generally have low solar utilization efficiency and high recombination rate of photo-generated electron-hole pairs, and proposes a D-A structure type heterogeneous catalyst COF BTTC-PY and a preparation method and application thereof.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: a D-A structure type heterogeneous catalyst COF BTTC-PY which is constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) as unit structures, wherein the D-A structure type heterogeneous catalyst COF BTTC-PY has the following structural formula: .

[0006] The application also provides a preparation method of the D-A structure type heterogeneous catalyst COF BTTC-PY , comprising the following steps: adding 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxaldehyde) into a first reaction container, then adding a mixed solvent of o-dichlorobenzene, n-butanol and acetic acid, and then placing the first reaction container in an oven for sufficient reaction, and after the reaction is completed, performing filtration and washing under reduced pressure to obtain the D-A structure type heterogeneous catalyst COF BTTC-PY .

[0007] In one embodiment, the molar ratio of 1,3,6,8-tetra-(p-aminophenyl)-pyrene to 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxaldehyde) is 1:2, and the volume ratio of o-dichlorobenzene, n-butanol and acetic acid is 1~1.3:2~2.3:0.3~0.5.

[0008] In one embodiment, the reaction condition in the oven is that the reaction is carried out at 120℃~125℃ for 72h.

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

[0010] The application also provides an application of the D-A structure type heterogeneous catalyst COF BTTC-PY as a photocatalyst in catalyzing an oxidation reaction of benzylamine or a derivative thereof.

[0011] In one embodiment, the application comprises the following steps: first placing benzylamine or a derivative thereof, the D-A structure type heterogeneous catalyst COF BTTC-PY , and acetonitrile in a second reaction container, and then placing the second reaction container under irradiation of a 30W white LED lamp for sufficient reaction; after the reaction is completed, performing centrifugation, rotary evaporation and silica gel column purification to obtain a corresponding target product; and recovering the precipitate after centrifugation to obtain the D-A structure type heterogeneous catalyst COF BTTC-PY .

[0012] In one embodiment, the reaction temperature is 24℃~26℃, and the reaction time is 23h~25h.

[0013] In one embodiment, the molar ratio of benzylamine or a derivative thereof to the D-A structure type heterogeneous catalyst COF BTTC-PY is 1:0.05.

[0014] In one embodiment, the structure of the benzylamine derivative is , , .

[0015] Compared with the prior art, the application has the advantages and positive effects that the D-A structure type heterogeneous catalyst COF BTTC-PY is constructed by 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) as units, the D-A structure can regulate the energy band, has wide spectrum absorption, significantly enhances the visible light or even near-infrared light response, and improves the utilization rate of sunlight; the strong electron push-pull effect between the D-A units promotes the directional migration of photo-generated carriers and inhibits the electron-hole recombination, so that high-efficiency charge separation can be realized; the metal-free D-A structure type heterogeneous catalyst COF BTTC-PY has an all-organic skeleton, avoids heavy metal pollution, and has excellent chemical stability and light stability due to the crystallinity and covalent bond network of the COF BTTC-PY , and can be used for a long time; compared with traditional catalysts, the COF BTTC-PY material has the characteristics of high-efficiency light capture, low carrier recombination rate and green sustainability, and has high selectivity, high conversion rate and high yield when applied to the photocatalytic oxidation reaction of benzylamine and its derivatives. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a synthesis schematic diagram of the D-A structure type heterogeneous catalyst COF BTTC-PY provided in the embodiments of the application; Figure 2 is a powder X-ray diffraction spectrum of the D-A structure type heterogeneous catalyst COF BTTC-PY prepared in Embodiment 1 of the application; Figure 3 is an infrared spectrum of the D-A structure type heterogeneous catalyst COF BTTC-PY and a ligand prepared in Embodiment 1 of the application; Figure 4 is a yield diagram corresponding to the cycle experiment on the recycled D-A structure type heterogeneous catalyst COF BTTC-PY in Embodiment 7 of the application; Figure 5 is a powder X-ray diffraction spectrum of the D-A structure type heterogeneous catalyst COF BTTC-PY cycled for 5 times in Embodiment 7 of the application. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0018] Currently, in the photocatalytic oxidation of benzylamine, there are some restricting factors such as limited visible light absorption ability of traditional metal-based catalysts (such as metal oxides and metal sulfides), high recombination rate of photo-generated carriers, low energy conversion efficiency, poor stability of organic small molecule photosensitizers, and difficulty in recycling and reusing. The present application provides a metal-free donor-acceptor (D-A) structure type heterogeneous catalyst COF BTTC-PY , a preparation method and application thereof. The catalyst of the present application can realize efficient absorption in the visible light region through the designed D-A structure unit, and the extended pi-conjugated skeleton and ordered channel structure not only significantly promote the separation and migration of photo-generated electron-hole pairs, but also provide abundant active sites to accelerate the oxidation process of benzylamine. At the same time, the high crystallinity and insolubility of the COF BTTC-PY material make it have excellent chemical stability and easy recycling characteristics, overcoming the defect that traditional homogeneous catalysts are difficult to recycle. Compared with the existing catalytic system, the metal-free COF BTTC-PY catalyst of the present application can efficiently drive the selective oxidation of benzylamine under mild conditions of room temperature, normal pressure and visible light irradiation without adding any noble metal cocatalyst, and shows much higher turnover frequency and cycle stability than traditional materials, which fundamentally solves the core problems of traditional photocatalysts such as low solar energy utilization rate, serious carrier recombination, harsh reaction conditions and non-recyclable catalysts, and provides a new idea for developing green and efficient photocatalytic amine oxidation technology.

[0019] The D-A structure type heterogeneous catalyst COF BTTC-PY of the present application is constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) as unit, and has the following structure formula: BTTC-PY .

[0020] The preparation method of the D-A structure type heterogeneous catalyst COF BTTC-PY of the present application is shown in the accompanying drawing, and specifically includes the following steps: Figure 1 ​​1,3,6,8-tetra-(p-aminophenyl)pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxaldehyde) were added to a Schlenk tube, followed by a mixed solvent of o-dichlorobenzene, n-butanol, and acetic acid. The Schlenk tube was placed in an oven and reacted at 120℃~125℃ for 72 h. 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 DA-structured heterogeneous catalyst COF. BTTC-PY .

[0021] In a preferred embodiment of the present invention, the molar ratio of 1,3,6,8-tetra-(p-aminophenyl)-pyrene to 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxaldehyde) is 1:2.

[0022] In a preferred embodiment of the present invention, the volume ratio of o-dichlorobenzene, n-butanol, and acetic acid is 1~1.3:2~2.3:0.3~0.5, and more preferably, the volume ratio of o-dichlorobenzene, n-butanol, and acetic acid is 1:2:0.3.

[0023] In a preferred embodiment of the present invention, the volume of o-dichlorobenzene is 1 mL, the volume of n-butanol is 2 mL, the volume of acetic acid is 0.3 mL, and the concentration of acetic acid is 6 M.

[0024] 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.

[0025] In a preferred embodiment of the present invention, the reaction temperature is 120°C.

[0026] This invention prepares a metal-free DA-structured heterogeneous catalyst COF using the above-described preparation method. BTTC-PY It has the following advantages: First, the heterogeneous catalyst COF of the present invention BTTC-PY First, the DA structure allows for tunable bandgap absorption, exhibiting broad-spectrum absorption and significantly enhancing visible and even near-infrared light response, thereby improving solar energy utilization. Second, the strong electron push-pull interaction between DA units promotes the directional migration of photogenerated carriers and suppresses electron-hole recombination, enabling efficient charge separation. Third, this invention provides a metal-free DA-structured heterogeneous catalyst, COF. BTTC-PY The fully organic framework avoids heavy metal pollution, and COF BTTC-PY The crystallinity and covalent network of the catalyst endow it with excellent chemical and photostability, allowing for long-term recycling; fourth, compared with traditional catalysts, the COF of this invention... BTTC-PYThe material combines the characteristics of high-efficiency light capture, low carrier recombination rate and green sustainability, and exhibits high selectivity, high conversion rate and high yield when applied to photocatalytic benzylamine oxidation.

[0027] The DA-structured heterogeneous catalyst COF in this invention embodiment BTTC-PY It can be applied to the photocatalytic oxidation of benzylamine or its derivatives, and the reaction process is as follows: .

[0028] The DA-structured heterogeneous catalyst COF in this invention embodiment BTTC-PY The application in the photocatalytic oxidation reaction of benzylamine or its derivatives specifically includes the following steps: Under conditions of 24℃~26℃, first weigh benzylamine or its derivatives and DA-structured heterogeneous catalyst COF were added. BTTC-PY Acetonitrile was placed in a round-bottom flask, and the flask was then irradiated with a 30W white LED lamp for 23-25 ​​hours. After the reaction, the catalyst and solution were separated by centrifugation. The separated liquid was then purified by rotary evaporation and silica gel column chromatography to obtain the corresponding product. The precipitate after centrifugation was filtered out and allowed to air dry for recovery, yielding the DA-structured heterogeneous catalyst COF. BTTC-PY .

[0029] In one embodiment of the present invention, benzylamine or its derivatives, and the DA-structured heterogeneous catalyst COF are used. BTTC-PY The molar ratio is 1:0.05.

[0030] In a preferred embodiment of the present invention, the reaction temperature is 25°C and the stirring reaction time is 24 hours.

[0031] In one embodiment of the present invention, in the silica gel column purification step, the ratio of petroleum ether to dichloromethane is 10:1 to 12:1 V / V.

[0032] The heterogeneous catalyst COF of this invention BTTC-PY It has good stability, can be applied to photocatalytic benzylamine oxidation reaction, and can be recycled.

[0033] The novel DA-type COF obtained by this invention BTTC-PY Photocatalysts, through the rational selection of electron donor and acceptor units, achieve efficient charge separation, enabling rapid and efficient benzylamine oxidative coupling. Under mild conditions (room temperature, air atmosphere) without metals or added oxidants, COF... BTTC-PY It can catalyze the conversion of benzylamine to imine with high selectivity within 24 hours, with significantly better conversion and yield than traditional catalysts; cyclic experiments and large-scale reactions have demonstrated that COF BTTC-PY The stability and recyclability of the material, along with its expanded substrate range, demonstrate its applicability in synthesis.

[0034] In order to more clearly and specifically introduce the D-A structure type heterogeneous catalyst COF BTTC-PY provided by the embodiments of the present application, a preparation method and application thereof will be described below with specific examples. All raw materials used in the embodiments of the present application can be purchased in the market, wherein the raw material manufacturers of 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) are Jilin Zhongke Research Technology Co., Ltd., and the manufacturers of other raw materials are National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0035] Preparation of the D-A structure type heterogeneous catalyst COF BTTC-PY of Example 1 The preparation method of the D-A structure type heterogeneous catalyst COF BTTC-PY of the present embodiment comprises the following steps: 22.67 mg (0.04 mmol) of 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 28.5 mg (0.08 mmol) of 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) were weighed and added into a schlenk tube; 1 mL of o-dichlorobenzene, 2 mL of n-butanol and 0.3 mL of a mixed solvent of 6M acetic acid were further added; the schlenk tube was placed in an oven and reacted at 120°C for 72 h; after the reaction was completed, a 0.1Mpa negative pressure was generated in the filter bottle by using a circulating water vacuum pump, and the pressure was reduced and filtered; first, N,N-dimethylformamide was used to wash three times, and then ethanol was used to wash three times, to obtain the D-A structure type heterogeneous catalyst COF BTTC-PY .

[0036] The prepared D-A structure type heterogeneous catalyst COF BTTC-PY was characterized by powder X-ray diffraction (PXRD) and infrared absorption spectrum (IR), respectively, and the results are shown in Figure 2 and Figure 3 . Among them, Figure 2 is the powder X-ray diffraction spectrum, and it can be seen from Figure 2 that there is an obvious characteristic peak at 4.47°, indicating that the obtained COF BTTC-PY has good crystallinity; Figure 3 is the infrared spectrum of the COF BTTC-PY material prepared by the present application and the ligand, and it can be seen from Figure 3 that there are obvious characteristic peaks of primary amine groups and carbonyl groups in the monomer, and there are obvious characteristic peaks of imine groups in the obtained COF BTTC-PY material, indicating that the condensation of primary amine and carbonyl group obtains a Schiff base structure.

[0037] Example 2-Example 5 are D-A structured heterogeneous catalyst COF prepared by Example 1 BTTC-PY In the application of photocatalytic oxidation of benzylamine or its derivatives, the specific raw materials and amounts of Examples 2-5 are shown in Table 1.

[0038] Table 1 Raw materials and amounts of Examples 2-5

[0039] Example 2 D-A structured heterogeneous catalyst COF BTTC-PY Application in photocatalytic oxidation of benzylamine D-A structured heterogeneous catalyst COF of this example BTTC-PY Applied to photocatalytic oxidation of benzylamine, the reaction process is as follows: , Specifically includes the following steps: According to the molar ratio of benzylamine, D-A structured heterogeneous catalyst COF BTTC-PY , 15 mg of D-A structured heterogeneous catalyst COF BTTC-PY , 2 mL of acetonitrile were weighed into a 10 mL round-bottom flask, then the round-bottom flask was irradiated under a 30 W white LED lamp at 25°C for 24 h; After the reaction was completed, the catalyst and the solution were separated by centrifugation, and the liquid separated by centrifugation was rotary evaporated, then purified by silica gel column with petroleum ether: dichloromethane = 12:1 V / V, to obtain the product N-benzylidene benzylamine, the yield was 99%.

[0040] Example 3 D-A structured heterogeneous catalyst COF BTTC-PY Application in photocatalytic oxidation of 4-bromobenzylamine D-A structured heterogeneous catalyst COF of this example BTTC-PY Applied to photocatalytic oxidation of 4-bromobenzylamine, the reaction process is as follows: , Specifically includes the following steps: According to the molar ratio of 4-bromobenzylamine, D-A structured heterogeneous catalyst COF BTTC-PY , 15 mg of D-A structured heterogeneous catalyst COF BTTC-PY, 2 mL acetonitrile were placed in a 10 mL round-bottom flask, and then the round-bottom flask was irradiated under a 30 W white LED lamp at 25 °C for 24 h; after the reaction was completed, the catalyst was separated from the solution by centrifugation, and the liquid separated by centrifugation was rotary evaporated, and then purified by a silica gel column with petroleum ether:dichloromethane = 12:1 V / V to obtain the product N-(4-methoxybenzylidene)-4-methoxybenzylamine, and the yield was determined to be 83%.

[0041] Example 4 D-A structured heterogeneous catalyst COF BTTC-PY Application in photocatalytic oxidation of 4-methoxybenzylamine D-A structured heterogeneous catalyst COF in this example BTTC-PY Application in photocatalytic oxidation of 4-methoxybenzylamine, and the reaction process is as follows: , Specifically includes the following steps: According to the molar ratio of 4-methoxybenzylamine, D-A structured heterogeneous catalyst COF BTTC-PY , 15 mg of D-A structured heterogeneous catalyst COF BTTC-PY , 2 mL acetonitrile were placed in a 10 mL round-bottom flask, and then the round-bottom flask was irradiated under a 30 W white LED lamp at 25 °C for 24 h; after the reaction was completed, the catalyst was separated from the solution by centrifugation, and the liquid separated by centrifugation was rotary evaporated, and then purified by a silica gel column with petroleum ether:dichloromethane = 12:1 V / V to obtain the product N-(4-methoxybenzylidene)-4-methoxybenzylamine, and the yield was determined to be 83%.

[0042] Example 5 D-A structured heterogeneous catalyst COF BTTC-PY Application in photocatalytic oxidation of 4-methylbenzylamine D-A structured heterogeneous catalyst COF in this example BTTC-PY Application in photocatalytic oxidation of 4-methylbenzylamine, and the reaction process is as follows: , Specifically includes the following steps: According to the molar ratio of 4-methylbenzylamine, D-A structured heterogeneous catalyst COF BTTC-PY , 15 mg of D-A structured heterogeneous catalyst COF BTTC-PY2 mL of acetonitrile was placed in a 10 mL round-bottom flask, and the flask was then irradiated with a 30 W white LED lamp and reacted at 25 °C for 24 h. After the reaction was completed, the catalyst was separated from the solution by centrifugation. The centrifuged liquid was then purified by rotary evaporation and silica gel column chromatography with petroleum ether:dichloromethane = 12:1 V / V to obtain the product N-(4-methylbenzylene)-4-methylbenzylamine, with a yield of 94%.

[0043] The products and yields obtained in Examples 2-5 are shown in Table 2.

[0044] Table 2. Products and yields obtained in Examples 2-5

[0045] As can be seen from the above, Examples 2-5 are the DA-structured heterogeneous catalysts COF of the present invention. BTTC-PY When applied to the photocatalytic oxidation of benzylamine and its derivatives, the yields of the products were all greater than 80%, with the highest reaching 99%, demonstrating that the DA-structured heterogeneous catalyst COF of this invention... BTTC-PY It can achieve efficient conversion of benzylamine and its derivatives, benzylamine or its derivatives, and DA-structured heterogeneous catalyst COF. BTTC-PY The molar ratio is 1:0.05, which requires less catalyst and does not require high temperature for the reaction, resulting in high catalytic efficiency and reduced production costs.

[0046] Example 6: DA-structured heterogeneous catalyst COF BTTC-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 DA-structured heterogeneous catalyst COF. BTTC-PY ; Weigh out 10.7 mg of benzylamine and 15 mg of the recovered DA-structured heterogeneous catalyst COF. BTTC-PY 2 mL of acetonitrile was placed in a 10 mL round-bottom flask, and the flask was then irradiated with a 30 W white LED lamp and reacted at 25 °C for 24 h. After the reaction, the catalyst was separated from the solution by centrifugation. The centrifuged liquid was then purified by rotary evaporation using a silica gel column chromatography method with a petroleum ether:dichloromethane ratio of 12:1 V / V to obtain the product N-benzylbenzylamine. The yield of the product N-benzylbenzylamine was determined, and the catalytic cycle efficiency was as follows: Figure 4 As shown. By Figure 4 It can be seen that the DA-structured heterogeneous catalyst COF of the present invention BTTC-PY After being recycled and reused 5 times, the yield of the product was still greater than 96%, indicating that the catalyst of the present invention can be recycled and reused.

[0047] This invention recycles and reuses the DA-structured heterogeneous catalyst COF after 5 cycles. BTTC-PY Powder X-ray diffraction pattern as follows Figure 5 As shown. By Figure 5 It can be seen that the DA-structured heterogeneous catalyst COF of the present invention BTTC-PY The good preservation of the crystal form indicates that the novel covalent organic framework material prepared by this invention has very stable performance as a heterogeneous catalyst for the photocatalytic oxidation of benzylamine.

[0048] 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 D-A structured heterogeneous catalyst COF BTTC-PY characterized in that, Constructed from 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) as units, the D-A structural type heterogeneous catalyst COF BTTC-PY having the structural formula shown below: 。 2. A D-A structured heterogeneous catalyst COF according to claim 1, characterized by BTTC-PY a preparation method, characterized by, The method comprises the following steps: adding 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carboxaldehyde) into a first reaction container, then adding a mixed solvent of o-dichlorobenzene, n-butanol and acetic acid, and then placing the first reaction container in an oven for sufficient reaction; after the reaction is completed, performing vacuum filtration and washing to obtain a D-A structure type heterogeneous catalyst COF BTTC-PY .

3. The D-A structured heterogeneous catalyst COF according to claim 2. BTTC-PY The preparation method of claim 1, wherein the preparation method is characterized by, 1,3,6,8-tetra-(p-aminophenyl)-pyrene and 5,5'-(benzo[C][1,2,5]thiadiazole-4,7-diyl)bis(thiophene-2-carbaldehyde) are in a molar ratio of 1:2, and the volume ratio of o-dichlorobenzene, n-butanol, acetic acid is 1~1.3:2~2.3:0.3~0.

5.

4. The D-A structured heterogeneous catalyst COF according to claim 2 BTTC-PY The preparation method of claim 1, wherein the preparation method is characterized by, The reaction condition in the oven is: constant temperature reaction at 120~125℃ for 72h.

5. The D-A structured heterogeneous catalyst COF according to claim 2 BTTC-PY A method for producing the same, characterized by, The washing step includes: first washing with N,N-dimethylformamide for three times, and then washing with ethanol for three times.

6. The D-A structured heterogeneous catalyst COF according to claim 1 BTTC-PY Use as a photocatalyst in the catalytic oxidation of benzylamine or derivatives thereof.

7. Use according to claim 6, characterized in that, The method comprises the following steps: benzylamine or its derivative, D-A structure type heterogeneous catalyst COF BTTC-PY , acetonitrile in the second reaction vessel, then the second reaction vessel under the irradiation of 30W white LED lamp reaction; after the reaction, centrifugal, rotary evaporation, silica gel column purification, the corresponding target product is obtained; The precipitate after centrifugation is recovered to obtain a D-A structure type heterogeneous catalyst COF BTTC-PY .

8. Use according to claim 7, characterized in that, The reaction temperature is 24~26℃, and the reaction time is 23~25h.

9. Use according to claim 7, characterized in that, The molar ratio of benzylamine or its derivative and D-A structure type heterogeneous catalyst COFBTTC-PY is 1:0.

05.

10. Use according to any one of claims 6 to 9, characterized in that, The benzylamine derivatives have the structural formula of any one of , , .

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