Perylene diimide derivative-based COF material for photocatalysis of OER

Abstract

The invention provides a perylene diimide derivative based covalent organic framework material and a covalent organic framework compound which can be used for photocatalysis. The synthesis method of the compound is simple and green, raw materials are cheap and easy to obtain, the whole synthesis process is simple, and the compound is expected to be put into industrial production. In addition, the compound has excellent photocatalytic performance.

Description

Technical Field

[0001] The present invention belongs to the fields of organic molecular material synthesis and photocatalysis, and specifically relates to a preparation method and application of a perylene diimide derivative-based COF material. Background Art

[0002] With the continuous increase in global energy demand and the increasingly severe problem of climate change, it is urgent to develop new clean and alternative energy sources to reduce dependence on fossil fuels and thus achieve the goal of carbon neutrality. Solar energy is the most abundant clean and renewable energy source on Earth, and artificial photosynthesis technology driven by it is one of the most promising sustainable energy technologies. In recent years, various artificial photosynthesis systems such as photocatalytic water splitting, carbon dioxide reduction, nitrogen reduction, and biomass conversion have gradually become research hotspots. It is worth noting that in these systems, the photocatalytic oxygen evolution reaction (POER) always accompanies and restricts the generation process of clean, high-energy-density, and high-value-added fuels, plays a crucial role in energy conversion and storage systems, and has a decisive impact on the development of renewable energy technologies. However, OER involves a complex proton-coupled electron transfer process and has a high energy barrier, which is one of the main bottlenecks restricting the efficiency of artificial photosynthesis systems. Among them, perylene diimide (PDI) materials have been widely used in the field of POER due to their unique optoelectrochemical properties. Therefore, the development of efficient PDI-based catalysts is of great significance for the development of new clean and renewable fuels and the improvement of solar energy conversion efficiency. Summary of the Invention

[0003] The present invention provides a perylene diimide derivative-based covalent organic framework material for photocatalytic oxygen evolution reaction (POER), which is formed by covalently connecting a perylene diimide derivative PDID and a linker L;

[0004] The perylene diimide derivative PDID is selected from the compounds shown in formula (I):

[0005]

[0006] Wherein, R is selected from C 1-30 alkyl, C 6-20 aryl, 5-20 membered heteroaryl;

[0007] The linker L is selected from the compounds shown in formula (II) (any one selected from L1-L9):

[0008]

[0009] Wherein, R a , R b are the same or different and are independently selected from H, halogen (such as F, Cl, Br), OH, NO2, CN, C 1-10 alkyl;

[0010] A1, A2, A3, A4, A5, A6, A7, A8 are the same or different and are independently selected from N, CH;

[0011] B1, B2 are the same or different and are independently selected from O, S, Se;

[0012] C1, C2, C3, C4 are the same or different and are independently selected from sulfonyl group (SO2, O=S=O), sulfinyl group (S=O), C=O;

[0013] The dotted lines in Formula (I) and Formula (II) represent the connection points of the perylene diimide derivative PDID, the linker L and the covalent bond.

[0014] According to an embodiment of the present invention, the covalent bond is selected from any one or more of the following: -C=N-, -C=C-.

[0015] According to an embodiment of the present invention, the perylene diimide derivative PDID is selected from the compounds represented by the following Formula (I-1) or Formula (I-2):

[0016]

[0017] wherein, R1, R2, R3, R4 are the same or different and are independently selected from C1-C 20 alkyl, preferably C1-C 16 alkyl, C1-C 10 alkyl, such as C9 alkyl, C8 alkyl, C7 alkyl, C6 alkyl, C5 alkyl, C4 alkyl, C3 alkyl, C2 alkyl;

[0018] R5, R6 are the same or different and are independently selected from C1-C 20 alkyl, C 6-20 aryl, 5-20 membered heteroaryl, preferably C1-C 16 alkyl, C 6-16 aryl, 5-16 membered heteroaryl, more preferably C1-C 10 alkyl, C 6-14 aryl, 5-14 membered heteroaryl; such as phenyl, naphthyl, anthryl, biphenyl, C9 alkyl, C8 alkyl, C7 alkyl, C6 alkyl, C5 alkyl, C4 alkyl, C3 alkyl, C2 alkyl.

[0019] According to an embodiment of the present invention, R1, R2, R3, R4 are the same. According to an embodiment of the present invention, R5, R6 are the same.

[0020] According to an embodiment of the present invention, the perylene diimide derivative PDID is selected from the following compounds:

[0021]

[0022] According to a specific embodiment of the present invention, the linker L is selected from the following compounds:

[0023]

[0024] According to an embodiment of the present invention, when the linking mode is -C=N-, the substoichiometric framework compound of the perylene diimide derivative includes the units shown in Formula (III) and Formula (IV):

[0025]

[0026] L represents the linker L and has the above definition.

[0027] According to an embodiment of the present invention, when the linking mode is -C=C-, the substoichiometric framework compound of the perylene diimide derivative includes the backbone units shown in Formula (V) and Formula (VI):

[0028]

[0029] L represents the linker L and has the above definition.

[0030] According to an embodiment of the present invention, the perylene diimide derivative-based covalent organic framework material is selected from any one of the following:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041] The present invention provides a method for preparing the above perylene diimide derivative-based covalent organic framework material, and the preparation method includes the following steps:

[0042] React the perylene diimide compound represented by formula (I0-1) with the linker compound represented by formula (L0-1) to obtain the perylene diimide derivative-based covalent organic framework material;

[0043]

[0044] wherein, R and L have the above definitions;

[0045] When R s is an aldehyde group, R t is an amino group or a cyano group; when R s is an amino group or a cyano group, R t is an aldehyde group.

[0046] According to an embodiment of the present invention, the molar ratio of the perylene diimide compound represented by formula (I0-1) to the linker compound represented by formula (L0-1) is 1:0.2 to 1:5, preferably 1:1 to 1:3, such as 1:1, 1:2, 1:3.

[0047] According to an embodiment of the present invention, the reaction is carried out in an organic solvent; preferably, the organic solvent is selected from one, two or more of o-dichlorobenzene, n-butanol, mesitylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile. According to an embodiment of the present invention, the organic solvent is a single solvent or a combined solvent; preferably, the combined solvent is selected from a combination of a high-polarity solvent and a low-polarity solvent among the above solvents. Preferred combined solvents are: mesitylene / dioxane, o-dichlorobenzene / n-butanol, dimethyl sulfoxide / o-dichlorobenzene, N-methylpyrrolidone / mesitylene; preferably, in the combined solvent, the volume ratio of the two solvents is optimally 1:1.

[0048] According to an embodiment of the present invention, the reaction is carried out in the presence of a catalyst; preferably, the selected catalyst includes but is not limited to at least one of acetic acid, p-toluenesulfonic acid (PTSA), scandium trifluoromethanesulfonate, pyrrolidine, sodium hydroxide. Preferably, the concentration of acetic acid is 3M - 12M, the concentration of p-toluenesulfonic acid is 5mM - 30mM, for example, acetic acid is selected from 6M - 9M, p-toluenesulfonic acid is selected from 10mM - 30mM, and sodium hydroxide is selected from 2M - 6M; examples: acetic acid 6M, 9M, sodium hydroxide 2M, 4M.

[0049] According to an embodiment of the present invention, the total volume ratio of the catalyst to the solvent is selected from 1:2 to 1:10. Preferably, when the catalyst is acetic acid, the total volume of the solvent is 2 mL and the amount of acetic acid used is 0.2 mL; when the catalyst is PTSA, the total volume of the solvent is 2 mL and the amount of sodium hydroxide solution used is 0.1 mL.

[0050] According to an embodiment of the present invention, the reaction is a solvothermal synthesis method, and the specific reaction conditions are: 80°C to 180°C, and the reaction time is 12 to 72 hours. Preferably, the reaction temperature is: 100°C, 120°C, 150°C, 180°C; and the reaction time is: 24 hours, 48 hours, 72 hours.

[0051] The present invention also provides the application of the above-mentioned perylene diimide derivative-based covalent organic framework material in photocatalysis.

[0052] According to an embodiment of the present invention, the application is photocatalytic water splitting to produce oxygen.

[0053] Beneficial effects

[0054] The present invention provides a perylene diimide derivative-based covalent organic framework material covalent organic framework compound that can be used in photocatalysis. The synthesis method of the compound is simple and green, the raw materials are cheap and easily available, the overall synthesis process is simple, and it is expected to be put into industrial production. Moreover, the compound has excellent photocatalytic performance. Description of the drawings

[0055] Figure 1 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-1.

[0056] Figure 2 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-2.

[0057] Figure 3 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-3.

[0058] Figure 4 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-4.

[0059] Figure 5 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-5.

[0060] Figure 6 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-6.

[0061] Figure 7 It is the X-ray diffraction pattern (XRD) of PDID-1-COF-7.

[0062] Figure 8 It is the X-ray diffraction pattern (XRD) of PDID-2-COF-1.

[0063] Figure 9 It is the X-ray diffraction pattern (XRD) of PDID-2-COF-2.

[0064] Figure 10 X-ray diffraction pattern (XRD) of PDID-2-COF-3.

[0065] Figure 11 XRD and crystal structure simulation diagram of PDID-1-COF-4 in Example 4.

[0066] Figure 12 Infrared (FTIR) comparison diagram of PDID-1-COF-4 and reaction raw materials in Example 4.

[0067] Figure 13 Diagram of the amount of oxygen generated at different time points within 3 h of photocatalysis by COFs in Examples 1, 2, 4, 8, 9, and 10.

[0068] Figure 14 Diagram of the average oxygen release rate of COFs photocatalyzed for 3 h in Examples 1, 2, 4, 8, 9, and 10.

[0069] Term Definitions and Explanations

[0070] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be combined and combined with each other arbitrarily. The group definitions and compound structures after such combination and combination should be understood to be within the scope recorded in the specification and / or claims of this application.

[0071] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-20" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-20", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0072] The term "halogen" means fluorine, chlorine, bromine, or iodine.

[0073] The term "C 1-30 alkyl" and "C 1-20 alkyl" should be understood to represent straight-chain or branched-chain saturated monovalent hydrocarbon groups having 1 to 30 and 1 to 20 carbon atoms, respectively. For example, "C 1-6 alkyl" represents straight-chain and branched-chain alkyls having 1, 2, 3, 4, 5, or 6 carbon atoms and their isomers. "C 10-18 alkyl" represents straight-chain and branched-chain alkyls having 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms and their isomers.

[0074] The term "5- to 20-membered heterocyclic group" refers to a group of a 5- to 20-membered non-aromatic ring system having 1 to 6 ring heteroatoms (where each heteroatom is independently selected from nitrogen, oxygen, sulfur, boron, phosphorus, and silicon). In a heterocyclic group containing one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, provided that the valence is permitted. The heterocyclic group can be saturated or can be partially unsaturated. Each instance of the heterocyclic group can be optionally substituted or unsubstituted, and when substituted, the substituent can be at any available point of attachment.

[0075] The "C 6-20 aryl" of the present invention refers to an aromatic system containing 6 to 20 carbon atoms that can include a monocyclic or fused polycyclic ring, preferably an aromatic system containing a monocyclic or fused bicyclic ring, preferably containing 6 to 12 carbon atoms. Suitable aryl groups include, but are not limited to, phenyl, naphthyl, anthryl, tetrahydronaphthyl, fluorenyl, indanyl. The aryl group can be optionally substituted or unsubstituted, and when substituted, the substituent can be at any available point of attachment. Detailed Description of the Invention

[0076] The following will clearly describe the implementation solutions in the embodiments of the present invention in combination with some preferred embodiments of the present invention. Of course, the described examples are only a part of the present invention, not all of it. All other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention.

[0077] Example 1 Synthesis of PDID-1-COF-1

[0078] 27.23 mg (0.1 mmol) of dibenzo[b,d]thiophene-3,7-dicarboxaldehyde 5,5-dioxide and 44.75 mg (0.05 mmol) of N,N'-bis(pentaalkyl)-2,5,8,11-tetrakis(4-aminophenyl)perylene-3,4,9,10-dicarboximide (PDID-1) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.3 mL of 6 M aqueous acetic acid solution was added, and it was quickly flash frozen at 77 K. After removing water and oxygen through 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-1-COF-1. The synthesis of the raw material PDID-1 refers to the reference (Angew. Chem. Int. Ed. 2023, e202216729).

[0079] The reaction formula is as follows:

[0080]

[0081] The X-ray diffraction pattern (XRD) of PDID-1-COF-1 is as Figure 1 shown below.

[0082] Example 2 Synthesis of PDID-1-COF-2

[0083] 41.00 mg (0.1 mmol) of benzobis(benzothiophene sulfone)-3,7-dicarbaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-aminophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-1) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.3 mL of 6 M aqueous acetic acid solution was added, and the mixture was quickly flash frozen at 77 K. After removing water and oxygen by 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-1-COF-2.

[0084] The reaction formula is as follows:

[0085]

[0086] The X-ray diffraction pattern (XRD) of PDID-1-COF-2 is as Figure 2 shown below.

[0087] Example 3 Synthesis of PDID-1-COF-3

[0088] 28.83 mg (0.1 mmol) of 4,4'-(4,6-pyrimidinediyl)dibenzaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-aminophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-1) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.3 mL of 6 M aqueous acetic acid solution was added, and the mixture was quickly flash frozen at 77 K. After removing water and oxygen by 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-1-COF-3.

[0089] The reaction formula is as follows:

[0090]

[0091] The X-ray diffraction pattern (XRD) of PDID-1-COF-3 is as Figure 3 shown below.

[0092] Example 4 Synthesis of PDID-1-COF-4

[0093] Add 16.61 mg (0.1 mmol) of 2,5-dihydroxyterephthalaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-aminophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-1) into a 10 mL Pyrex tube with a vacuum side arm. Add 1 mL of o-dichlorobenzene and 1 mL of n-butanol thereto, sonicate for 10 min, add 0.3 mL of 6 M aqueous acetic acid solution, quickly flash-freeze at 77 K, and after removing water and oxygen by 3 freeze-degas-N2 replacement cycles, seal under vacuum. Heat the Pyrex tube at 120 °C for 3 days to obtain PDID-1-COF-4.

[0094] The reaction formula is as follows:

[0095]

[0096] The X-ray diffraction pattern (XRD) of PDID-1-COF-4 is as Figure 4 shown. Figure 11 is the XRD and crystal structure simulation diagram of PDID-1-COF-4, Figure 12 is the infrared (FTIR) comparison diagram of PDID-1-COF-4 and the reaction raw materials.

[0097] Example 5 Synthesis of PDID-1-COF-5

[0098] Add 21.22 mg (0.1 mmol) of 2,2'-bipyridine-5,5'-dicarboxaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-aminophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-1) into a 10 mL Pyrex tube with a vacuum side arm. Add 1 mL of o-dichlorobenzene and 1 mL of n-butanol thereto, sonicate for 10 min, add 0.3 mL of 6 M aqueous acetic acid solution, quickly flash-freeze at 77 K, and after removing water and oxygen by 3 freeze-degas-N2 replacement cycles, seal under vacuum. Heat the Pyrex tube at 120 °C for 3 days to obtain PDID-1-COF-5.

[0099] The reaction formula is as follows:

[0100]

[0101] The X-ray diffraction pattern (XRD) of PDID-1-COF-5 is as Figure 5 shown.

[0102] Example 6 Synthesis of PDID-1-COF-6

[0103] Add 22.23 mg (0.1 mmol) of [2,2']-bithiophene-5,5'-dicarboxaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetra(4-aminophenyl)perylene-3,4,9,10-di(dicarboximide) (PDID-1) into a 10 mL Pyrex tube with a vacuum side arm. Add 1 mL of o-dichlorobenzene and 1 mL of n-butanol thereto, sonicate for 10 min, add 0.3 mL of 6 M aqueous acetic acid solution, quickly flash freeze at 77 K, and after removing water and oxygen through 3 freeze-degas-N2 replacement cycles, seal under vacuum. Heat the Pyrex tube at 120 °C for 3 days to obtain PDID-1-COF-6.

[0104] The reaction formula is as follows:

[0105]

[0106] The X-ray diffraction pattern (XRD) of PDID-1-COF-6 is as Figure 6 shown.

[0107] Example 7 Synthesis of PDID-1-COF-7

[0108] Add 24.83 mg (0.1 mmol) of benzo[1,2-d:4,5-d']bis(thiazole)-2,6-dicarboxaldehyde and 44.75 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetra(4-aminophenyl)perylene-3,4,9,10-di(dicarboximide) (PDID-1) into a 10 mL Pyrex tube with a vacuum side arm. Add 1 mL of o-dichlorobenzene and 1 mL of n-butanol thereto, sonicate for 10 min, add 0.3 mL of 6 M aqueous acetic acid solution, quickly flash freeze at 77 K, and after removing water and oxygen through 3 freeze-degas-N2 replacement cycles, seal under vacuum. Heat the Pyrex tube at 120 °C for 3 days to obtain PDID-1-COF-7.

[0109] The reaction formula is as follows:

[0110]

[0111] The X-ray diffraction pattern (XRD) of PDID-1-COF-7 is as Figure 7 shown.

[0112] Example 8 Synthesis of PDID-2-COF-1

[0113] 27.23 mg (0.1 mmol) of dibenzo[b,d]thiophene-3,7-dicarbaldehyde 5,5-dioxide and 49.56 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-cyanophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-2) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.1 mL of 4 M sodium hydroxide solution was added, and it was quickly flash-frozen at 77 K. After removing water and oxygen by 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-2-COF-1.

[0114] The reaction formula is as follows:

[0115]

[0116] The X-ray diffraction pattern (XRD) of PDID-2-COF-1 is as Figure 8 shown.

[0117] Among them, the perylene diimide derivative monomer PDID-2 was synthesized with some modifications based on the references (Angew. Chem. Int. Ed. 2023, e202216729, Org. Lett. 2011, 13, 3012).

[0118] Example 9 Synthesis of PDID-2-COF-2:

[0119] 41.00 mg (0.1 mmol) of benzobis(benzothiophene sulfone)-3,7-dicarbaldehyde and 49.56 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-cyanophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-2) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.1 mL of 4 M sodium hydroxide solution was added, and it was quickly flash-frozen at 77 K. After removing water and oxygen by 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-2-COF-2.

[0120] The reaction formula is as follows:

[0121]

[0122] The X-ray diffraction pattern (XRD) of PDID-2-COF-2 is as Figure 9 shown.

[0123] Synthesis of Example 10 PDID-2-COF-3

[0124] 16.61 mg (0.1 mmol) of 2,5-dihydroxyterephthalaldehyde and 49.56 mg (0.05 mmol) of N,N'-bis(pentyl)-2,5,8,11-tetrakis(4-cyanophenyl)perylene-3,4,9,10-bis(dicarboximide) (PDID-2) were added to a 10 mL Pyrex tube with a vacuum side arm. 1 mL of o-dichlorobenzene and 1 mL of n-butanol were added thereto, and the mixture was sonicated for 10 min. 0.1 mL of 4 M sodium hydroxide solution was added, and it was quickly flash-frozen at 77 K. After removing water and oxygen through 3 freeze-degas-N2 replacement cycles, it was sealed under vacuum. The Pyrex tube was heated at 120 °C for 3 days to obtain PDID-2-COF-3.

[0125] The reaction formula is as follows:

[0126]

[0127] The X-ray diffraction pattern (XRD) of PDID-2-COF-3 is as Figure 10 shown.

[0128] Example 11 Test Example

[0129] 5 mg of COFs powder from Example 1 (PDID-1-COF-1), Example 2 (PDID-1-COF-2), Example 3 (PDID-1-COF-3), Example 4 (PDID-1-COF-4), Example 5 (PDID-1-COF-5), Example 6 (PDID-1-COF-6), Example 7 (PDID-1-COF-7), Example 8 (PDID-2-COF-1), Example 9 (PDID-2-COF-2), and Example 10 (PDID-2-COF-3) were respectively sonicated in 100 mL of deionized water for 30 min to mix evenly. 2.38 g of Na2S2O8 powder was added as a sacrificial agent, and the photocatalytic OER performance was tested using a Perfect Light (Labsolar 6A) online photocatalytic test system. A 300 W xenon lamp was used as the light source, and the generated gas was analyzed and detected by a GC9790 gas chromatograph.

[0130] Figures 13 - 14It is a comparison chart of the OER performance of COFs photocatalysis for 3 h in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, showing the oxygen production amounts at different time points and the average oxygen release rate for 3 h. The results show that due to the presence of perylene nuclei in PDID-based COFs, all PDID-based COFs possess excellent OER performance. Different PDID-based COFs have different OER performances due to the differences in the electron-donating / withdrawing abilities of their functional groups and the conjugation degrees of their linking bonds.

[0131] The above has given an exemplary description of the implementation schemes of the present invention. It should be understood that the protection scope of the present disclosure is not limited to the above implementation manners. The above implementation manners are only partial excerpts. Any modifications, equivalent replacements, improvements, etc. made by those of ordinary skill in the art within the spirit and principle of the disclosure should be included within the protection scope of the claims of this application.

Claims

1. A perylene diimide derivative-based covalent organic framework material for photocatalytic oxygen evolution reaction, which is formed by covalently bonding a perylene diimide derivative PDID and a linker L; The perylene diimide derivative PDID is selected from the compounds shown in formula (I): Among them, R is selected from C 1-30 alkyl, C 6-20 aryl, 5- to 20-membered heteroaryl; The linker L is selected from the compounds shown in formula (II): Among them, R a , R b are the same or different and are each independently selected from H, halogen, OH, NO2, CN, C 1-10 alkyl; A1, A2, A3, A4, A5, A6, A7, A8 are the same or different and are independently selected from N, CH; B1, B2 are the same or different and are independently selected from O, S, Se; C1, C2, C3, C4 are the same or different and are independently selected from sulfone group, sulfoxide group, C=O; The dotted lines in formula (I) and formula (II) represent the connection points of the perylene diimide derivative PDID, the linker L and the covalent bond.

2. The covalent organic framework material according to claim 1, characterized in that The covalent bond is selected from any one or more of the following: -C=N-, -C=C-.

3. The covalent organic framework material according to claim 1 or 2, characterized in that, The perylene diimide derivative PDID is selected from the compounds shown in the following formula (I-1) or formula (I-2): Among them, R1, R2, R3, and R4 are the same or different and are independently selected from C1-C 20 alkyl; R5 and R6 are the same or different and are each independently selected from C1-C 20 alkyl, C 6-20 aryl, 5-20 membered heteroaryl; Preferably, the perylene diimide derivative PDID is selected from the following compounds:

4. The covalent organic framework material according to any one of claims 1-3, characterized in that, The linker L is selected from the following compounds:

5. The covalent organic framework material according to any one of claims 1-4, characterized in that, When the connection mode is -C=N-, the sub-stoichiometric framework compound of the perylene imide derivative includes the units shown in formula (III) and formula (IV): L represents the linker L and has the definition described in any one of claims 1-4; Preferably, when the connection mode is -C=C-, the sub-stoichiometric framework compound of the perylene imide derivative includes the skeleton units shown in formula (V) and formula (VI): L represents the linker L and has the definition described in any one of claims 1-4.

6. The covalent organic framework material according to any one of claims 1-5, characterized in that, The perylene diimide derivative-based covalent organic framework material is selected from any one of the following:

7. A preparation method of the covalent organic framework material according to any one of claims 1-6, the preparation method comprising the following steps: Reacting the perylene diimide compound shown in formula (I0-1) with the linker compound shown in formula (L0-1) to obtain the perylene diimide derivative-based covalent organic framework material; Among them, R, L have the definition described in any one of claims 1-6; When R s is an aldehyde group, R t is an amino group or a cyano group; when R s is an amino group or a cyano group, R t is an aldehyde group.

8. The preparation method according to claim 7, characterized in that, The molar ratio of the perylene diimide compound shown in formula (I0-1) to the linker compound shown in formula (L0-1) is 1:0.2 to 1:5; Preferably, the reaction is carried out in an organic solvent; preferably, the organic solvent is selected from one, two or more of ortho-dichlorobenzene, n-butanol, mesitylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile; Preferably, the reaction is carried out in the presence of a catalyst; preferably, the selected catalyst includes but is not limited to at least one of acetic acid, p-toluenesulfonic acid (PTSA), scandium trifluoromethanesulfonate, pyrrolidine, sodium hydroxide; Preferably, the total volume ratio of the catalyst to the solvent is selected from 1:2 to 1:10; Preferably, the reaction is a solvothermal synthesis method; preferably, the reaction conditions are: 80°C to 180°C, and the reaction time is 12 to 72 h.

9. Application of the covalent organic framework material according to any one of claims 1-6 in photocatalysis.

10. The application according to claim 9, wherein The application is photocatalytic water splitting to produce oxygen.

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