二维共价有机框架作为光催化剂在有机合成中的研究进展

doi:10.1016/j.actphy.2025.100086

物理化学学报 >> 2025, Vol. 41 >> Issue (8): 100086.doi: 10.1016/j.actphy.2025.100086

二维共价有机框架作为光催化剂在有机合成中的研究进展

袁乐汪¹^,†, 彭垚垚¹^,†, 管宗杰¹, 方煜¹^,²^,*()

¹ 湖南大学化学化工学院, 湖南长沙 410082
² 中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福建福州 350002

收稿日期:2025-02-11 修回日期:2025-03-18 录用日期:2025-03-28 发布日期:2025-06-07
通讯作者: Email: yu.fang@hnu.edu.cn (方煜)
作者简介:
^† These authors contributed equally to this work.
基金资助:
国家自然科学基金(22371067)

Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis

Lewang Yuan¹, Yaoyao Peng¹, Zong-Jie Guan¹, Yu Fang¹^,²^,*()

¹ College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan Province, China
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian Province, China

Received:2025-02-11 Revised:2025-03-18 Accepted:2025-03-28 Published:2025-06-07
Contact: Email: yu.fang@hnu.edu.cn (Yu Fang)
Supported by:
National Natural Science Foundation of China(22371067)

摘要/Abstract

摘要：

二维共价有机框架(2D COFs)具有拓扑可调性、大比表面积、易于功能化以及出色的稳定性等特性，这些特性使得它们在多相光催化领域中的应用日益广泛。本文首先概述了2D COFs的合成方法，包括溶剂热、离子热、机械化学、微波辅助、声化学和界面合成方法。它简要介绍了影响光催化性能的各种因素，包括结晶度和稳定性、能带结构、电荷转移能力、孔径和比表面积以及光源。随后，讨论转向总结和分析2D COFs作为光催化剂在有机小分子转化反应(如光催化氧化、还原和偶联反应)中的进展。最后，对2D COFs在光催化有机转化领域面临的机遇和挑战进行了总结和展望。

关键词: 二维, 共价有机框架, 光催化, 氧化反应, 还原反应, 偶联反应

Abstract:

Two-dimensional covalent organic frameworks (2D COFs) exhibit distinctive characteristics, including tunable topology, an extensive specific surface area, susceptibility to functionalization, and robust stability, making them frequently utilizedin multiphase photocatalytic applications. This article begins with an overview of the synthesis methods for 2D COFs, covering solvothermal, ionothermal, mechanochemical, microwave-assisted, sonochemical, and interfacial synthesis techniques. It provides a concise introduction to various factors influencing photocatalytic performance, such as crystallinity and stability, band structure, charge transfer capability, pore size and specific surface area, and the nature of the light source. Subsequently, the discussion shifts to summarizing and analyzing advancements in the use of 2D COFs as photocatalysts for organic small molecule conversion reactions, particularly in photocatalytic oxidation, reduction, and coupling reactions. Finally, summary and outlook are presented regarding the opportunities and challenges that 2D COFs face in photocatalytic organic transformations.

Key words: Two-dimension, Covalent organic framework, Photocatalysis, Oxidation reaction, Reduction reaction, Cross-coupling reaction

袁乐汪, 彭垚垚, 管宗杰, 方煜. 二维共价有机框架作为光催化剂在有机合成中的研究进展[J]. 物理化学学报, 2025, 41(8), 100086. doi: 10.1016/j.actphy.2025.100086

Lewang Yuan, Yaoyao Peng, Zong-Jie Guan, Yu Fang. Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis[J]. Acta Phys. -Chim. Sin. 2025, 41(8), 100086. doi: 10.1016/j.actphy.2025.100086

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100086

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I8/100086

图/表 21

表1

Catalysts		Synthesis method	Reaction		Ref.
Original	Renamed	Synthesis method	Reaction type	Conversion type	Ref.
COF-1	1	solvothermal	–		[25]
COF-5	2	solvothermal	–		[25]
TAPB-TaBr₂	3	solvothermal	–		[43]
CTF-1	4	ionic thermal	–		[44]
CTF-2	5	ionic thermal	–		[45]
TzPm-COF	6	microwave-assisted	Cross-coupling	C–N Cross-coupling	[46]
CONs	7	sonochemical	–		[47]
TPDA-DHBD	8	interface synthesis	–		[48]
ivCOF-O	9	solvothermal	–		[49]
vCOF-N	10	modification	–		[49]
TBC-COF	11	solvothermal	H₂O₂ Production		[50]
TBD-COF	12	solvothermal	H₂O₂ Production		[50]
BTT-BPy-PCOF	13	solvothermal/protonation	Hydrogen Evolution		[51]
Cu₃-TPA-COF	14	solvothermal	CO₂ Reduction		[52]
Cu₃-TAPB-COF	15
Cu₃-TAPT-COF	16
PTH-S-COF	17	solvothermal	H₂O₂ Production		[53]
PTH-SO-COF	18
PTH-SO₂-COF	19
LZU-190	20	solvothermal	Oxidation	Aryl Boronic Acid Oxidation	[54]
Cy-N₃-COF	21	photocatalytic			[55]
TAD-COF	22	solvothermal			[56]
PyPor-COF	23	solvothermal		Oxidation of Sulfides	[57]
COF-366 (Ni)	24	solvothermal			[58]
TpBpy-COF	25	solvothermal			[59]
TPBD-H-COF	26	solvothermal		Oxidative Coupling of Amines	[60]
TPBD-F-COF	27
TPBD-NO₂-COF	28
TPBD-CN-COF	29
TpDAF-COF	30	solvothermal			[61]
TpMFC-COF	31
TpFFC-COF	32
TpDPP-Py COFs	33	solvothermal			[62]
DPP-Py COFs	34	solvothermal			[62]
COF-JLU22	35	solvothermal	Reduction	Dehalogenation Reduction	[63]
D_TF-A_NDI-COF	36	solvothermal			[64]
COF_D5	37	solvothermal			[65]
COF_D19	38
Am-COF_D5	39	modification (NHC)
Am-COF_D19	40
COF-V_x	41	solvothermal		Nitro Reduction	[66]
COF-S_x	42	modification
Pt@COF-S_x	Pt@42
TAPP-COF	43	solvothermal			[67]
Ag₁₀@TAPP-COF	Ag@43	modification
Tsc-COF	44	solvothermal	Cross-coupling	C–C Cross-coupling	[68]
Tch-COF	45
TU-COF	46
Pd@TU-COF	Pd@46	modification	Cross-coupling	C–C Cross-coupling	[68]
AntCOF	47	solvothermal			[69]
Pd/AntCOF	Pd/47	modification			[69]
Tp-Bpy	48	solvothermal		C–N Cross-coupling	[70]
Ir@Tp-Bpy	Ir@48	modification
Ni-Ir@Tp-Bpy	Ni-Ir@48	modification
TTT-DHTD-COF	49	solvothermal			[71]
SCN	50	solvothermal		C–O Cross-coupling	[72]
NiSCN	51	modification			[72]
BPh-COF	52	solvothermal			[73]
AC-COF	53	solvothermal			[73]
Ace-COF	54	solvothermal		C–S Cross-coupling	[74]
Ace-COF-Ni	54-Ni	modification			[74]
Bpy-sp²c-COF	55	solvothermal			[75]
Ni@Bpy-sp²c-COF	Ni@55	modification			[75]
NQ-COF_E5	56	solvothermal	C-H Functionalization		[76]
NQ-COF_E5-O	57	modification (m-CPBA)	C-H Functionalization		[76]
TpAzo	58	solvothermal	C-H Borylation		[77]
TpDpp	59
TpTab	60
COF-316	61	solvothermal	C-H Activation		[78]
COF-316-COOH	62	modification
Rh-COF-316	Rh-62	modification
COF-318	63	solvothermal
COF-318-COOH	64	modification
Rh-COF-318	Rh-64	modification

表1

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

图13

图14

图15

图16

图17

图18

图19

图20

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二维共价有机框架作为光催化剂在有机合成中的研究进展

Insights into the development of 2D covalent organic frameworks as photocatalysts in organic synthesis

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