面向实用光催化的共价有机框架多尺度工程:从异质结结构设计到膜制备

doi:10.1016/S1872-2067(26)65055-3

催化学报 ›› 2026, Vol. 89: 142-176.DOI: 10.1016/S1872-2067(26)65055-3

面向实用光催化的共价有机框架多尺度工程:从异质结结构设计到膜制备

郭姿显^a, 何有杭^a, 于明飞^a, 李留义^a^,^*(), 毕进红^b^,^*(), 于岩^a, 吴棱^c^,^*()

^a福州大学材料科学与工程学院,生态材料先进技术重点实验室,福建福州 350108
^b福州大学环境与安全工程学院,福建福州 350108
^c福州大学化学学院,能源与环境光催化国家重点实验室,福建福州 350116

收稿日期:2026-02-01 接受日期:2026-02-27 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: lyli@fzu.edu.cn (李留义),
bijinhong@fzu.edu.cn (毕进红),
wuling@fzu.edu.cn (吴棱).
基金资助:
国家重点研发计划(2020YFA0710303);国家自然科学基金(52172188);福建省自然科学基金(2025J01471)

Multiscale engineering of COFs toward practical photocatalysis: From heterojunction design to membrane fabrication

Zixian Guo^a, Youhang He^a, Mingfei Yu^a, Liuyi Li^a^,^*(), Jinhong Bi^b^,^*(), Yan Yu^a, Ling Wu^c^,^*()

^aKey Laboratory of Eco-materials Advanced Technology, College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
^bCollege of Environment and Safety Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
^cState Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2026-02-01 Accepted:2026-02-27 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:lyli@fzu.edu.cn(L. Li),bijinhong@fzu.edu.cn(J. Bi),wuling@fzu.edu.cn(L. Wu).
About author:Liuyi Li (College of Materials Science and Engineering, Fuzhou University) received his M.S. degree in Organic Chemistry from Huazhong University of Science and Technology in 2007 and his Ph.D. degree in Environmental Chemistry from Fuzhou University in 2017. He has been working at Fuzhou University since 2017, and was promoted to a full professor in 2021. His research interests currently focus on the rational design of covalent organic frameworks for photocatalysis, with emphasis on CO₂ reduction and water splitting
Jinhong Bi (College of Environment and Safety Engineering, Fuzhou University) received her Ph.D. degree from Fuzhou University in 2009. From 2012 to 2017, she served as an associate professor at Fuzhou University, and was exceptionally promoted to a full professorship in 2017. Her research interests currently focus on pollution control technology and resource utilization, with emphasis on photocatalytic CO₂ reduction, removal of emerging contaminants, and water disinfection.
Ling Wu (College of Chemistry, Fuzhou University) received his M.Sc. degree from Dalian University of Technology in 1985 and his Ph.D. degree from The Chinese University of Hong Kong in 2004. From 1987 to 2001, he held the position of Deputy Director of the Office of Science and Technology and served as an Associate Researcher at the Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. In 2004, he joined the faculty of Fuzhou University. Currently, he is a professor at the State Key Laboratory of Photocatalysis on Energy and Environment. His research interests focus on heterogeneous photocatalysis, with emphasis on the controllable preparation of 2D transition metal oxides, activation of organic molecules on ultrathin nanosheets, and MOFs-based biomimetic nitrogen fixation.
Supported by:
National Key Research and Development Program of China(2020YFA0710303);National Natural Science Foundation of China(52172188);Fujian Provincial Natural Science Foundation(2025J01471)

摘要/Abstract

摘要：

面对日益严峻的能源危机与环境挑战, 太阳能驱动的光催化转化已成为实现可持续发展的关键技术路径之一. 共价有机框架材料凭借其结构可调性、高结晶度及有序孔道等优势, 为突破传统无机半导体材料在分子水平上难以精准调控的瓶颈提供了全新平台. 然而, 当前基于COF粉末的光催化体系仍受制于光生载流子复合率高、光响应范围窄等局限, 同时, 在宏观应用中面临催化剂回收困难、易团聚失活、难以集成于连续流反应系统等工程难题, 严重阻碍了其从基础研究向实际应用的转化. 因此, 开发兼具高效电荷分离能力与宏观可操作性的新型COF光催化体系, 具有重要的科学意义和应用价值.

本文系统阐述了一种从分子到宏观尺度的跨尺度工程策略, 旨在通过协同纳米尺度的异质结设计与宏观尺度的膜结构工程, 以破解上述瓶颈. 首先, 从分子工程视角出发, 系统梳理了COF基异质结的设计思路与优势, 总结了将COF与无机半导体、金属及量子点等材料复合的多样化策略, 重点分析了S型异质结在促进空间电荷分离、保持强氧化还原能力方面的独特机制, 并归纳了决定其光催化性能提升的构效关系, 揭示了界面相互作用对载流子迁移路径的关键影响. 其次, 从宏观结构工程层面, 详细评述了COF膜的制备技术(如界面聚合法、原位生长法、层层堆叠法), 阐明了通过调控膜厚、孔道取向、孔隙率及表面润湿性等参数优化光吸收、反应物富集与传质效率的机制, 进而构建高效的宏观反应界面. 在此基础上, 前瞻性地提出并重点阐述了COF异质结膜这一集成平台: 在纳米尺度上, 利用界面内建电场显著加速载流子动力学, 有效抑制体相复合; 在宏观尺度上, 借助膜结构实现催化剂固定化与连续流操作, 大幅提升催化剂的运行稳定性和可回收性. 二者的协同作用不仅实现了光生电荷的空间分离, 同时优化了反应物在孔道内的扩散行为, 展现出显著的增效机制. 得益于异质结界面的高效电荷分离与膜结构提供的快速传质通道, 所构建的COF异质结膜在光催化产氢、污染物降解等应用中表现出优异的性能提升.

综上, 本文系统梳理了COF光催化剂从分子设计到宏观组装的跨尺度研究, 揭示了异质结与膜结构的协同集成是突破粉末体系应用瓶颈的关键路径. 未来研究应聚焦于规模化制备技术、应用导向的材料设计, 以及系统集成与可持续性评估. 本文旨在为开发兼具高本征活性与工程适用性的新型COF光催化体系提供理论借鉴, 推动光催化技术的实用化进程.

关键词: 共价有机框架, S-型异质结, 膜, 光催化, 工程

Abstract:

Transitioning covalent organic frameworks (COFs) from laboratory-scale photocatalysts to practical technologies requires overcoming two fundamental bottlenecks: rapid charge recombination at the microscopic level and mass transfer limitations coupled with the engineering challenges of particulate suspensions at the macroscopic level. This review presents a multiscale engineering strategy to bridge this gap, progressing from heterojunction design to membrane fabrication. We first provide a systematic assessment of COF-based heterostructures, incorporating metals, metal oxides, and inorganic semiconductors, to elucidate the structure-activity relationships governing excitonic dynamics. Special emphasis is placed on S-scheme COF-based heterojunctions, highlighting their superior capability in facilitating interfacial charge transfer while preserving high redox potentials. Subsequently, the focus shifts to the engineering of COF membranes via techniques such as interfacial polymerization and in-situ growth, emphasizing their structural merits in macroscopic processability. Critically, we propose the integration of heterojunction concepts into membrane architectures as a pivotal strategy to resolve the inherent trade-offs between the aggregation of powder catalysts and the limited semiconductor properties of traditional polymer membranes. By analyzing recent advances in heterostructured COF membranes, we highlight how this synergistic approach simultaneously enhances charge separation efficiency, substrate flux, and operational stability. We further discuss the application of these heterojunction and membrane systems in key photocatalytic processes, including H₂ production, CO₂ reduction, H₂O₂ production, and pollutant degradation. The review concludes by outlining a roadmap for overcoming scalability hurdles, offering a blueprint for the development of efficient, robust, and industrially relevant COF photocatalytic systems.

Key words: Covalent organic frameworks, S-Scheme Heterojunction, Membrane, Photocatalysis, Engineering

郭姿显, 何有杭, 于明飞, 李留义, 毕进红, 于岩, 吴棱. 面向实用光催化的共价有机框架多尺度工程:从异质结结构设计到膜制备[J]. 催化学报, 2026, 89: 142-176.

Zixian Guo, Youhang He, Mingfei Yu, Liuyi Li, Jinhong Bi, Yan Yu, Ling Wu. Multiscale engineering of COFs toward practical photocatalysis: From heterojunction design to membrane fabrication[J]. Chinese Journal of Catalysis, 2026, 89: 142-176.

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图/表 30

Fig. 1. Schematic representation of COF-based heterojunction membranes for photocatalysis.

Fig. 2. Reaction mechanism of semiconductor photocatalysis.

Fig. 3. Advantages of COFs as photocatalysts.

Fig. 4. Timeline of major linkages in photoactive covalent organic framework synthesis. The amide linkage is a representative stable motif.

Fig. 5. (a) Type-II heterojunction. (b) Z-scheme heterojunction. (c) S-scheme heterojunction. (d) Charge transfer processes in S-scheme heterojunction.

Fig. 6. Fabrication of COF-based photocatalysts via combination with different materials.

Fig. 7. (a) Schematic illustration of the TpPa-1/MIS and TpPa-2/MIS heterojunction preparation. (b) S-scheme charge migration in TpPa/MIS heterojunctions. Reprinted with permission from Ref. [69]. Copyright 2025, John Wiley and Sons.

Fig. 8. (a) Schematic of the synthesis for PtNPs@CTF-1. (b) TEM image of PtNPs@CTF-1 (scale bar: 10 nm) showing the lattice fringes of PtNPs. (c) The reaction mechanism for PtNPs@CTF-1. Reprinted with permission from Ref. [70]. Copyright 2024, Springer Nature. (d) Proposed photocatalytic CO2-to-CO mechanism over Fe SAS/Tr-COFs. (e) Top-view charge density difference of Fe SAS/Tr-COFs. Skyblue, electron accumulation; yellow, depletion. Reprinted with permission from Ref. [74]. Copyright 2022, American Chemical Society.

Fig. 10. (a) Structure and Synthesis of the TpPa/TpDz Heterojunction. (b) Electrostatic potential surfaces (EPSs) of TpPa/TpDz. (c) Mechanism for H2O2 photoproduction on the TpPa/TpDz heterojunction. Reprinted with permission from Ref. [82]. Copyright 2025, Springer Nature.

Fig. 11. (a) Synthesis of PRGO/TP-COF Nanocomposites. (b) CO Yield Performance of 25% PRGO/TP-COF under Varied Conditions. (c) Photocatalytic CO2 Reduction by 25% PRGO/TP-COF Nanocomposites. Reprinted with permission from Ref. [88]. Copyright 2024, Elsevier.

Fig. 12. (a) Schematic illustration of the synthesis process for TT-COF/ZCS composites. High-resolution XPS spectra of N 1s (b) and Zn 2p (c) for TT-COF, ZCS, and TZ-40 before and after illumination. (d) Decay pathways of photogenerated electrons in TZ-40. Reprinted with permission from Ref. [90]. Copyright 2024, John Wiley and Sons. (e) Schematic synthesis and porous cage structure of the COF/ZnSe composite. Surface potential of (f) COF and (g) COF/ZnSe-1 under dark and 365 nm light illumination. (h) Schematic relaxation pathways of photogenerated charge carriers in the COF/ZnSe composite. Reprinted with permission from Ref. [93]. Copyright 2025, John Wiley and Sons.

Table 1 COF-based heterojunction photocatalysts for various photocatalytic applications.

Photocatalyst	Type	Synthesis method	Application	Light source	Activity	Ref.
COF@CeO₂	Z	in-situ reaction	CO₂ reduction	300 W λ > 420 nm	66.2 μmol g^-1	[97]
JUC-X@ZIS	Z	in-situ growth	H₂ generation	10 W LED λ = 420 nm	9.46 mmol g^-1 h^-1	[98]
TiO₂/T-COF	Z	in-situ growth	CO₂ reduction	PLS-SXE 300	2.3 μmol h^-1	[99]
Ag₃PO₄/COF	Z	in-situ synthesis	RhB degradation	300 W λ > 420 nm	96.7% (40 min)	[100]
ZnIn₂S₄/Tp-Tta COF	S	in-situ growth	organic transformations	LED 80 W	12.1 mmol g^-1 h^-1	[101]
MAPbBr₃/COF	S	self-assembly	organic transformations	blue LED	PTD, 100%	[102]
Rh-COF@COF	S	in-situ growth	organic transformations	300 W λ ≥ 420 nm	2.6 mmol g^-1 h^-1	[103]
W₁₈O₄₉@TpPa-H	S	in-situ growth	organic transformations	10 W 420 nm LED	99% within 4 h	[104]
TpPa-COF/2D g-C₃N₄	S	in-situ growth	H₂ generation	λ ≥ 420 nm	17600 μmol g^-1 h^-1	[105]
TB-1	S	solvothermal	H₂O₂ production	λ > 420 nm	723 μmol g^-1 h^-1	[106]
sp²c-COF/Py-NH₂-COF	S	solvothermal	purification	300 W Xe lamp	TC, 94.8%, 1.5 h	[107]
ZnO/TpPa-Cl	S	in-situ growth	H₂O₂ production	300 W Xe lamp	2443 μmol g^-1 h^-1	[108]
CdS/BiVO₄@T-COF	S	self-assembly	CO₂ reduction	300 W 420 ~780 nm	183.8 μmol g^-1 h^-1	[109]
PRGO/TP-COF	S	self-assembly	CO₂ reduction	300 W λ > 400 nm	9.76 μmol g^-1 h^-1	[88]
TpMA/In₂S₃	S	hydrothermal	H₂O₂ production	300 W λ ≥ 420 nm	311.07 μmol L^-1	[110]
TiO₂/COF	S	in-situ growth	H₂O₂ production	300 W 350 ~780 nm	740 μmol L^-1 h^-1	[111]
g-C₃N₄(NH)/COF	S	solvothermal	CO₂ reduction	300 W λ > 400 nm	11.25 μmol h^-1	[112]
TiO₂/TpPa-Cl	S	solvothermal	H₂O₂ production	300W 350 ~800 nm	2082.6 μmol g^-1 h^-1	[113]
COF/Ni-ZIF-8	S	in-situ growth	CO₂ reduction	300 W λ > 420 nm	28.7 μmol g^-1 h^-1 (CH₄)	[114]
ZnO/COF	S	in-situ growth	H₂O₂ generation	365 nm	AQY = 5%	[115]
BiOBr/COF	S	hydrothermal	degradation	300 W	94.6% (120 min)	[116]
20N-COF/BOB	S	in-situ growth	TC degradation	300 W λ > 420 nm	81.2% (120 min)	[117]
TiO₂/COF	S	in-situ growth	H₂ generation	300 W λ > 380 nm	3962 μmol g^-1 h^-1	[118]
TpPa-1/MIS-5%	S	in-situ growth	H₂ generation	300 W λ ≥ 420 nm	13.16 mmol g^-1 h^-1	[69]
CZS-FOCTF	S	hydrothermal	H₂ generation	300 W λ > 420 nm	247.62 mmol g^-1 h^-1	[119]
M_OS₂/COF	Type-II	hydrothermal	TC degradation	300W AM 1.5	98% (30 min)	[120]
CuPor-Ph-COF/g-C₃N₄	Type-II	in-situ synthesis	RhB degradation	300 W λ > 400 nm	94.5% (90 min)	[121]
Au₂-COF	Schottky junction	deposition	nitrate reduction	300 W AM 1.5	382.48 μmol g^-1 h^-1	[122]

Table 1 COF-based heterojunction photocatalysts for various photocatalytic applications.

Photocatalyst	Type	Synthesis method	Application	Light source	Activity	Ref.
COF@CeO₂	Z	in-situ reaction	CO₂ reduction	300 W λ > 420 nm	66.2 μmol g^-1	[97]
JUC-X@ZIS	Z	in-situ growth	H₂ generation	10 W LED λ = 420 nm	9.46 mmol g^-1 h^-1	[98]
TiO₂/T-COF	Z	in-situ growth	CO₂ reduction	PLS-SXE 300	2.3 μmol h^-1	[99]
Ag₃PO₄/COF	Z	in-situ synthesis	RhB degradation	300 W λ > 420 nm	96.7% (40 min)	[100]
ZnIn₂S₄/Tp-Tta COF	S	in-situ growth	organic transformations	LED 80 W	12.1 mmol g^-1 h^-1	[101]
MAPbBr₃/COF	S	self-assembly	organic transformations	blue LED	PTD, 100%	[102]
Rh-COF@COF	S	in-situ growth	organic transformations	300 W λ ≥ 420 nm	2.6 mmol g^-1 h^-1	[103]
W₁₈O₄₉@TpPa-H	S	in-situ growth	organic transformations	10 W 420 nm LED	99% within 4 h	[104]
TpPa-COF/2D g-C₃N₄	S	in-situ growth	H₂ generation	λ ≥ 420 nm	17600 μmol g^-1 h^-1	[105]
TB-1	S	solvothermal	H₂O₂ production	λ > 420 nm	723 μmol g^-1 h^-1	[106]
sp²c-COF/Py-NH₂-COF	S	solvothermal	purification	300 W Xe lamp	TC, 94.8%, 1.5 h	[107]
ZnO/TpPa-Cl	S	in-situ growth	H₂O₂ production	300 W Xe lamp	2443 μmol g^-1 h^-1	[108]
CdS/BiVO₄@T-COF	S	self-assembly	CO₂ reduction	300 W 420 ~780 nm	183.8 μmol g^-1 h^-1	[109]
PRGO/TP-COF	S	self-assembly	CO₂ reduction	300 W λ > 400 nm	9.76 μmol g^-1 h^-1	[88]
TpMA/In₂S₃	S	hydrothermal	H₂O₂ production	300 W λ ≥ 420 nm	311.07 μmol L^-1	[110]
TiO₂/COF	S	in-situ growth	H₂O₂ production	300 W 350 ~780 nm	740 μmol L^-1 h^-1	[111]
g-C₃N₄(NH)/COF	S	solvothermal	CO₂ reduction	300 W λ > 400 nm	11.25 μmol h^-1	[112]
TiO₂/TpPa-Cl	S	solvothermal	H₂O₂ production	300W 350 ~800 nm	2082.6 μmol g^-1 h^-1	[113]
COF/Ni-ZIF-8	S	in-situ growth	CO₂ reduction	300 W λ > 420 nm	28.7 μmol g^-1 h^-1 (CH₄)	[114]
ZnO/COF	S	in-situ growth	H₂O₂ generation	365 nm	AQY = 5%	[115]
BiOBr/COF	S	hydrothermal	degradation	300 W	94.6% (120 min)	[116]
20N-COF/BOB	S	in-situ growth	TC degradation	300 W λ > 420 nm	81.2% (120 min)	[117]
TiO₂/COF	S	in-situ growth	H₂ generation	300 W λ > 380 nm	3962 μmol g^-1 h^-1	[118]
TpPa-1/MIS-5%	S	in-situ growth	H₂ generation	300 W λ ≥ 420 nm	13.16 mmol g^-1 h^-1	[69]
CZS-FOCTF	S	hydrothermal	H₂ generation	300 W λ > 420 nm	247.62 mmol g^-1 h^-1	[119]
M_OS₂/COF	Type-II	hydrothermal	TC degradation	300W AM 1.5	98% (30 min)	[120]
CuPor-Ph-COF/g-C₃N₄	Type-II	in-situ synthesis	RhB degradation	300 W λ > 400 nm	94.5% (90 min)	[121]
Au₂-COF	Schottky junction	deposition	nitrate reduction	300 W AM 1.5	382.48 μmol g^-1 h^-1	[122]

Fig. 13. (a) Synthesis schematic of the TATF COF/PUP heterojunction. (b) Proposed S-scheme mechanism in TATF-COF/PUP heterojunction. Reprinted with permission from Ref. [125]. Copyright 2022, Elsevier. (c) Synthesis of the TpBD COF@ZIS heterojunction. (d) SEM images. (e) H2 production rate versus ZIS loading in TpBD COF@ZIS. Reprinted with permission from Ref. [128]. Copyright 2023, Elsevier. (f) Synthesis process and structure of PY-DHBD-COF. (g) H2 evolution versus time for PY-DHBD-COF with varying Pt loadings. (h) Longterm H2 production for 3 wt% Pt loaded PY-DHBD-COF. Reprinted with permission from Ref. [129]. Copyright 2022, Springer Nature.

Fig. 14. (a) Preparation of TTCOF/NUZ composites with varying TTCOF contents. (b) Photocatalytic CO2 conversion rates of TTCOF, NUZ, and x% TTCOF/NUZ (x = 5, 10, 15, 20, 30). Reprinted with permission from Ref. [134]. Copyright 2022, American Chemical Society. (c) Schematic illustration of the synthetic route toward Ru-Th-CTF/RGO. (d) Photocatalytic pathway and free energy changes for CO2 reduction to HCOO- on the Ru center. Reprinted with permission from Ref. [135]. Copyright 2023, John Wiley and Sons.

Fig. 15. (a) Schematic of the fabrication process for the Bi3TiNbO9@C4N heterojunction. (b) Schematic of H2O2 photosynthesis coupled with photoinduced charge transfer in the Bi3TiNbO9@C4N heterojunction. Reprinted with permission from Ref. [139]. Copyright 2025, John Wiley and Sons. (c) Schematic illustration of the preparation of the Tph-Dha-COF@Nb2C heterojunction. (d) Proposed 2e- ORR mechanism of H2O2 generation on Tph-Dha-COF@Nb2C. Reprinted with permission from Ref. [140]. Copyright, 2025, Elsevier.

Fig. 16. (a) Schematic synthesis process of the TiO2/TD COF composite. (b) TEM image of the TiO2/TD COF composite. (c) RhB photodegradation over different photocatalyst. (d) Schematic for the decay pathways of photogenerated electrons in TiO2/TD COF heterojunction. Reprinted with permission from Ref. [144]. Copyright, 2025, Elsevier. (e) Synthetic routes and the photo of MT-COF-Au. (f) Possible degradation pathways of BTA in the photocatalytic system. Reprinted with permission from Ref. [146]. Copyright 2024, Elsevier.

Fig. 17. Representative linkages involved in the COF membranes formation.

Fig. 18. Schematic illustration of common strategies for COF membrane fabrication. (a) Interfacial polymerization; (b) layer-by-layer assembly; (c) in-situ growth approach.

Fig. 19. (a) Synthesis scheme of COF thin membranes. (b) SEM images. Reprinted with permission from Ref. [159]. Copyright 2017, American Chemical Society. (c) Schematic of the COF membrane formation via vapor-solid interfacial reaction. (d) Evolution of XRD patterns of the TFP-PDA membranes over time. Reprinted with permission from Ref. [164]. Copyright 2020, American Chemical Society.

Fig. 20. (a) Synthesis of NCOFN Nanosheets via Oil-Water-Oil Triphase Method. (b) N2 Isotherms (77 K) and Pore Size Distributions of NCOFM-0 and NCOFM-50 Freestanding Membranes. Reprinted with permission from Ref. [169]. Copyright 2022, John Wiley and Sons. (c) Schematic of COF assembly forming an hourglass-shaped channel. (d) Digital photograph of the ultra-large-area membrane. Reprinted with permission from Ref. [171]. Copyright 2025, John Wiley and Sons.

Fig. 21. (a) Synthetic scheme for TB-TMT and TFPT-TMT membranes. (b) XRD patterns of TFPT-TMT membrane, powder, and structure stimulation. Reprinted with permission from Ref. [175]. Copyright 2023, American Chemical Society (c) Surface-initiated growth of a TA/TpPa-COF membrane via TA-mediated nucleation. (d) SEM image of the TA/TpPa-COF membrane surface. Reprinted with permission from Ref. [179]. Copyright 2021, John Wiley and Sons. (e) Schematic structure of CTF membranes. (f) shows a free-standing CTF membrane with a diameter of over 10?cm. Reprinted with permission from Ref. [183]. Copyright 2023, Springer Nature.

Fig. 22. (a) Reaction steps. (b) Synthetic procedure for the fabrication of CTF membrane on DMSO surface assisted by imine precursor. (c) PXRD of collected CTF membrane and its simulated XRD pattern with AA stacking. (d) Photocatalytic HER performance of membrane on glass in four cycles under visible light (> 420 nm). Reprinted with permission from Ref. [185]. Copyright 2021, Springer Nature. (e) Chemical structures of anthracene-based COFs. (f) Proposed photocatalytic HER mechanism in COF membranes. (g) AntTTH membrane under diffuse sunlight inside a photocatalytic reactor. Reprinted with permission from Ref. [187]. Copyright 2024, Royal Society of Chemistry.

Fig. 23. (a) Synthesis Scheme of a TaTpBpy-Ni COFs membrane Photocatalyst. (b) AFM images of the TaTpBpy-Ni@PET. Reprinted with permission from Ref. [190]. Copyright 2024, American Chemical Society. (c) Schematic illustration for the synthesis of 0N-COF, 1NCOF, and 2N-COF membranes at the ionic liquid-H2O interface. (d) Experimental XRD patterns of the COF membranes. (e) Time courses of the photocatalytic activity and durability based on the 2N-COF membrane. Reprinted with permission from Ref. [191]. Copyright 2023, American Chemical Society.

Fig. 24. (a) Schematic formation of CTF-DA-Film and CTF-SA-Film via in-situ polymerization on glass. (b) Free energy of the photocatalytic H2O2 production process over the CTF-DA segment. (c) Production rate of CTF-DA-Film after 1-5 growth cycles. Reprinted with permission from Ref. [194]. Copyright 2024, John Wiley and Sons. (d) Schematic of interfacial polymerization for thickness-tunable COF membrane fabrication. (e) SEM image of COF-M180. Inset: photo of the large-area membrane (20 cm × 30 cm) on PAN. (f) Characterization of surface roughness (AFM) and wettability (contact angle) on both sides of the membrane. (g) Temperature-dependent integrated PL intensity for COF-M180. (h) Photocurrent response measurements of COF-M180 and COF-P. (i) Schematic illustration of the photocatalytic membrane reactor. Reprinted with permission from Ref. [195]. Copyright 2025, John Wiley and Sons.

Fig. 25. (a) Synthetic strategy and procedure of the representative AmCOF-1 membrane. (b) XRD patterns. (c) Cyclic H2O2 production over AICOF-1 and AmCOF-1. (d) H2O2 production over AICOF-1 and AmCOF-1 membranes (natural light). Inset: the 208 cm2 AmCOF-1 membrane. Reprinted with permission from Ref. [196]. Copyright 2025, John Wiley and Sons.

Fig. 26. (a) Diagram of the COF/CNT Membrane Synthesis and the Photocatalytic Degradation Process. (b) PXRD pattern of TpBD. (c) MB17 degradation by various catalysts. Reprinted with permission from Ref. [198]. Copyright 2021, American Chemical Society.

Fig. 27. (a) Schematic illustration of the in-plane oriented COF/MoS2 PN heterostructure membrane. (b) GIXRD pattern and in-plane GIXRD profile of the TAPB-DMTA COF membrane grown on a SiO2/Si substrate. (c) AFM image of a COF membrane grown on a MoS2 substrate. (d) Schematic showing charge separation and photocatalytic H2O2 production in a COF/MoS2 PN heterojunction membrane under visible light. (e) Time-resolved PL decay of oriented TAPB-DMTA/MoS2 membranes and non-oriented TAPT-TFPA COFs. (f) H2O2 production over powder, non-oriented, and oriented TAPB-DMTA COFs. Reprinted with permission from Ref. [203]. Copyright 2025, John Wiley and Sons.

Fig. 28. (a) Energy diagram and schematic of solar reforming over a COF-NiME composite, coupling H2 evolution with oxidation of organics (polyols and sugars) to formate. (b) Photograph of a standalone COF|ITO|CNx. (c) Control experiments for photocatalytic H2 evolution with varied catalyst components and ratios (NiME: 1.25 μmol L-1, H2O, 0.2 mol L-1 EG, 21 h). (d) Photograph of the solar plastic reforming reactor under direct sunlight (inset: close-up view). Reprinted with permission from Ref. [206]. Copyright 2025, John Wiley and Sons.

Fig. 29. (a) Schematic illustration of the synthetic process for MIL-68@COF-V heterostructures. (b) Proposed photogenerated electron-transfer pathway within the heterojunction. (c) Comparative degradation of Rh?6G by 10%-MIL-68@COF-V powder and membrane. Reprinted with permission from Ref. [207]. Copyright 2024, John Wiley and Sons.

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面向实用光催化的共价有机框架多尺度工程:从异质结结构设计到膜制备

Multiscale engineering of COFs toward practical photocatalysis: From heterojunction design to membrane fabrication

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