COFs‐Based Metal‐Free Heterojunctions for Solar‐to‐Chemical Energy Conversion DOI
Tianyu Zhou, Yunchao Ma, Hao Feng

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(49)

Published: Aug. 17, 2024

Abstract Covalent organic frameworks (COFs) are a promising class of polymers with the merits robust framework, ultrahigh porosity, and molecularly precise backbones, which reveals great potential for solar‐to‐chemical energy conversion in context mitigating environmental crises. However, photochemical activities individual COFs not as desired, primarily due to their limited light absorption, insufficient dissociation photogenerated excitons readily recombined carriers. Recently, COFs‐based metal‐free heterojunctions synergistic effects provide feasible route boost photocatalytic activity more environmentally friendly cost‐competitive manners. Herein, it is first systematically overview advances from heterojunction types, heterointerfaces interactions, primary design mechanisms. Then, typical photocatalysts (e.g., g‐C 3 N 4 ‐COFs, carbon materials‐COFs, polymer semiconductor‐COFs, COFs‐COFs heterojunction) summarized. Finally, challenges long‐term outlooks future offered terms efficiency, yield, stability, cost reaction mechanisms, well standardized evaluation method activities. It anticipated that this review can deliver new insights into fundamental engineering conversion, further accelerate development area.

Language: Английский

Covalent Organic Frameworks Enable Sustainable Solar to Hydrogen Peroxide DOI
Deming Tan, Rong Zhuang, Ruichong Chen

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(12)

Published: Dec. 6, 2023

Abstract As a chemical product with rapidly expanding demand in the field of modern energy and environmental applications, hydrogen peroxide (H 2 O ) has garnered widespread attention. However, existing industrial production H is plagued by high consumption, harmful waste emission, severe safety issues, making it difficult to satisfy environmental/economic concept. Artificial photosynthesis offers viable strategy for green sustainable since uses sunlight as an source initiate reaction oxygen water produce . Among various photocatalysts, covalent organic frameworks (COFs), featuring highly ordered skeletons well‐defined active sites, have emerged promising photocatalysts production. This review presents nascent burgeoning area photocatalytic based on COFs. First, brief overview technology provided, followed detailed introduction principles evaluation generation. Subsequently, latest research progress judicious design COFs expounded, particular emphasis manipulating electronic structures redox sites. Finally, outlook challenges future opportunities proposed, hope stimulating further explorations novel molecular‐designed photosynthesis.

Language: Английский

Citations

85
Efficient Photosynthesis of Hydrogen Peroxide by Cyano‐Containing Covalent Organic Frameworks from Water, Air and Sunlight DOI

Yanghui Hou,

Peng Zhou,

Fuyang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 28, 2023

Abstract The insufficient exciton ( e − ‐ h + pair) separation/transfer and sluggish two‐electron water oxidation are two main factors limiting the H 2 O photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate reduce energy barrier in COFs via a dicyano functionalization. situ characterization theoretical calculations reveal that functionalization improves amount charge transfer channels between donor acceptor units from COF‐0CN without cyano three COF‐1CN with mono‐cyano four COF‐2CN functionalization, leading highest COF‐2CN. More importantly, group activates neighbouring C atom produce key *OH intermediate for effectively reducing rate‐determining photosynthesis. enhanced result high yield (1601 μmol g −1 ) oxygen using sacrificial reagent under visible‐light irradiation. can wide pH range, different real samples, scaled‐up reactor natural sunlight irradiation, continuous‐flow consecutively producing solution decontamination.

Language: Английский

Citations

69
Engineering 2D Photocatalysts for Solar Hydrogen Peroxide Production DOI
Jindi Yang, Xiangkang Zeng, Mike Tebyetekerwa

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(23)

Published: April 3, 2024

Abstract Solar energy can be utilized in photocatalysis technology to realize light‐driven hydrogen peroxide (H 2 O ) production, a green chemical synthesis route. Designing high‐performance photocatalysts is critical achieving practical solar H production. During the past decade, significant research progress made photocatalytic materials for Particularly 2D materials‐based stand out due their unique physical and properties. This review highlights intricate relationship between material innovation photochemical It starts with fundamental principles of generation, focusing on crucial steps such as photon absorption, carrier dynamics, surface reactions, challenges that solve at each step. Then, various production are introduced detail. Engineering strategies optimize performance discussed afterward. Finally, future opportunities designing outlined. expected inspire engineering conversion other chemicals.

Language: Английский

Citations

68
Structural Motifs in Covalent Organic Frameworks for Photocatalysis DOI

Liyang Qin,

Chengdi Ma,

Jian Zhang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: March 10, 2024

Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization

Language: Английский

Citations

61
Vinyl‐Group‐Anchored Covalent Organic Framework for Promoting the Photocatalytic Generation of Hydrogen Peroxide DOI
Hong Yu,

Fengtao Zhang,

Qian Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 16, 2024

The artificial photosynthesis of H

Language: Английский

Citations

59
Boosting CO2 Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework DOI
Lei Zou, Ziao Chen, Duan‐Hui Si

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Language: Английский

Citations

54
A Novel Dual-Channel Carbon Nitride Homojunction with Nanofibrous Carbon for Significantly Boosting Photocatalytic Hydrogen Peroxide Production DOI

Jianwen Zhou,

Tianshang Shan, Fengshan Zhang

et al.

Advanced Fiber Materials, Journal Year: 2024, Volume and Issue: 6(2), P. 387 - 400

Published: Jan. 9, 2024

Language: Английский

Citations

54
Custom‐Design of Strong Electron/Proton Extractor on COFs for Efficient Photocatalytic H2O2 Production DOI
Liyao Li, Ximeng Lv,

Yuanyuan Xue

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 14, 2024

The development of photocatalysts with continuous electron extraction and rapid proton transfer could kinetically accelerate the artificial photosynthesis, but remains a challenge. Herein, we report topology-guided synthesis high-crystalline triazine covalent organic framework (COF) decorated by uniformly distributed polar oxygen functional groups (sulfonic group or carboxyl) as strong electron/proton extractor for efficient photocatalytic H

Language: Английский

Citations

54
Hierarchical assembly of donor–acceptor covalent organic frameworks for photosynthesis of hydrogen peroxide from water and air DOI
Yongzhi Chen, Ruoyang Liu, Yuanyuan Guo

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(8), P. 998 - 1010

Published: May 17, 2024

Language: Английский

Citations

51
Cyanide‐based Covalent Organic Frameworks for Enhanced Overall Photocatalytic Hydrogen Peroxide Production DOI
Enbo Zhou,

F.S. Wang,

Xiang Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 16, 2024

Abstract Photocatalytic oxygen reduction to produce hydrogen peroxide (H 2 O ) is a promising route providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts efficient overall H production in pure water has impeded ongoing research and practical thrusts. Here we present cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting hole accumulated BTT electron‐rich TBTN block. Under one sun, 11013 μmol h −1 g yield rate achieved without any sacrificial agent, outperforming most previous reports. Furthermore, DFT calculation situ DRIFTS spectrums suggesting Yeager‐type absorption *O ⋅ − intermediate cyanide active site, which prohibits formation superoxide radical revealing favored pathway.

Language: Английский

Citations

43