Rational Design of Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production DOI Open Access
Yang Ou, Yifan Zhang, Wen Luo

et al.

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

Abstract Photocatalytic production of hydrogen peroxide (H 2 O ) represents a significant approach to achieving sustainable energy generation through solar energy, addressing both shortages and environmental pollution. Among various photocatalytic materials, covalent organic frameworks (COFs) have gained widespread attention in‐depth research due their unique advantages, including high porosity, predesignability, atomic‐level tunability. In recent years, progress has been made in the development, performance enhancement, mechanistic understanding COF‐based photocatalysts. This review focuses on latest advancements H using COFs, particularly emphasizing rational design COF structures regulate catalytic exploring fundamental processes involved photocatalysis. Based current achievements this field, paper also discusses existing challenges future opportunities, aiming provide reference for application COFs production.

Language: Английский

Solar‐to‐H2O2 Catalyzed by Covalent Organic Frameworks DOI Creative Commons
Zi‐Jun Yong, Tianyi Ma

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 14, 2023

Abstract Benefiting from the excellent structural tunability, robust framework, ultrahigh porosity, and rich active sites, covalent organic frameworks (COFs) are widely recognized as promising photocatalysts in chemical conversions, emerged hydrogen peroxide (H 2 O ) photosynthesis 2020. H , serving an environmental‐friendly oxidant a liquid fuel, has attracted increasing researchers to explore its potential. Over past few years, numerous COFs‐based developed with encouraging achievements production, whereas no comprehensive review articles exist summarize this specific significant area. Herein we provide systematic overview of advances challenges COFs photocatalytic production. We first introduce priorities photosynthesis. Then, various strategies improve efficiency discussed. The perspective outlook for future emerging field finally offered. This timely will pave way development highly efficient practical production value‐added chemicals not limited .

Language: Английский

Citations

177
Recent Advances in the Use of Covalent Organic Frameworks as Heterogenous Photocatalysts in Organic Synthesis DOI Creative Commons
Alberto López‐Magano, Saba Daliran, Ali Reza Oveisi

et al.

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(24)

Published: Dec. 23, 2022

Abstract Organic photochemistry is intensely developed in the 1980s, which nature of excited electronic states and energy electron transfer processes are thoroughly studied finally well‐understood. This knowledge from molecular organic can be transferred to design covalent frameworks (COFs) as active visible‐light photocatalysts. COFs constitute a new class crystalline porous materials with substantial application potentials. Featured outstanding structural tunability, large porosity, high surface area, excellent stability, unique photoelectronic properties, potential candidates various research areas (e.g., photocatalysis). review aims provide state‐of‐the‐art insights into COF photocatalysts (pristine, functionalized, hybrid COFs) for transformations. The catalytic reaction mechanism COF‐based influence dimensionality crystallinity on heterogenous photocatalysis performance also discussed, followed by perspectives prospects main challenges opportunities future

Language: Английский

Citations

144
Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity DOI

Zonglin Weng,

Yuanfang Lin,

Siyuan Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(43)

Published: Sept. 5, 2023

Singlet oxygen (1 O2 ) is an excellent reactive species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to huge dilemma synthesizing single-site type catalysts, control and regulation 1 generation AOPs still challenging underlying mechanism remains largely obscure. Here, taking advantage well-defined flexibly tunable sites covalent frameworks (COFs), we report first achievement precisely regulating ROSs peroxymonosulfate (PMS)-based by site engineering COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway 100 % , whereas biphenyl-based (BPD-COFs) almost identical structures activate produce radicals (⋅OH SO4.- ). The BPY-COFs/PMS system delivers boosted performance degradation target pollutants from water, which ca. 9.4 times that its BPD-COFs counterpart, surpassing most reported PMS-based systems. Mechanism analysis indicated highly electronegative pyridine-N atoms on BPY-COFs provide extra adsorb terminal H PMS, resulting simultaneous adsorption O one pyridine ring, facilitates cleavage S-O bond generate .

Language: Английский

Citations

115
Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions DOI
Meng Lu, Shuai‐Bing Zhang, Mingyi Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 7, 2023

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+ /Fe(bpy)32+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer suitable band gap for highly photocatalytic hydrogen (H2 evolution. Rubpy-ZnPor COF achieved the highest H2 yield (30 338 μmol g-1 h-1 with apparent quantum efficiency (AQE) 9.68 %@420 nm, showed one best performances among all reported based photocatalysts. Furthermore, in situ produced was successfully tandem used alkyne hydrogenation ≈99.9 % conversion efficiency. Theoretical calculations reveal both photosensitizer units MCOFs can be photoexcited thus contribute optimal activity. This work develops general strategy shows great potential using multiple photosensitive materials field photocatalysis.

Language: Английский

Citations

67
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

67
Regulating Keto–Enol Tautomerism of β-Ketoenamine Covalent–Organic Frameworks for Photocatalytic Oxidative Coupling of Amines DOI

Feng Chu,

Guangtong Hai,

Danfeng Zhao

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13167 - 13180

Published: Sept. 28, 2023

Covalent–organic frameworks (COFs), as promising metal-free porous catalysts, have become a hot research topic in the field of (photo)catalysis. Herein, series β-ketoenamine COFs are synthesized using different amino and aldehyde monomers, these exhibit diverse characteristics terms crystallinity, chemical structure, microscopic morphology, optoelectronic properties. TpBD-(CH3)2 from 2,4,6-triformylphloroglucinol o-tolidine exhibits an extended π-conjugated structure higher crystallinity well more suitable redox potential, which greatly enhances photocatalytic activity benzylamine oxidation. Besides, increased number hydroxyl groups on trialdehyde-based monomer contributes to ketoamines TpTAB skeleton, is favorable for photocatalysis. Meanwhile, can rapidly increase their own temperature through internal structural evolution under light irradiation, thus boosting oxidative coupling amines with high efficiency. This work could provide some guidance rational design functional advanced organic transformations.

Language: Английский

Citations

61
Structural regulation of covalent organic frameworks for advanced electrocatalysis DOI
Liyuan Xiao, Luoluo Qi,

Jingru Sun

et al.

Nano Energy, Journal Year: 2023, Volume and Issue: 120, P. 109155 - 109155

Published: Dec. 2, 2023

Language: Английский

Citations

60
Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis DOI
Hong‐Guang Jin, Pengcheng Zhao, Yunyang Qian

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(18), P. 9378 - 9418

Published: Jan. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Language: Английский

Citations

59
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

58
Enhanced Energy Transfer in A π‐Conjugated Covalent Organic Framework Facilitates Excited‐State Nickel Catalysis DOI Creative Commons
Yingjie Fan, Dong Won Kang, Steven Labalme

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 18, 2023

Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long-range π-conjugation photosensitizing building blocks been explored for sustainable photocatalysis. Herein, we report the first example of COF-based energy transfer Ni catalysis. A pyrene-based COF sp2 carbon-conjugation was synthesized used coordinate NiII centers through bipyridine moieties. Under light irradiation, enhanced in facilitated excitation catalyze borylation trifluoromethylation reactions aryl halides. The showed two orders magnitude higher efficiency these than its homogeneous control could be recovered reused without significant loss catalytic activity.

Language: Английский

Citations

57