Solar Light Driven H2O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction DOI Creative Commons
Prasenjit Das,

Jérôme Roeser,

Arne Thomas

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 8, 2023

A chemically stable 2D microporous COF (PMCR-1) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term photocatalytic H2 O2 production rate (60 h) from pure sea water under visible light. The is markedly enhanced when benzyl alcohol (BA) added as reductant, which also due to strong π-π interaction of BA with dangling phenyl moieties in pores introduced by Motivated concomitant oxidation benzaldehyde during formation, various organic substrates such amine methyl sulfide derivatives investigated. It shown that well-defined micropores enable size-selective oxidation.

Language: Английский

Molecularly Engineered Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis DOI Creative Commons

Mingpu Kou,

Yongye Wang,

Yixue Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(19)

Published: Feb. 15, 2022

Synthesizing H

Language: Английский

Citations

429
Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis DOI Creative Commons

Chencheng Qin,

Xiaodong Wu, Lin Tang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 28, 2023

Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative reductive reaction centers remain a challenge. In this study, benzotrithiophene-based with spatially separated redox are rationally designed for the photocatalytic production of hydrogen peroxide from water oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity H2O2 photogeneration, yield rate 2111 μM h-1 (21.11 μmol 1407 g-1 h-1) solar-to-chemical conversion efficiency 0.296%. Codirectional charge transfer large energetic differences between linkages linkers verified in double donor-acceptor structures periodic frameworks. sites mainly concentrated on electron-acceptor fragments near imine bond, which regulate electron distribution adjacent carbon atoms to optimally reduce Gibbs free energy O2* OOH* intermediates during formation H2O2.

Language: Английский

Citations

219
Metalated covalent organic frameworks: from synthetic strategies to diverse applications DOI
Qun Guan, Lele Zhou, Yu‐Bin Dong

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Language: Английский

Citations

214
A novel organic/inorganic S-scheme heterostructure of TCPP/Bi12O17Cl2 for boosting photodegradation of tetracycline hydrochloride: Kinetic, degradation mechanism, and toxic assessment DOI
Chunchun Wang, Ruyu Yan, Mingjie Cai

et al.

Applied Surface Science, Journal Year: 2022, Volume and Issue: 610, P. 155346 - 155346

Published: Oct. 30, 2022

Language: Английский

Citations

208
Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H2O2 Production DOI
Prasenjit Das,

Gouri Chakraborty,

Jérôme Roeser

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 2975 - 2984

Published: Jan. 25, 2023

Multicomponent reactions (MCRs) can be used to introduce different functionalities into highly stable covalent organic frameworks (COFs). In this work, the irreversible three-component Doebner reaction is utilized synthesize four chemically quinoline-4-carboxylic acid DMCR-COFs (DMCR-1-3 and DMCR-1NH) equipped with an acid-base bifunctionality. These show superior photocatalytic H2O2 evolution (one of most important industrial oxidants) compared imine COF analogue (Imine-1). This achieved sacrificial oxidants but also in pure water under oxygen or air atmosphere. Furthermore, high photostability, durability, recyclability. MCR-COFs thus provide a viable materials' platform for solar chemical energy conversion.

Language: Английский

Citations

196
Developing Ni single-atom sites in carbon nitride for efficient photocatalytic H2O2 production DOI Creative Commons
Xu Zhang, Hui Su, Peixin Cui

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 6, 2023

Photocatalytic two-electron oxygen reduction to produce high-value hydrogen peroxide (H2O2) is gaining popularity as a promising avenue of research. However, structural evolution mechanisms catalytically active sites in the entire photosynthetic H2O2 system remains unclear and seriously hinders development highly-active stable photocatalysts. Herein, we report high-loading Ni single-atom photocatalyst for efficient synthesis pure water, achieving an apparent quantum yield 10.9% at 420 nm solar-to-chemical conversion efficiency 0.82%. Importantly, using situ synchrotron X-ray absorption spectroscopy Raman directly observe that initial Ni-N3 dynamically transform into high-valent O1-Ni-N2 after O2 adsorption further evolve form key *OOH intermediate before finally forming HOO-Ni-N2. Theoretical calculations experiments reveal structure reduces formation energy barrier suppresses O=O bond dissociation, leading improved production activity selectivity.

Language: Английский

Citations

192
Pyrene‐Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production DOI
Jiamin Sun, Himanshu Sekhar Jena, Chidharth Krishnaraj

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 10, 2023

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H2 O2 production. The experimental studies are complemented by density functional theory calculations, proving that the unit is more active production than bipyridine (diarylamino)benzene reported previously. decomposition experiments verified distribution of over a large surface area COFs plays an important role in catalytic performance. Py-Py-COF though contains other which induces high due to dense concentration close proximity limited area. Therefore, two-phase reaction system (water-benzyl alcohol) was employed inhibit decomposition. This first report on applying pyrene-based generation.

Language: Английский

Citations

184
Sulfone‐Modified Covalent Organic Frameworks Enabling Efficient Photocatalytic Hydrogen Peroxide Generation via One‐Step Two‐Electron O2 Reduction DOI
Yu Luo, Beiping Zhang, Chenchen Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 25, 2023

Abstract Photocatalytic oxygen reduction reaction (ORR) offers a promising hydrogen peroxide (H 2 O ) synthetic strategy, especially the one‐step two‐electron (2e − ORR route holds great potential in achieving highly efficient and selectivity. However, 2e is rarely harvested underlying mechanism for regulating pathways remains greatly obscure. Here, by loading sulfone units into covalent organic frameworks (FS‐COFs), we present an photocatalyst H generation via from pure water air. Under visible light irradiation, FS‐COFs exert superb yield of 3904.2 μmol h −1 g , outperforming most reported metal‐free catalysts under similar conditions. Experimental theoretical investigation reveals that accelerate separation photoinduced electron‐hole (e ‐h + pairs, enhance protonation COFs, promote adsorption Yeager‐type, which jointly alters process two‐step to one, thereby with high

Language: Английский

Citations

178
Constructing Synergistic Triazine and Acetylene Cores in Fully Conjugated Covalent Organic Frameworks for Cascade Photocatalytic H2O2 Production DOI
Lipeng Zhai,

Zhipeng Xie,

Cheng‐Xing Cui

et al.

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(11), P. 5232 - 5240

Published: May 16, 2022

Covalent organic frameworks (COFs) are an ideal template for photocatalytic H2O2 synthesis because of the tunable chemical structures and semiconductor properties. However, photoactivity COFs is still under-improved due to inefficient intrinsic charge generation, fast recombination photogenerated charges, limited electron transport along frameworks. Herein, spatially separated synergistic triazine acetylene units first integrated into (EBA-COF BTEA-COF) production. The spatial separation cores leads efficient suppressed recombination, C═C linkage facilitates electrons over skeletons. Both experimental computational results suggested that synergistically promote in a two-electron pathway. EBA-COF showed attractive activity with production rate 1830 μmol h–1 gcat–1, superior most other COF-based catalysts. This study provides method designing photocatalysts active sites based on vinylene-linked COFs.

Language: Английский

Citations

172
Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2 DOI

Jia‐Nan Chang,

Qi Li, Jingwen Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(9)

Published: Dec. 30, 2022

The full reaction photosynthesis of H2 O2 that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization overcome complex reaction-process anthraquinone-oxidation. Here, a kind oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through covalent-coupling tetrathiafulvalene (photo-oxidation site) benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency photo-redox sites enables generation . Specifically, record-high yield (TTF-BT-COF, ≈276 000 μM h-1 g-1 ) for achieved among porous crystalline photocatalysts. This first work design COFs , might extend scope in production.

Language: Английский

Citations

171