Enhancing Photocatalytic Hydrogen Production via the Construction of Robust Multivariate Ti‐MOF/COF Composites DOI Creative Commons
Cheng‐Xia Chen, Yang‐Yang Xiong, Xin Zhong

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(3)

Published: Nov. 15, 2021

Titanium metal-organic frameworks (Ti-MOFs), as an appealing type of artificial photocatalyst, have shown great potential in the field solar energy conversion due to their well-studied photoredox activity (similar TiO2 ) and good optical responsiveness linkers, which serve antenna absorb visible-light. Although much effort has been dedicated developing Ti-MOFs with high photocatalytic activity, performances are still poor. Herein, we implemented a covalent-integration strategy construct series multivariate Ti-MOF/COF hybrid materials PdTCPP⊂PCN-415(NH2 )/TpPa (composites 1, 2, 3), featuring excellent visible-light utilization, suitable band gap, surface area for H2 production. Notably, resulting composites demonstrated remarkably enhanced visible-light-driven evolution performance, especially composite 2 maximum rate 13.98 mmol g-1 h-1 (turnover frequency (TOF)=227 ), is higher than that (0.21 TpPa (6.51 ). Our work thereby suggests new approach highly efficient photocatalysts beyond.

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

421
Application of MOFs and COFs for photocatalysis in CO2 reduction, H2 generation, and environmental treatment DOI
Yifeng Zhang, Hangxi Liu,

Feixue Gao

et al.

EnergyChem, Journal Year: 2022, Volume and Issue: 4(4), P. 100078 - 100078

Published: June 25, 2022

Language: Английский

Citations

373
Reconstructed covalent organic frameworks DOI Creative Commons
Weiwei Zhang, Linjiang Chen, Sheng Dai

et al.

Nature, Journal Year: 2022, Volume and Issue: 604(7904), P. 72 - 79

Published: April 6, 2022

Abstract Covalent organic frameworks (COFs) are distinguished from other polymers by their crystallinity 1–3 , but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions poorly reversible 4,5 . More chemistry can improve 6–9 this typically yields with poor physicochemical stability and limited application scope 5 Here we report a general scalable protocol prepare imine COFs, based on an unexpected framework reconstruction. In contrast standard approaches in which monomers initially randomly aligned, our method involves pre-organization of using removable covalent tether, followed confined polymerization. This reconstruction route produces reconstructed greatly enhanced much higher porosity means simple vacuum-free synthetic procedure. The increased improves charge carrier transport, leading sacrificial photocatalytic hydrogen evolution rates up 27.98 mmol h −1 g nanoconfinement-assisted strategy is step towards programming function materials through atomistic structural control.

Language: Английский

Citations

357
Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance DOI Creative Commons
Zhongshan Chen, Jingyi Wang, Mengjie Hao

et al.

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

Published: Feb. 27, 2023

Covalent organic frameworks (COFs) represent an emerging class of photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry construct a family isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties local pore characteristics COFs modulated using different linkers. The excited state electronic distribution transport pathways in are probed host experimental methods theoretical calculations at molecular level. One our developed (denoted as COF-4) exhibits remarkable electron utilization efficiency charge transfer properties, achieving record-high uranium extraction performance ~6.84 mg/g/day natural seawater among all techniques reported so far. This study brings new understanding operation COF-based guiding design improved photocatalysts for many applications.

Language: Английский

Citations

281
A Crystalline Partially Fluorinated Triazine Covalent Organic Framework for Efficient Photosynthesis of Hydrogen Peroxide DOI
Haozhen Wang, Chao Yang,

Fangshuai Chen

et al.

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

Published: March 1, 2022

A partially fluorinated, metal-free, imine-linked two-dimensional triazine covalent organic framework (TF50 -COF) photocatalyst was developed. Fluorine (F)-substituted and nonsubstituted units were integrated in equimolar amounts on the edge aromatic units, where they mediated two-electron O2 photoreduction. F-substitution created an abundance of Lewis acid sites, which regulated electronic distribution adjacent carbon atoms provided highly active sites for adsorption, widened visible-light-responsive range catalyst, while enhancing charge separation. Varying proportion F maximized interlayer interactions TF50 -COF, resulting improved crystallinity with faster carrier transfer robust photostability. The -COF catalyst demonstrates high selectivity stability photoreduction into H2 , a yield rate 1739 μmol h-1 g-1 remarkable apparent quantum efficiency 5.1 % at 400 nm, exceeding performance previously reported nonmetal COF-based photocatalysts.

Language: Английский

Citations

274
In situ photodeposition of platinum clusters on a covalent organic framework for photocatalytic hydrogen production DOI Creative Commons
Yimeng Li, Li Yang, Huijie He

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: March 15, 2022

Photocatalytic hydrogen production has been considered a promising approach to obtain green energy. Crystalline porous materials have arisen as key photocatalysts for efficient production. Here, we report strategy in situ photodeposit platinum clusters cocatalyst on covalent organic framework, which makes it an photocatalyst light-driven evolution. Periodically dispersed adsorption sites of species are constructed by introducing adjacent hydroxyl group and imine-N the region framework structural unit where photogenerated electrons converge, leading reduction adsorbed into metal electrons. The widespread expose large active surface greatly facilitate electron transfer, finally contributing high photocatalytic evolution rate 42432 μmol g-1 h-1 at 1 wt% loading. This work provides direction design frameworks precisely manipulate morphologies positions atomic level developing photocatalysts.

Language: Английский

Citations

272
Three-Component Donor−π–Acceptor Covalent–Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution DOI
Ziping Li, Tianqi Deng, Si Ma

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8364 - 8374

Published: March 14, 2023

Two-dimensional covalent-organic frameworks (2D COFs) have recently emerged as great prospects for their applications new photocatalytic platforms in solar-to-hydrogen conversion; nevertheless, inefficient solar energy capture and fast charge recombination hinder the improvement of hydrogen production performance. Herein, two photoactive three-component donor-π-acceptor (TCDA) materials were constructed using a multicomponent synthesis strategy by introducing electron-deficient triazine electron-rich benzotrithiophene moieties into through sp2 carbon imine linkages, respectively. Compared with two-component COFs, novel TCDA-COFs are more convenient regulating inherent photophysical properties, thereby realizing outstanding activity evolution from water. Remarkably, first carbon-linked TCDA-COF displays an impressive rate 70.8 ± 1.9 mmol g-1 h-1 excellent reusability presence 1 wt % Pt under visible-light illumination (420-780 nm). Utilizing combination diversified spectroscopy theoretical prediction, we show that full π-conjugated linkage not only effectively broadens harvesting COFs but also enhances transfer separation efficiency.

Language: Английский

Citations

247
Covalent organic frameworks for photocatalysis: Synthesis, structural features, fundamentals and performance DOI
Yun‐Nan Gong, Xinyu Guan, Hai‐Long Jiang

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 475, P. 214889 - 214889

Published: Oct. 15, 2022

Language: Английский

Citations

242
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

216
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