Molecular Level Modulation of Anthraquinone‐containing Resorcinol‐formaldehyde Resin Photocatalysts for H2O2 Production with Exceeding 1.2 % Efficiency DOI Creative Commons
Chen Zhao, Xinyao Wang, Yanfeng Yin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(12)

Published: Dec. 29, 2022

Abstract Designing polymeric photocatalysts at the molecular level to modulate photogenerated charge behavior is a promising and challenging strategy for efficient hydrogen peroxide (H 2 O ) photosynthesis. Here, we introduce electron‐deficient 1,4‐dihydroxyanthraquinone (DHAQ) into framework of resorcinol‐formaldehyde (RF) resin, which modulates donor/acceptor ratio from perspective design promoting separation. Interestingly, H can be produced via oxygen reduction water oxidation pathways, verified by isotopic labeling in situ characterization techniques. Density functional theory (DFT) calculations elucidate that DHAQ reduce energy barrier production. RF‐DHAQ exhibits excellent overall photosynthesis with solar‐to‐chemical conversion (SCC) efficiency exceeding 1.2 %. This work opens new avenue high‐efficiency artificial

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

436

Photocatalytic H2O2 production Systems: Design strategies and environmental applications DOI
Zhong Chen,

Ducheng Yao,

Chengcheng Chu

et al.

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 451, P. 138489 - 138489

Published: Aug. 5, 2022

Language: Английский

Citations

349

Accelerated Synthesis and Discovery of Covalent Organic Framework Photocatalysts for Hydrogen Peroxide Production DOI Creative Commons
Wei Zhao, Peiyao Yan, Boyu Li

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(22), P. 9902 - 9909

Published: May 30, 2022

A high-throughput sonochemical synthesis and testing strategy was developed to discover covalent organic frameworks (COFs) for photocatalysis. In total, 76 conjugated polymers were synthesized, including 60 crystalline COFs of which 18 previously unreported. These then screened photocatalytic hydrogen peroxide (H2O2) production using water oxygen. One these COFs, sonoCOF-F2, found be an excellent photocatalyst H2O2 even in the absence sacrificial donors. However, after long-term tests (96 h), imine sonoCOF-F2 transformed into amide-linked COF with reduced crystallinity loss electronic conjugation, decreasing activity. When benzyl alcohol introduced form a two-phase catalytic system, photostability greatly enhanced, leading stable at least 1 week.

Language: Английский

Citations

347

Piperazine-Linked Metalphthalocyanine Frameworks for Highly Efficient Visible-Light-Driven H2O2 Photosynthesis DOI

Qianjun Zhi,

Wenping Liu, Rong Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21328 - 21336

Published: Nov. 9, 2022

Artificial photosynthesis of H2O2 from O2 reduction provides an energy-saving, safe, and green approach. However, it is still critical to develop highly active selective 2e– oxygen reaction photocatalysts for efficient production owing the unsatisfactory productivity. Herein, two new two-dimensional piperazine-linked CoPc-based covalent organic frameworks (COFs), namely, CoPc-BTM-COF CoPc-DAB-COF, were afforded nucleophilic substitution hexadecafluorophthalocyaninato cobalt(II) (CoPcF16) with 1,2,4,5-benzenetetramine (BTM) or 3,3′-diaminobenzidine (DAB). Powder X-ray diffraction analysis in combination electron microscopy a series spectroscopic technologies reveals their crystalline porous framework fully conjugated structure eclipsed π-stacking model. Ultraviolet–visible diffuse reflectance absorption spectra unveil excellent light capacity wide range 400–1000 nm. This, together enhanced photo-induced charge separation transport efficiency as disclosed by photocurrent response photoluminescence measurements, endows as-prepared COFs superior photocatalytic activity toward O2-to-H2O2 conversion under visible-light irradiation (λ > 400 nm). In particular, exhibits record-high yield 2096 μmol h–1 g–1 among COF-based impressive apparent quantum 7.2% at 630 The present result should be helpful fabricating high-performance low-cost visible-light-driven photosynthesis.

Language: Английский

Citations

252

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

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

203

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

193

Photocatalytic hydrogen peroxide evolution: What is the most effective strategy? DOI
Wenying Yu, Cheng Hu, Liqi Bai

et al.

Nano Energy, Journal Year: 2022, Volume and Issue: 104, P. 107906 - 107906

Published: Oct. 19, 2022

Language: Английский

Citations

192

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

186

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

178