Solar‐to‐H₂O₂ Catalyzed by Covalent Organic Frameworks

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

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Covalent Organic Frameworks Containing Dual O₂Reduction Centers for Overall Photosynthetic Hydrogen Peroxide Production

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

Published: Dec. 28, 2022

Covalent organic frameworks (COFs) are highly desirable for achieving high-efficiency overall photosynthesis of hydrogen peroxide (H2 O2 ) via molecular design. However, precise construction COFs toward photosynthetic H2 remains a great challenge. Herein, we report the crystalline s-heptazine-based (HEP-TAPT-COF and HEP-TAPB-COF) with separated redox centers efficient production from pure water. The spatially orderly active sites in HEP-COFs can efficiently promote charge separation enhance photocatalytic production. Compared HEP-TAPB-COF, HEP-TAPT-COF exhibits higher efficiency integrating dual reduction s-heptazine triazine moieties. Accordingly, bearing remarkable solar-to-chemical energy 0.65 % high apparent quantum 15.35 at 420 nm, surpassing previously reported COF-based photocatalysts.

Language: Английский

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Thiophene‐Containing Covalent Organic Frameworks for Overall Photocatalytic H₂O₂ Synthesis in Water and Seawater

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: Aug. 1, 2023

H2 O2 is a significant chemical widely utilized in the environmental and industrial fields, with growing global demand. Without sacrificial agents, simultaneous photocatalyzed synthesis through oxygen reduction reaction (ORR) water oxidation (WOR) dual channels from seawater green sustainable but still challenging. Herein, two novel thiophene-containing covalent organic frameworks (TD-COF TT-COF) were first constructed served as catalysts for via indirect 2e- ORR direct WOR channels. The photocatalytic production performance can be regulated by adjusting N-heterocycle modules (pyridine triazine) COFs. Notably, no just using air raw materials, TD-COF exhibited high yields of 4060 μmol h-1 g-1 3364 deionized natural seawater, respectively. Further computational mechanism studies revealed that thiophene was primary photoreduction unit ORR, while benzene ring (linked to imine bond) central photooxidation WOR. current work exploits COFs overall provides fresh insight into creating innovative photocatalyzing synthesis.

Language: Английский

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An organic perspective on photocatalytic production of hydrogen peroxide

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(7), P. 553 - 558

Published: July 25, 2023

Language: Английский

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Regulating Relative Nitrogen Locations of Diazine Functionalized Covalent Organic Frameworks for Overall H₂O₂ Photosynthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 26, 2023

Nitrogen-heterocycle-based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H2 O2 ). However, effects relative nitrogen locations remain obscured and photocatalytic performances COFs need to be further improved. Herein, a collection functionalized by various diazines including pyridazine, pyrimidine, pyrazine have been judiciously designed synthesized photogeneration H2 without sacrificial agents. Compared with pyrimidine pyrazine, pyridazine embedded in TpDz tends stabilize endoperoxide intermediate species, leading toward more efficient direct 2e- oxygen reduction reaction (ORR) pathway. Benefiting from effective electron-hole separation, low charge transfer resistance, high-efficiency ORR pathway, an excellent production rate 7327 μmol g-1 h-1 solar-to-chemical conversion (SCC) value 0.62 % has achieved TpDz, which ranks one best COF-based photocatalysts. This work might shed fresh light on rational design functional targeting photocatalysts production.

Language: Английский

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Design of metal-organic framework catalysts for photocatalytic hydrogen peroxide production

Chem, Journal Year: 2022, Volume and Issue: 8(11), P. 2924 - 2938

Published: Nov. 1, 2022

Language: Английский

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Solar Light Driven H₂O₂ Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

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

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Conjugated Organic Polymers with Anthraquinone Redox Centers for Efficient Photocatalytic Hydrogen Peroxide Production from Water and Oxygen under Visible Light Irradiation without Any Additives

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(20), P. 12954 - 12963

Published: Oct. 11, 2022

The photocatalytic generation of hydrogen peroxide (H2O2) from H2O and O2 under visible light irradiation is a hopeful approach to achieve solar-to-chemical energy transformation. While the lack specific redox reaction centers still main reason for low H2O2 production efficiency, herein, we present conjugated organic polymer (AQTEE-COP) containing anthraquinone by Sonogashira cross-coupling between 2,6-dibromoanthraquinone (AQ) 1,1,2,2-tetrakis(4-ethynylphenyl)ethene. extended π-conjugated framework with an electron push–pull effect electron-donating tetraphenylethene moieties electron-withdrawing not only broadened absorption range but also promoted separation migration photo-induced charge carriers. Meanwhile, can serve as accept electrons transfer them adsorbed molecules subsequent production. well-defined structure AQTEE-COP task-specific anthracene provides molecular-level insights into mechanistic understanding O2. exhibits efficient initial rate 3204 μmol g–1 h–1 (λ ≥ 400 nm) without any additional photosensitizers, scavengers, or co-catalysts. This article protocol rational design pre-functionalized polymer-based materials

Language: Английский

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Highly crystalline carbon nitrogen polymer with a strong built-in electric fields for ultra-high photocatalytic H2O2 production

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 342, P. 123340 - 123340

Published: Sept. 26, 2023

Language: Английский

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Covalent Organic Frameworks Enable Sustainable Solar to Hydrogen Peroxide

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

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