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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The photocatalytic H2O2 production by metal-free photocatalysts under visible-light irradiation

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 341, P. 123271 - 123271

Published: Sept. 6, 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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Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 26, 2024

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction H2O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able directly synthesize H2O2 (4784 μmol h-1 g-1 at λ > 400 nm) oxygen and alkaline water (pH = 13) in absence any sacrificial reagents. The strong alkalinity resulted formation OH-(H2O)n clusters water, were adsorbed on keto moieties within then dissociated into O2 active hydrogen, because was largely lowered. produced reacted with generate anthrahydroquinone, subsequently oxidized by produce H2O2. This study ultimately sheds light importance H2O for demonstrates synthesis achievable under conditions.

Language: Английский

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A photocatalytic redox cycle over a polyimide catalyst drives efficient solar-to-H2O2 conversion

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 22, 2024

Abstract Circumventing the conventional two-electron oxygen reduction pathway remains a great problem in enhancing efficiency of H 2 O photosynthesis. A promising approach to achieve outstanding photocatalytic activity involves utilization redox intermediates. Here, we engineer polyimide aerogel photocatalyst with photoreductive carbonyl groups for non-sacrificial production. Under photoexcitation, on surface are reduced, forming an anion radical intermediate. The produced intermediate is oxidized by produce and subsequently restores group. high catalytic ascribed cycle mediated anion, which not only promotes adsorption but also lowers energy barrier reaction generation. An apparent quantum yield 14.28% at 420 ± 10 nm solar-to-chemical conversion 0.92% achieved. Moreover, demonstrate that mere 0.5 m self-supported exposed natural sunlight 6 h yields significant production 34.3 mmol −2 .

Language: Английский

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Anthraquinone centers modified covalent organic frameworks for boosted photocatalytic O2-to-H2O2 synthesis: Inhibiting the in-situ decomposition of H2O2

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 481, P. 148494 - 148494

Published: Jan. 4, 2024

Language: Английский

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Synergistic Interfacial Reconstruction and Surface Polarization in a Compact ZnIn₂S₄–CdIn₂S₄ Heterojunction for Enhanced Photocatalytic H₂O₂ Production

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7726 - 7735

Published: May 2, 2024

Constructing compact heterostructures proves to be a productive approach achieving charge separation and photocatalytic efficiency. However, the stochastic nature of interface orientation lattice mismatch in an apparently heterostructure often misleads carrier migration molecular activation interface. Here, S defect-enriched ZnIn2S4–CdIn2S4 heterojunctions were prepared for H2O2 production. Notably, this study utilized only water oxygen as raw materials without additional reagents, yield 843.02 μmol g–1 h–1. A plethora experimental results substantiate that existence internal stress initiates restructuring interwoven surface misfit dislocation networks. On one hand, interfacial coherency establishes central transmission channel significantly mitigate transfer resistance caused by vacancies. Furthermore, induces structural reconstruction enhance polarization adsorption O2, well reduce reaction energy. Our findings offer valuable insights into underlying mechanism governing activity through uncover relationship between compacted

Language: Английский

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Progress and perspective on covalent organic frameworks for photo-catalytic hydrogen peroxide production

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(7), P. 100963 - 100963

Published: July 1, 2024

Language: Английский

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Facile Transformation of Imine Linkages and Functionalization of Aldehyde in the Covalent Organic Frameworks for Stable and Enhanced Photocatalytic Hydrogen Peroxide Production

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Imine-based covalent organic frameworks (COFs) have been widely applied in photocatalytic hydrogen peroxide (H2O2) production because of their highly crystalline properties and tunable chemical structures. However, the inherent polarization C═N linkage brings a high energy barrier for π-electron delocalization, impeding in-plane photoelectron transfer process, which leads to an inadequate efficiency H2O2 photosynthesis. In addition, stability most imine-COFs remains insufficient due reversible nature imine linkage. Herein, quinoline-linked COF (Ald-TTB-TTA) bearing polar aldehyde groups was constructed by postsynthetic conversion (TTB-TTA). The expanded conjugate planes facilitate charge transfer, accelerating proton-coupled electron oxygen reduction reaction (ORR) process. As expected, Ald-TTB-TTA achieves considerable rate 3169 μmol g–1 h–1 without sacrificial agent, surpassing its imine-linked counterpart (1944 h–1). Therefore, this work provides facile strategy designing functional COFs is expected aid construction high-performance catalysts photosynthesis H2O2.

Language: Английский

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Tuning the interlayer stacking of a vinylene-linked covalent organic framework for enhancing sacrificial agent-free hydrogen peroxide photoproduction

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This work reports an efficient strategy to tailor the stacking mode in 2D vinylene-linked covalent triazine frameworks by regulating base-catalyst with different alkali-metal ions.

Language: Английский

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