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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Direct Assembly of Metal‐Phenolic Network Nanoparticles for Biomedical Applications

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Oct. 6, 2023

Coordination assembly offers a versatile means to developing advanced materials for various applications. However, current strategies assembling metal-organic networks into nanoparticles (NPs) often face challenges such as the use of toxic organic solvents, cytotoxicity because synthetic ligands, and complex synthesis procedures. Herein, we directly assemble NPs using metal ions polyphenols (i.e., metal-phenolic (MPNs)) in aqueous solutions without templating or seeding agents. We demonstrate role buffers (e.g., phosphate buffer) governing NP formation engineering physicochemical properties tunable sizes from 50 270 nm) by altering conditions. A library MPN is prepared natural ions. Diverse functional cargos, including anticancer drugs proteins with different molecular weights isoelectric points, are readily loaded within applications biocatalysis, therapeutic delivery) direct mixing, surface modification, owing strong affinity guest molecules. This study provides insights mechanism complexes simple strategy engineer nanosized desired diverse biotechnological

Language: Английский

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Molecular Co-Catalyst Confined within a Metallacage for Enhanced Photocatalytic CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2275 - 2285

Published: Jan. 12, 2024

The construction of structurally well-defined supramolecular hosts to accommodate catalytically active species within a cavity is promising way address catalyst deactivation. resulting catalysts can significantly improve the utilization catalytic sites, thereby achieving highly efficient chemical conversion. In this study, Co-metalated phthalocyanine (

Language: Английский

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Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(18), P. 9378 - 9418

Published: Jan. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Language: Английский

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Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 19, 2024

Abstract The self‐assembled metal‐organic cages (MOCs) have been evolved as a paradigm of enzyme‐mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components constitute microenvironments characteristic enzymatic spatial confinement versatile host–guest interactions, thus facilitating unconventional transformations via unique driving‐forces such weak noncovalent binding electron/energy transfer. Recently, MOC‐based photoreactors emerged burgeoning platform supramolecular photocatalysis, displaying anomalous reactivities selectivities distinct from bulk solution. This perspective recaps two decades journey the photoinduced radical reactions by using photoactive (PMOCs) artificial reactors, outlining how cage‐confined photocatalysis was stoichiometric photoreactions photocatalytic turnover, high‐energy UV‐irradiation sustainable visible‐light photoactivation, simple multi‐level chemo‐ stereoselectivities. We will focus on PMOCs that merge structural functional biomimicry into single‐cage behave multi‐role photoreactors, emphasizing their potentials tackling current challenges through single‐electron transfer (SET) or energy (EnT) pathways simple, green while feasible manner.

Language: Английский

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Switchover from singlet oxygen to superoxide radical through a photoinduced two-step sequential energy transfer process

Chemical Science, Journal Year: 2024, Volume and Issue: 15(5), P. 1870 - 1878

Published: Jan. 1, 2024

We present an efficient method for the transformation of type II photosensitizers ( 1 O 2 ) into I (O ˙− through implementation artificial light-harvesting system involving a two-step sequential energy transfer process.

Language: Английский

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Guest‐Regulated Generation of Reactive Oxygen Species from Porphyrin‐Based Multicomponent Metallacages for Selective Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 2, 2024

Abstract The development of novel materials for highly efficient and selective photocatalysis is crucial their practical applications. Herein, we employ the host‐guest chemistry porphyrin‐based metallacages to regulate generation reactive oxygen species further use them photocatalytic oxidation benzyl alcohols. Upon irradiation, sole metallacage ( 6 ) can generate singlet 1 O 2 effectively via excited energy transfer, while its complex with C 70 ⊃C opens a pathway electron transfer promote formation superoxide anion (O ⋅ − ), producing both . addition 4,4′‐bipyridine (BPY) forms more stable ⊃BPY) coordination Zn‐porphyrin faces BPY, which drives fullerenes out cavities restores ability generation. Therefore, alcohols are oxidized into aldehydes upon irradiation in presence or ⊃BPY, they benzoic acids when employed as photosensitizing agent. This study demonstrates strategy that utilizes photooxidation reactions, could utilization related complexes

Language: Английский

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Heterometallic cages: synthesis and applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 25 - 46

Published: Dec. 1, 2023

The general methods used for synthesizing heterometallic cages are described. intrinsic properties and applications of these as host–guest systems catalysts also examined.

Language: Английский

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Multi-channel charge transfer in self-supporting B-g-C3Nx/Bi2S3/CdS dual S-scheme heterojunction toward enhanced photothermal-photocatalytic performance

Nano Energy, Journal Year: 2023, Volume and Issue: 120, P. 109164 - 109164

Published: Dec. 5, 2023

Language: Английский

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Isoreticular Preparation of Tetraphenylethylene‐based Multicomponent Metallacages towards Light‐Driven Hydrogen Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 19, 2023

Abstract Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal‐coordination‐driven self‐assembly, we report preparation a series isoreticular tetraphenylethylene‐based metallacages, which are well characterized by multinuclear NMR, ESI‐TOF‐MS and single‐crystal X‐ray diffraction techniques. The suitable integration photosensitizing tetraphenylethylene units as faces Re catalytic complexes pillars into single metallacage offers high photocatalytic hydrogen production rate 1707 μmol g −1 h , is one highest values among reported metallacages. Femtosecond transient absorption DFT calculations reveal that serve platform precise organized arrangement two blocks, enabling efficient directional electron transfer highly performance. This study provides general strategy multifunctional ligands certain improve efficiency production, will guide future design towards photocatalysis.

Language: Английский

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