Three-Dimensional Covalent Organic Frameworks with Ultra-Large Pores for Highly Efficient Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 3248 - 3254

Published: Jan. 31, 2023

Benefiting from their unique structural merits, three-dimensional (3D) large-pore COF materials demonstrate high surface areas and interconnected large channels, which makes these promising in practical applications. Unfortunately, functionalization strategies application research are still absent structures. To this end, a series of functional 3D stp-topologized COFs designed based on porphyrin or metalloporphyrin moieties, named JUC-640-M (M = Co, Ni, H). Interestingly, JUC-640-H exhibits record-breaking low crystal density (0.106 cm3 g-1) among all crystalline materials, along with the largest pore size (4.6 nm) COFs, area (2204 m2 g-1), abundant exposed moieties (0.845 mmol g-1). Inspired by characteristics photoelectrical performance, JUC-640-Co is utilized for photoreduction CO2 to CO demonstrates production rate (15.1 g-1 h-1), selectivity (94.4%), stability. It should be noted that has exceeded those reported COF-based materials. This work not only produces novel channels but also provides new guidance applications COFs.

Language: Английский

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Copper-decorated covalent organic framework as a heterogeneous photocatalyst for phosphorylation of terminal alkynes

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(10), P. 4071 - 4081

Published: Jan. 1, 2022

A copper decorated covalent organic framework has been prepared and identified as an efficient heterogeneous photocatalyst for the phosphorylation of terminal alkynes.

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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Porphyrin-based metal–organic frameworks for photo(electro)catalytic CO₂ reduction

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(15), P. 5311 - 5335

Published: Jan. 1, 2024

The panorama of the latest developments emerging porphyrin-based MOFs for photo(electro)catalytic CO 2 reduction is shown.

Language: Английский

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Photophysical properties and photonic applications of porphyrin-based MOFs

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 510, P. 215794 - 215794

Published: March 28, 2024

Metal-organic frameworks (MOFs) are a notorious class of porous materials that gained significant attention in recent years due to their unique structural and rich functional properties. Porphyrin-based MOFs, PMOFs, have been studied extensively for potential applications areas such as energy storage, capture, delivery, catalysis, sensing. Particularly, this work first briefly discusses the different types porphyrin-based electronic structures, how they interact with light. Furthermore, article describes wealth photophysical events occurring MOFs leading properties sustainable upon visible-light irradiation. These include efficient light harvesting, singlet triplet emissions aggregation induced emissions, thermally activated delayed fluorescence, nonlinear optical properties, multi-photon absorption, up conversion, singlet-singlet triplet-triplet excited state annihilation, time-resolved processes, ultrafast electron transfers, exciton migration, photosensitization, photo-conductivity, photo-induced charge separation, optoelectronics, dye sensitized bulk heterojunction solar cells.

Language: Английский

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Design of porphyrin-based frameworks for artificial photosynthesis and environmental remediation: Recent progress and future prospects

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 514, P. 215944 - 215944

Published: May 16, 2024

Language: Английский

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Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

ACS Applied Nano Materials, Journal Year: 2022, Volume and Issue: 5(5), P. 6055 - 6082

Published: April 15, 2022

Porphyrin-based materials are excellent chromophores because they strongly absorb visible light and their relatively low-energy lowest unoccupied molecular orbitals thermodynamically favor photoinduced electron transfer. They can generate charge-transfer excited states with without cocatalyst(s) ease energy transfer ultrafast excitation migration. Combined synthetic accessibility, these qualities make them ideal building blocks for porous metal–organic framework (MOF)- covalent–organic (COF)-based photocatalysts to produce solar fuels. This review first describes the structures of most common porphyrinic MOFs COFs excited-state properties semiconducting behavior as well that derived composites. The generally accepted mechanisms formation H2, CH4 derivatives, N2 then reviewed, followed by detailed examples nano-MOFs nano-COFs used said purpose: characteristic parameters such rates production, turnover numbers (TONs), frequencies (TOFs), apparent quantum efficiencies described compared. shows porphyrin-based efficient solar-fuel-producing photocatalysts, characteristics comparable those nonporphyrinic MOF COF although, on some occasions, production fall short record values. Conversely, exhibit greatest TONs TOFs any or but still face shortcomings concerning selectivity in many possible side products. Importantly, while best rate photoproduction fuels has been observed from nanoscale there seem be no drastic differences (within μmol–1 h–1 mmol g–1 h–1) between microscale heterogeneous photocatalysts. observation suggests more active sites mostly located at near surface particles. Overall, nanosized show rich promising photocatalytic generating have room improvement.

Language: Английский

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Metal-organic frameworks for photocatalytical carbon dioxide reduction reaction

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 521, P. 216179 - 216179

Published: Aug. 28, 2024

Language: Английский

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Recent Developments in Porphyrin-Based Metal–Organic Framework Materials for Water Remediation under Visible-Light Irradiation

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(8), P. 4183 - 4183

Published: April 10, 2024

Access to clean drinking water is a basic requirement, and eliminating pollutants from wastewater important for saving ecosystems. The porous structure surface characteristics of metal–organic frameworks (MOFs) can function as perfect scaffold removing toxic compounds wastewater. Porphyrins are promising building blocks constructing MOFs. Porphyrin-based (P-MOFs) have been fabricated using porphyrin ligands, metal clusters, or ions. These materials harvest light wide region the solar spectrum, their framework morphology physicochemical properties be controlled by changing peripheral subunits crystalline generated interest because distinctive characteristics, including large permanent porosity, interesting morphology, broad conformational diversity, high photostability, semiconducting nature. This article discusses recent progress usefulness P-MOFs. fabrication procedures P-MOFs discussed, followed adsorptive photocatalytic removal contaminants relationships between geometries light-harvesting charge-transfer mechanisms degradation highlighted. Finally, some future perspectives obstacles in photodegradation usage along with feasible research directions standardize efficient photocatalysts improved treatment.

Language: Английский

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Covalent Organic Frameworks as Heterogeneous Photocatalysts for Cross-Coupling Reactions

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(18), P. 9619 - 9651

Published: Jan. 1, 2024

This review focuses on advances in covalent organic framework (COF) photocatalysts for cross-coupling reactions, which provide a greener catalytic route transformations.

Language: Английский

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