Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(22), P. 7949 - 8004

Published: Jan. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

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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Enhanced Charge Transfer Process and Photocatalytic Activity over a Phosphonate‐based MOF via Amorphization Strategy

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

Published: Feb. 16, 2024

Recently, amorphous materials have gained great attention as an emerging kind of functional material, and their characteristics such isotropy, absence grain boundaries, abundant defects are very likely to outrun the disadvantages crystalline counterparts, low conductivity, ultimately lead improved charge transfer efficiency. Herein, we investigated effect amorphization on process photocatalytic performance with a phosphonate-based metal-organic framework (FePPA) research object. Comprehensive experimental results suggest that compared FePPA, FePPA has more distorted metal nodes, which affects electron distribution consequently improves photogenerated separation Meanwhile, nodes in also greatly promote adsorption activation O

Language: Английский

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Metal–cyanide hybrid materials exhibiting photochromic and photomagnetic responses based on viologen receptors

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(17), P. 6326 - 6332

Published: Jan. 1, 2024

A photochromic material based on viologen was synthesized. During the photo-induced color transition, DC magnetic susceptibility enhanced by 48%, and an increase in relaxation time after illumination observed.

Language: Английский

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Polyoxometalate-Embedded Metal–Organic Framework as an Efficient Copper-Based Monooxygenase for C(sp³)–H Bond Oxidation via Multiphoton Excitation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(15), P. 9969 - 9978

Published: July 17, 2023

The complex and precise structure of natural monooxygenases makes it difficult to clone their activity, the reported artificial copper-based monooxygenase catalysts for oxidation inert C(sp3)–H bonds exhibit limited catalytic activities. Inspired by monooxygenases, we report a metal–organic framework (SiW12@CuMOF-1) comprising binuclear copper HAT catalyst, photosensitizing nicotinamide adenine dinucleotide (NAD+) mimic bridging ligand, embedded polyoxometalate. SiW12@CuMOF-1 accelerates oxidative dehydrogenation 3,5-DTBC with efficiency comparable that polyphenol oxidase. In presence pyridine hydrochloride, irradiation afforded highly active chlorine radical CuI species via ligand-to-metal charge transfer process. abstracts hydrogen atom selectively from generate intermediate. interacted oxygen 1O2 formed photoinduced energy excited state NAD+ mimics, giving O2•– further oxidization. well-modified sites cleave O–O bond give final products selectively. Meanwhile, polyoxometalates alcohol substrates bonding interactions help conversion high efficiency. well-defined structural characters, finely modified properties, sustainable multiphoton excitation photocatalytic processes provide new avenue develop robust enzymes uniform improved performances.

Language: Английский

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Modifying the Oxidative Potentials of Imines in a Dye Loaded Capsule for Photocatalytic Cyclization with Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 13, 2024

Abstract Modifying redox potential of substrates and intermediates to balance pairs steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration iridium photosensitizer imine substrate within one packet a metal‐organic capsule shift the potentials substrate, herein, we reported multiphoton enzymatic strategy generation heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated pre‐equilibrium substrate‐involving clathrate that cathodic shifts oxidation substrate‐dye‐host ternary complex configuration inversion via spatial constraints in confined space. new two photon excitation enabled precise control electron transfer between each pair (photosensitizer, capsule), endowing catalytic system proceeding smoothly with an fashion. Three kinds 2‐subsituted (−OH, −NH 2 , −SH) imines N‐aryl enamines all give corresponding cyclization products efficiently under visible light irradiation, demonstrating promising microenvironment driven thermodynamic activation host‐dye‐substrate synergistic combination photocatalytic transformations.

Language: Английский

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Series of Viologen-Based Metal–Organic Polyhedra with Photo/Electrochromic Behavior for Inkless Printing and UV Detection

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(15), P. 6692 - 6700

Published: April 4, 2024

The fabrication of molecular crystalline materials with fast, multistimuli-responsive behavior and the construction corresponding structure–activity relationship are extraordinary significance for development smart materials. In this context, three functional metal–organic polyhedra (MOP), {[Dy2(bcbp)3(NO3)1.5(H2O)7]·Cl4.2·(NO3)0.3·H2O}n (1), {[Dy2(bcbp)4(H2O)8]Cl6}n (2), {[Eu2(bcbp)4(H2O)10]Cl6·H2O}n (3; bcbp = 1,1′-bis(4-carboxyphenyl)-4,4′-bipyridinium), were successfully prepared characterized. All compounds exhibit rapid reversible photochromic electrochromic dual-responsive behaviors. Furthermore, benefiting from well-defined crystal structure different responsive behaviors, photoinduced electron transfer (PIET) process explored. addition, considering excellent performance, function filter paper organic glass used ink-free printing UV light detection.

Language: Английский

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Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 511, P. 215868 - 215868

Published: April 22, 2024

Language: Английский

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Enhanced Charge Transfer Process and Photocatalytic Activity over a Phosphonate‐based MOF via Amorphization Strategy

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(15)

Published: Feb. 16, 2024

Abstract Recently, amorphous materials have gained great attention as an emerging kind of functional material, and their characteristics such isotropy, absence grain boundaries, abundant defects are very likely to outrun the disadvantages crystalline counterparts, low conductivity, ultimately lead improved charge transfer efficiency. Herein, we investigated effect amorphization on process photocatalytic performance with a phosphonate‐based metal–organic framework (FePPA) research object. Comprehensive experimental results suggest that compared FePPA, FePPA has more distorted metal nodes, which affects electron distribution consequently improves photogenerated separation Meanwhile, nodes in also greatly promote adsorption activation O 2 . Hence, exhibits better C(sp 3 )−H bond for selective oxidation toluene benzaldehyde. This work illustrates advantages MOFs process, is conducive further development high MOFs‐based photocatalysts.

Language: Английский

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2D Co-Based Metal–Organic Framework Nanosheets for the One-Pot Synthesis of Cyclic Carbonates from Olefins and CO₂

Industrial & Engineering Chemistry Research, Journal Year: 2024, Volume and Issue: 63(13), P. 5629 - 5636

Published: March 22, 2024

One-pot catalysis of olefins and CO2 provides an economical energy-efficient way for the fixation production cyclic carbonates. In this work, a two-dimensional Co-1,4-benzenedicarboxylate MOF (2D CoBDC) was synthesized via facile solvothermal reflux method further examined in one-pot synthesis The results activity evaluations detailed kinetics showed that 2D CoBDC exhibited enhanced catalytic performance (92% styrene conversion 85% carbonate yield) under cocatalyst-free conditions 100 °C, 1 bar, 12 h, compared with 3D counterpart. from effectiveness factors Thiele modulus revealed full utilization negligible mass transfer limitations catalyst. A recycle experiment confirmed excellent reusability little loss after at least 5 runs. Finally, possible mechanism reaction catalyzed by proposed.

Language: Английский

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