Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(22), С. 7949 - 8004

Опубликована: Янв. 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.

Язык: Английский

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Atomic-level design of metalloenzyme-like active pockets in metal–organic frameworks for bioinspired catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 137 - 162

Опубликована: Ноя. 29, 2023

Natural metalloenzymes with astonishing reaction activity and specificity underpin essential life transformations. Nevertheless, enzymes only operate under mild conditions to keep sophisticated structures active, limiting their potential applications. Artificial that recapitulate the catalytic of can not circumvent enzymatic fragility but also bring versatile functions into practice. Among them, metal-organic frameworks (MOFs) featuring diverse site-isolated metal sites supramolecular have emerged as promising candidates for move toward unparalleled properties behaviour enzymes. In this review, we systematically summarize significant advances in MOF-based metalloenzyme mimics a special emphasis on active pocket engineering at atomic level, including primary secondary coordination spheres. Then, deep understanding mechanisms advanced applications are discussed. Finally, perspective emerging frontier research is provided advance bioinspired catalysis.

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2024, Номер 53(18), С. 9378 - 9418

Опубликована: Янв. 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.

Язык: Английский

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Heterogeneous Photocatalytic Strategies for C(sp³)−H Activation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Янв. 16, 2024

Abstract Activation of ubiquitous C(sp 3 )−H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers promising and sustainable approach for activation has been fast developing in the past decade. This Minireview focuses on mechanism strategies heterogeneous photocatalytic activation. After introducing mechanistic insights, including precise design active sites, regulation reactive radical species, improving charge separation reactor innovations are discussed. In addition, recent advances hydrocarbons, alcohols, ethers, amines amides by summarized. Lastly, challenges opportunities outlined to encourage more efforts development this exciting field.

Язык: Английский

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Yolk–Shell and Hollow Zr/Ce-UiO-66 for Manipulating Selectivity in Tandem Reactions and Photoreactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 17164 - 17175

Опубликована: Июль 13, 2023

One of the hallmarks multicomponent metal-organic frameworks (MOFs) is to finely tune their active centers achieve product selectivity. In particular, obtaining bimetallic MOF hollow structures with precisely tailored redox under same topology still challenging despite a recent surge such efforts. Herein, we present an engineering strategy named "cluster labilization" generate hierarchically porous composites and tunable centers. By partially replacing zirconium cerium in hexanuclear clusters UiO-66, unevenly distributed yolk-shell (YSS) were formed. Through acid treatment or annealing YSS precursor, single-shell (SSHS) double-shell (DSHS) can be obtained, respectively. The SSHS DSHS differ species, valence, spatial locations. More importantly, YSS, SSHS, distinct microenvironments exhibit catalytic activity, reversed selectivity, high stability tandem reaction photoreaction.

Язык: Английский

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Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2170 - 2182

Опубликована: Янв. 19, 2023

Nature's blueprint provides the fundamental principles for expanding use of abundant metals in catalysis; however, mimicking both structure and function copper enzymes simultaneously one artificial system selective C–H bond oxidation faces marked challenges. Herein, we report a new approach to assembly monooxygenases utilizing binuclear Cu2S2Cl2 cluster duplicate identical catalysis CuA enzyme. The designed monooxygenase Cu-Cl-bpyc facilitates well-defined redox potential that initially activated O2via photoinduced electron transfer, generated an active chlorine radical via ligand-to-metal charge transfer (LMCT) process from consecutive excitation situ formed copper(II) center. abstracts hydrogen atom selectively C(sp3)–H bonds generate intermediate; meanwhile, O2•– species interacted with mimic form mixed-valence species, giving desired oxidization products inherent product selectivity recovering catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, broad substrate scope, including some biological pharmacologically relevant targets. Mechanistic studies indicate cleavage was rate-determining step cuprous interactions were essential stabilize oxygen species. structural characters fine-modified catalytic properties open avenue develop robust uniform precise sites high performances.

Язык: Английский

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Enhancing energy transfer through visible-light-driven polymerization in a metal–organic framework

Journal of Materials Chemistry A, Год журнала: 2023, Номер 11(34), С. 18236 - 18246

Опубликована: Янв. 1, 2023

By utilizing an organic linker containing two photoactive groups, Zr-MOF with multiple photofunctionalities, such as photochromism, photo-induced structural transformation, and photo-catalysis, has been explored.

Язык: Английский

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Ultrathin 2D Cerium‐Based Metal–Organic Framework Nanosheet That Boosts Selective Oxidation of Inert C(sp³)H Bond through Multiphoton Excitation

Small, Год журнала: 2023, Номер 19(26)

Опубликована: Март 20, 2023

The development of methodologies for inducing and tailoring activities catalysts is an important issue in various catalysis. ultrathin 2D monolayer metal-organic framework (MOF) nanosheets with more accessible active sites faster diffusion obtained by exfoliating 3D layered MOFs are great potential as heterogeneous catalysts, but the rational design preparation remains a grand challenge. Herein, novel weak electrostatic interaction strategy to construct cerium-bearing MOF coordinating chlorine-capped cerium nodes linear photoactive methyl viologen (MV+ ) organic linkers used. Under multiphoton excitation, MV+ ligands CeCl chromophores triggered consecutively form high activity chlorine radical (Cl• activation inert C(sp3 )H bond through hydrogen atom transfer. Benefiting from confinement effects, synergistic effects two and/or flexibility surface utilization, observed increase order CeCl3 /MV+ < bulk crystals photocatalysis. This work not only contributes new their also paves way use nanostructured handle synergy multiple molecular catalysts.

Язык: Английский

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Mixed-valence metal–organic frameworks: concepts, opportunities, and prospects

Chemical Society Reviews, Год журнала: 2024, Номер unknown

Опубликована: Дек. 20, 2024

Mixed-valence MOFs have exhibited unique features in different practical fields, resulting from long-range charge delocalization and a tunable band gap within the framework.

Язык: Английский

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A superhydrophobic MOF facilitating efficient solvent-free catalytic chemical fixation of CO₂ and oxidation of hydrocarbons and MOF@cotton@starch composite-based selective sensing of a herbicide

Journal of Materials Chemistry C, Год журнала: 2024, Номер 12(12), С. 4460 - 4472

Опубликована: Янв. 1, 2024

Superhydrophobic Zr-MOF unveils solvent-free chemical fixation of CO 2 at 1 bar, along with efficient aerobic oxidation hydrocarbons into fine chemicals and fast, nanomolar detection aclonifen in wastewater, vegetables, fruits.

Язык: Английский

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