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

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 137 - 162

Published: Nov. 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.

Language: Английский

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MOFs materials as photocatalysts for CO2 reduction: Progress, challenges and perspectives

Carbon Capture Science & Technology, Journal Year: 2024, Volume and Issue: 11, P. 100191 - 100191

Published: Jan. 19, 2024

Photocatalytic reduction of carbon dioxide (CO2) presents a pivotal solution to address meteorological and ecological challenges. Currently, metal-organic frameworks (MOFs) with their crystalline porosity, adjustable structures, diverse chemical functionalities have garnered significant attention in the realm photocatalytic CO2 reduction. This review provides brief introduction MOF material applications Then, it undertakes comprehensive examination MOFs, summarizing key attributes, including large surface area, structural multifunctionalities, responsiveness visible light, along an analysis heterojunctions methods preparation. Additionally, elucidates fundamental principle photocatalysis reduction, encompassing both half overall reactions. Furthermore, classification MOF-based materials is explored, proposed mechanism for update on recent developments this field. Finally, outlines challenges potential opportunities utilizing MOFs offering valuable insights scholars seeking innovative approaches not only enhance but also advance other processes.

Language: Английский

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Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10798 - 10805

Published: April 5, 2024

Though the coordination environment of single metal sites has been recognized to be great importance in promoting catalysis, influence simultaneous precise modulation primary and secondary spheres on catalysis remains largely unknown. Herein, a series Ni(II) with altered have installed onto metal–organic frameworks (MOFs) UiO-67 skeleton, affording UiO–Ni–X–Y (X = S, O; Y H, Cl, CF3) X spheres, respectively. Upon deposition CdS nanoparticles, resulting composites present high photocatalytic H2 production rates, which optimized CdS/UiO–Ni–S–CF3 exhibits an excellent activity 13.44 mmol g–1, ∼500 folds pristine catalyst (29.6 μmol g–1 for CdS/UiO), 8 h, highlighting key role microenvironment around Ni sites. Charge kinetic analysis theoretical calculation results demonstrate that charge transfer dynamics reaction energy barrier are closely correlated their spheres. This work manifests advantages MOFs fabrication structurally catalysts elucidation particular influences catalytic performance.

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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Supramolecularly Built Local Electric Field Microenvironment around Cobalt Phthalocyanine in Covalent Organic Frameworks for Enhanced Photocatalysis

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

The local electric field (LEF) plays an important role in the catalytic process; however, precise construction and manipulation of microenvironment around active site remains a significant challenge. Here, we have developed supramolecular strategy for implementation LEF by introducing host macrocycle 18-crown-6 (18C6) into cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing interaction between 18C6 potassium ion (K+), locally enhanced K+ concentration CoPc can be built to generate catalytically Co site. COF with this supramolecularly realizes activity up 7.79 mmol mmolCo–1 h–1 photocatalytic CO2 reduction reaction (CO2RR), which is 180% improvement compared its counterpart without units. effect subtly controlled fully harnessing K+@18C6 changing salts different counterions. In situ spectroscopy density functional theory calculations show that complexation creates positive stabilizes critical intermediate *COOH involved CO2RR, tuned halide ion-mediated hydrogen-bonding interaction, consequently leading improved performance varying degrees.

Language: Английский

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Modification engineering over single-atom catalysts for efficient heterogeneous photocatalysis

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 529, P. 216468 - 216468

Published: Jan. 21, 2025

Language: Английский

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Metal-organic framework composites for photocatalysis

EnergyChem, Journal Year: 2023, Volume and Issue: 6(1), P. 100115 - 100115

Published: Nov. 22, 2023

Language: Английский

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Anion Modulation of Ag‐Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 20, 2024

How to achieve CO

Language: Английский

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Constructing Co and Zn atomic pairs in core-shell Co3S4/NC@ZnS/NC derived from MOF-on-MOF nanostructures for enhanced photocatalytic CO2 reduction to C2H4

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 352, P. 124019 - 124019

Published: April 21, 2024

Language: Английский

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Boosted Charge Transfer for Highly Efficient Photosynthesis of H₂O₂ over Z‐Scheme I⁻/K⁺ Co‐Doped g‐C₃N₄/Metal–Organic‐Frameworks in Pure Water under Visible Light

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(38)

Published: July 9, 2024

Abstract Photocatalytic oxygen reduction reaction (ORR) is an environmentally friendly and cost‐effective approach for H 2 O synthesis. However, the current photosynthesis system suffers from sluggish kinetics, rapid recombination of photoexcited charge carriers, weak redox potentials, resulting in unsatisfactory solar‐to‐chemical conversion efficiency. Herein, a Z‐scheme heterojunction (UiO/IKCN) constructed through coupling I − /K + co‐doped g‐C 3 N 4 (IKCN) with NH ‐UiO‐66, typical metal‐organic framework material. Under visible light irradiation, optimal UiO/IKCN exhibits exceptional production rates pure water (13.3 mM g −1 h ) isopropanol solution (72.6 ), that 48.4 times higher than pristine CN (1.5 ). A high apparent quantum yield 10.28% at 420 nm achieved by UiO/IKCN, surpassing most previously reported values. The dominating role two‐electron ORR elucidated detail. significantly enhanced photocatalytic activity can be attributed to facilitated separation transfer, which are unambiguously verified stable‐state surface photovoltage, transient photoluminescence, femtosecond absorption spectroscopy, in‐situ irradiated X‐ray photoelectron density functional theory calculations. This study represents first exploration using ‐UiO‐66 provides insights into rational design highly efficient photosynthesis.

Language: Английский

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