Tailoring metal–organic frameworks for photocatalytic H2O2 production

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 501, P. 215597 - 215597

Published: Dec. 11, 2023

Language: Английский

---

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

---

Building robust metal-organic frameworks with premade ligands

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 505, P. 215690 - 215690

Published: Feb. 1, 2024

Language: Английский

---

Modulating the Microenvironments of Robust Metal Hydrogen‐Bonded Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 21, 2024

Abstract Hydrogen‐bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and activity in the absence Pt cocatalyst. Herein, a series metal (Co 2 ‐HOF‐X, X=COOMe, Br, tBu OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional presence strong acid (12 M HCl) base (5 NaOH) at least 10 days. More impressively, by varying ‐X groups microenvironment Co ‐HOF‐X can be modulated, giving rise to obviously different H production rates, following −X group sequence −COOMe>−Br>−tBu>−OMe. The optimized ‐HOF‐COOMe shows generation rate up 12.8 mmol g −1 h any additional noble‐metal photosensitizers cocatalysts, is superior Pt‐assisted systems. Experiments theoretical calculations reveal that grafted possess electron‐withdrawing ability, thus regulating electronic structures catalytic centres proton activation barrier production, leading distinctly activity.

Language: Английский

---

Diffusion-programmed catalysis in nanoporous material

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 3, 2025

Abstract In the realm of heterogeneous catalysis, diffusion reactants into catalytically active sites stands as a pivotal determinant influencing both turnover frequency and geometric selectivity in product formation. While accelerated can elevate reaction rates, it often entails compromise selectivity. Porous catalysts, including metal-organic covalent organic frameworks, confront formidable obstacles regulating reactant rates. Consequently, chemical functionality catalysts typically governs This study presents an approach harnessing length to achieve improved manipulation reactant-active site residence time at augment kinetics. Through deployment thin film composed porous framework catalyst, we illustrate how programming within cross-flow microfluidic catalytic reactor concurrently amplify (exceeding 1000-fold) enhance ( ~ 2-fold) relative conventional nano/microcrystals catalyst one-pot reactor. diffusion-programed strategy represents robust solution surmount constraints imposed by bulk marking advancement design catalyst-driven reactions.

Language: Английский

---

Conductive Metal–Organic Frameworks and Their Electrocatalysis Applications

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

Recently, electrically conductive metal–organic frameworks (EC-MOFs) have emerged as a wealthy library of porous with unique properties, allowing their use in diverse applications energy conversion, including electrocatalysis. In this review, the electron conduction mechanisms EC-MOFs are examined, while electrical conductivities considered. There been various strategies to enhance MOFs ligand modification, incorporation conducting materials, and construction multidimensional architectures. With sufficient being established for EC-MOFs, there extensive pursuits electrocatalysis applications, such hydrogen evolution reaction, oxygen reduction N2 CO2 reaction. addition, computational modeling also exerts an important impact on revealing synthesis–structure–performance relationships. Finally, prospects current challenges discussed provide guidelines designing promising framework materials.

Language: Английский

---

Recent advances of ammonia synthesis under ambient conditions over metal-organic framework based electrocatalysts

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123161 - 123161

Published: Aug. 10, 2023

Language: Английский

---

Improving the removal efficiency of oxygenated volatile organic compounds by defective UiO-66 regulated with water

Journal of Hazardous Materials, Journal Year: 2024, Volume and Issue: 469, P. 134055 - 134055

Published: March 15, 2024

Language: Английский

---

Coordination environment modulation to optimize d-orbit arrangement of Mn-based MOF electrocatalyst for lithium-oxygen battery

Energy storage materials, Journal Year: 2024, Volume and Issue: 70, P. 103519 - 103519

Published: May 27, 2024

Language: Английский

---

Reticular Materials for Photocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Abstract Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional sources and has attracted significant research interest. Reticular materials, including metal‐organic frameworks (MOFs) covalent organic (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination bonds, respectively. function as heterogeneous catalysts, combining well‐defined structures high tailorability akin homogeneous catalysts. In this review, regulation light absorption, charge separation, surface in photocatalytic process through precise molecular‐level design based features reticular is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects performance delved, with emphasis their unique dynamic flexible microenvironments. For COFs, inherent excitonic effects due fully nature discussed highlight strategies regulate charge‐ and/or energy‐transfer‐mediated photocatalysis. Finally, current challenges future directions field, aiming provide comprehensive understanding how be optimized enhanced photocatalysis discussed.

Language: Английский

---