State of the Art and Prospects in Metal–Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis

Chemical Reviews, Journal Year: 2019, Volume and Issue: 120(2), P. 1438 - 1511

Published: June 27, 2019

Metal–organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability richness structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple selective heterogeneous interactions activations these MOF-based nanocatalysts. Pyrolysis MOF-nanoparticle composites forms highly N- P-doped graphitized MOF-derived that increasingly used as efficient catalysts especially electro- photocatalysis. This review first briefly summarizes this background MOF nanoparticle then comprehensively reviews fast-growing literature reported during last years. parts organic molecular reactions, electrocatalysis, photocatalysis, views prospects. Major challenges our society addressed using well-defined fields synthesis, energy, environment. In spite many achievements, enormous progress still necessary to improve understanding processes involved beyond proof-of-concept, particularly methane oxidation, hydrogen production, water splitting, CO2 reduction methanol, nitrogen fixation, depollution.

Language: Английский

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Metal–Organic Framework-Based Catalysts with Single Metal Sites

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(21), P. 12089 - 12174

Published: May 1, 2020

Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, high surface area, different types MOF-based single sites well exploited, including coordinately unsaturated from nodes metallolinkers, as active species immobilized MOFs. Furthermore, controllable thermal transformation MOFs can upgrade them nanomaterials functionalized with single-atom catalysts (SACs). These unique features derivatives enable serve highly versatile platform for catalysis, which has actually been becoming rapidly developing interdisciplinary research area. In this review, we overview the recent developments catalysis at in emphasis on structures applications thermocatalysis, electrocatalysis, photocatalysis. We also compare results summarize major insights gained works providing challenges prospects emerging field.

Language: Английский

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Glucose-oxidase like catalytic mechanism of noble metal nanozymes

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 7, 2021

Abstract Au nanoparticles (NPs) have been found to be excellent glucose oxidase mimics, while the catalytic processes rarely studied. Here, we reveal that process of oxidation catalyzed by NPs is as same natural oxidase, namely, a two-step reaction including dehydrogenation and subsequent reduction O 2 H two electrons. Pt, Pd, Ru, Rh, Ir can also catalyze glucose, except preferably reduced O. By electron transfer feature noble metal NPs, overcame limitation must produced in traditional assay realize rapid colorimetric detections glucose. Inspired transport pathway enzymes, mimic various enzymatic reactions cytochrome c, coenzymes well nitrobenzene reductions.

Language: Английский

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Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(17), P. 6273 - 6328

Published: Jan. 1, 2020

Reductive aminations constitute an important class of reactions widely applied in research laboratories and industries for the synthesis amines as well pharmaceuticals, agrochemicals biomolecules. In particular, catalytic reductive using molecular hydrogen are highly valued essential cost-effective sustainable production different kinds their functionalization. These couple easily accessible carbonyl compounds (aldehydes or ketones) with ammonia, nitro presence suitable catalysts that enable preparation linear branched primary, secondary tertiary including N-methylamines molecules used life science applications. general, represent valuable fine bulk chemicals, which serve key precursors central intermediates advanced molecules, dyes polymers. Noteworthily, amine functionalities present a large number biomolecules, play vital roles function these active compounds. challenging processes, especially syntheses primary amines, often non-selective suffer from over-alkylation reduction to corresponding alcohols. Hence, development perform efficient selective manner is crucial continues be attracts scientific interest. this regard, both homogeneous heterogeneous have successfully been developed access various amines. There need comprehensive review on discuss potential applicability methodology commercial, industrial medicinal importance. Consequently, we applications functionalized structurally diverse benzylic, heterocyclic aliphatic more complex drug targets. addition, mechanisms formation desired products possible side emphasized. This aims at communities working fields organic synthesis, catalysis, biological chemistry.

Language: Английский

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Electrochemical oxidation of biomass derived 5-hydroxymethylfurfural (HMF): pathway, mechanism, catalysts and coupling reactions

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(12), P. 4228 - 4254

Published: Jan. 1, 2021

HMF electrooxidation is emerging as a powerful and promising method to produce wide range of high-value chemicals on account mild operation conditions, controllable selectivity, scalability.

Language: Английский

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Designing High‐Valence Metal Sites for Electrochemical Water Splitting

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(16)

Published: Feb. 17, 2021

Abstract Electrochemical water splitting is a critical energy conversion process for producing clean and sustainable hydrogen; this relies on low‐cost, highly active, durable oxygen evolution reaction/hydrogen reaction electrocatalysts. Metal cations (including transition metal noble cations), particularly high‐valence that show high catalytic activity can serve as the main active sites in electrochemical processes, have received special attention developing advanced In review, heterogenous electrocatalyst design strategies based are presented, associated materials designed summarized. discussion, emphasis given to combined with modulation of phase/electronic/defect structure performance improvement. Specifically, importance using situ operando techniques track real metal‐based during highlighted. Remaining challenges future research directions also proposed. It expected comprehensive discussion electrocatalysts containing be instructive further explore other energy‐related reactions.

Language: Английский

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Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9618 - 9678

Published: July 17, 2021

Value-added chemicals, fuels, and pharmaceuticals synthesized by organic transformation from raw materials via catalytic techniques have attracted enormous attention in the past few decades. Heterogeneous catalysts with high stability, long cycling life, good environmental-friendliness, economic efficiency are greatly desired to accomplish transformations. With advantages of reversible Ce3+/Ce4+ redox pairs, tailorable oxygen vacancies, surface acid–base properties, ceria-based been actively investigated fields synthesis. In this Review, we summarize fundamentals latest applications heterogeneous for transformations thermocatalytic photocatalytic routes. The fabricating approaches various ceria their structure/composition–activity relationship discussed prospected. advanced characterization theoretical methods reaction mechanism studies over CeO2-based summarized discussed. This comprehensive Review provides a basic understanding structure–performance relationships addition, it also some insights outlooks design research direction better performance.

Language: Английский

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Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(7), P. 4259 - 4298

Published: Jan. 1, 2021

This review summarizes the concepts, mechanisms, drawbacks and challenges of state-of-the-art catalysis for CO₂ to MeOH under mild conditions. Thoughtful guidelines principles future research are presented discussed.

Language: Английский

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Highly-efficient RuNi single-atom alloy catalysts toward chemoselective hydrogenation of nitroarenes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 8, 2022

The design and exploitation of high-performance catalysts have gained considerable attention in selective hydrogenation reactions, but remain a huge challenge. Herein, we report RuNi single atom alloy (SAA) which Ru atoms are anchored onto Ni nanoparticle surface via Ru-Ni coordination accompanied with electron transfer from sub-surface to Ru. optimal catalyst 0.4% SAA exhibits simultaneously improved activity (TOF value: 4293 h-1) chemoselectivity toward 4-nitrostyrene 4-aminostyrene (yield: >99%), is, the best our knowledge, highest level compared reported heterogeneous catalysts. In situ experiments theoretical calculations reveal that interfacial sites as intrinsic active centers facilitate preferential cleavage N-O bond decreased energy barrier by 0.28 eV. addition, synergistic catalysis promotes formation intermediates (C8H7NO* C8H7NOH*) accelerates rate-determining step (hydrogenation C8H7NOH*).

Language: Английский

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Insights into the Interfacial Effects in Heterogeneous Metal Nanocatalysts toward Selective Hydrogenation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(12), P. 4483 - 4499

Published: March 16, 2021

Heterogeneous metal catalysts are distinguished by their structure inhomogeneity and complexity. The chameleonic nature of heterogeneous have prevented us from deeply understanding catalytic mechanisms at the molecular level thus developing industrial with perfect selectivity toward desired products. This Perspective aims to summarize recent research advances in deciphering complicated interfacial effects hydrogenation nanocatalysts design practical clear mechanism nearly selectivity. insights on how three key components (i.e., metal, support, ligand modifier) a nanocatalyst induce effective interfaces determining activity provided. influence not only H2 activation pathway but also interaction substrates be hydrogenated surface hydrogen transfer process. As for alloy nanocatalysts, together electronic geometric ensemble effects, spillover occurring catalytically "inert" utilizing atom active is highlighted. metal–support interface then discussed emphasis involvement ligands located as well cationic species support hydrogenation. organic modifiers, ability both 3D steric manipulate pathways demonstrated. A brief summary finally provided perspective development enzyme-like catalysts.

Language: Английский

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