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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MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(3), P. 1045 - 1097

Published: Jan. 1, 2022

This review illustrates molecular-scale confinement, containment, isolation, and related concepts to present MOF-centric catalysts realize desired chemical transformations.

Language: Английский

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Electronic Structure Modeling of Metal–Organic Frameworks

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(16), P. 8641 - 8715

Published: July 16, 2020

Owing to their molecular building blocks, yet highly crystalline nature, metal-organic frameworks (MOFs) sit at the interface between molecule and material. Their diverse structures compositions enable them be useful materials as catalysts in heterogeneous reactions, electrical conductors energy storage transfer applications, chromophores photoenabled chemical transformations, beyond. In all cases, density functional theory (DFT) higher-level methods for electronic structure determination provide valuable quantitative information about properties that underpin functions of these frameworks. However, there are only two general modeling approaches conventional software packages: those treat extended, periodic solids, discrete molecules. Each approach has features benefits; both have been widely employed understand emergent chemistry arises from formation interface. This Review canvases date, with emphasis placed on application explore reactivity electron using periodic, molecular, embedded models. includes (i) computational considerations such how functional, k-grid, other model variables selected insights into MOF properties, (ii) extended solid models MOFs rather than molecules, (iii) mechanics cluster extraction subsequent enabled by models, (iv) catalytic studies solids clusters thereof, (v) embedded, mixed-method approaches, which simulate a fraction material one level remainder another dissimilar theoretical implementation.

Language: Английский

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Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(23), P. 9292 - 9304

Published: May 22, 2019

Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal–organic framework (MOF) via cation exchange subsequent oxidation 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol 150–200 °C. At 150 1 bar methane, approximately a third centers involved methanol. Methanol productivity increased by 3–4-fold selectivity from 70% 90% increasing pressure 40 bar. Density functional theory showed that reaction pathways on various sites able convert methanol, oxyl with much lower free energies activation. Combining studies stoichiometric activity characterization situ X-ray absorption spectroscopy density theory, we conclude dehydrated formed after activation responsible activity.

Language: Английский

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Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(4), P. 2182 - 2234

Published: Feb. 4, 2021

Oxidative dehydrogenation of propane to propylene can be achieved using conventional, oxygen-assisted (O2–ODHP) or via the use soft oxidants, such as CO2, N2O, S-containing compounds, and halogens/halides. The major roles oxidants include inhibiting overoxidation improving selectivity, which are considered current challenges in O2-assisted dehydrogenation. For both CO2– N2O–ODHP reactions, significant efforts have been devoted developing redox-active (e.g., chromium, vanadate, iron, etc.), nonredox-type main group metal oxide IIIA, gallium), other transition metal/metal catalysts molybdenum, palladium platinum, rhodium, ruthenium, well zeolite-based with adjustable acid–base properties, unique pore structures, topologies. Metal sulfides shown promising performance DHP, whereas development suitable has lagged for SO2- S-assisted ODHP. Recently, focused on homogeneous heterogeneous ODHP halogens Br2, I2, Cl2, etc.) hydrogen halides HCl HBr) facile processes C3H6 synthesis. This Review aims provide a critical, comprehensive review recent advances oxidative these particularly highlighting state understanding following factors: (i) relationships between composition, structure, catalytic performance, (ii) effects support, acidity, promoters, (iii) reaction pathway mechanistic insights, (iv) various oxidants. Theoretical computational insights toward mechanisms catalyst design principles also covered. Future research opportunities discussed terms synthesis, deactivation regeneration, mechanisms, alternative approaches.

Language: Английский

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Structure–Activity Relationships That Identify Metal–Organic Framework Catalysts for Methane Activation

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(4), P. 3576 - 3587

Published: March 8, 2019

In this work, we leverage advances in computational screening based on periodic density functional theory (DFT) to study a diverse set of experimentally derived metal–organic frameworks (MOFs) with accessible metal sites for the oxidative activation methane. We find that thermodynamic favorability forming metal-oxo active site has strong, inverse correlation reactivity toward C–H bond wide range MOFs. This scaling relationship is found hold over MOFs varying coordination environments and compositions, provided bonds framework atoms are conserved. The need conserve an important constraint correlations but also demonstrates route intentionally break generate novel catalytic reactivity. Periodic trends observed across data screened MOFs, later transition metals less stable more reactive sites. Collectively, results work provide robust rules-of-thumb choosing investigate methane at moderate reaction conditions.

Language: Английский

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Metal–organic frameworks as catalysts and biocatalysts for methane oxidation: The current state of the art

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 481, P. 215042 - 215042

Published: Feb. 9, 2023

Language: Английский

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Progress and challenges in nitrous oxide decomposition and valorization

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(16), P. 8379 - 8423

Published: Jan. 1, 2024

Nitrous oxide (N

Language: Английский

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Direct Methane to Methanol Conversion: An Overview of Non‐Syn Gas Catalytic Strategies

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Abstract Direct methane to methanol conversion is a dream reaction in industrial chemistry, which takes inspiration from the biological production catalysed by monooxygenase enzymes (MMOs). Over years, extensive studies have been conducted on this topic bioengineering MMOs, and tailoring methods isolate MMOs active form. Similarly, remarkable achievements noted other activation strategies such as use of heterogeneous catalysts or molecular catalysts. In review, we outline metabolism performed methanotrophs detail latest advancements site structures catalytic mechanisms both types MMOs. Also, recent progress bioinspired approaches using various catalysts, especially first‐row transition metal zeolites mechanistic insights are discussed. addition, complexes “Periana catalyst” for through methyl ester formation presence strong acids also detailed. Compared zeolites‐mediated field, utilisation application still its nascent phase further research required overcome limitations these effectively.

Language: Английский

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Catalytic Oxidation of Methane to Oxygenated Products: Recent Advancements and Prospects for Electrocatalytic and Photocatalytic Conversion at Low Temperatures

Advanced Science, Journal Year: 2020, Volume and Issue: 7(23)

Published: Oct. 27, 2020

Methane is an important fossil fuel and widely available on the earth's crust. It a greenhouse gas that has more severe warming effect than CO

Language: Английский

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