Oxo dicopper anchored on carbon nitride for selective oxidation of methane

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Март 16, 2022

Selective conversion of methane (CH4) into value-added chemicals represents a grand challenge for the efficient utilization rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu2@C3N4) advanced catalysts CH4 partial oxidation. The copper-dimer demonstrate high selectivity oxidation under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H2O2) oxygen (O2) being used oxidizer, respectively. In particular, O2 achieves >10% conversion, >98% toward methyl oxygenates mass-specific activity 1399.3 mmol g Cu-1h-1. Mechanistic studies reveal that reactivity Cu2@C3N4 can be ascribed to symphonic mechanisms among bridging oxygen, two sites semiconducting C3N4 substrate, which do not only facilitate heterolytic scission C-H bond, but also promotes H2O2 activation in photocatalysis,

Язык: Английский

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Methane Oxidation to Methanol

Chemical Reviews, Год журнала: 2022, Номер 123(9), С. 6359 - 6411

Опубликована: Дек. 2, 2022

The direct transformation of methane to methanol remains a significant challenge for operation at larger scale. Central this is the low reactivity conditions that can facilitate product recovery. This review discusses issue through examination several promising routes and an evaluation performance targets are required develop process We explore methods currently used, emergence active heterogeneous catalysts their design reaction mechanisms provide critical perspective on future operation. Initial experiments discussed where identification gas phase radical chemistry limited further development by approach. Subsequently, new class catalytic materials based natural systems such as iron or copper containing zeolites were explored milder conditions. key issues these technologies conversion often overoxidation products. Despite this, interest high in wider appeal effective route products from C–H activation, particularly with need transition net carbon zero renewable sources exciting.

Язык: Английский

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Au-ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2

Nature Catalysis, Год журнала: 2022, Номер 5(1), С. 45 - 54

Опубликована: Янв. 6, 2022

Язык: Английский

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Activation and conversion of alkanes in the confined space of zeolite-type materials

Chemical Society Reviews, Год журнала: 2021, Номер 50(15), С. 8511 - 8595

Опубликована: Янв. 1, 2021

Microporous zeolite-type materials are able to activate and efficiently convert stable C₁⁺alkanes. This review analyzes, at the molecular level, role of active sites contribution diffusion, shape-selectivity confinement effects.

Язык: Английский

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Methane Oxidation to Methanol in Water

Accounts of Chemical Research, Год журнала: 2021, Номер 54(11), С. 2614 - 2623

Опубликована: Май 19, 2021

ConspectusMethane represents one of the most abundant carbon sources for fuel or chemical production. However, remote geographical locations and high transportation costs result in a substantial proportion being flared at source. The selective oxidation methane to methanol remains grand challenge catalytic chemistry due large energy barrier initial C–H activation prevention overoxidation CO2. Indirect methods such as steam reforming produce CO H2 building blocks, but they consume amounts over multistage processes. This makes development low-temperature highly desirable explains why it has remained an active area research last 50 years.The thermodynamically favorable would ideally use only molecular oxygen. Nature effects this transformation with enzyme monooxygenase (MMO) aqueous solution ambient temperature addition 2 equiv reducing cofactor. MMO sites are Fe Cu oxoclusters, incorporation these metals into zeolitic frameworks can biomimetic activity. Most approaches using metal-doped zeolites oxygen N2O; however, demonstrations cycles without catalyst regeneration limited. Over 10 years, we have developed Fe-Cu-ZSM-5 materials under conditions °C H2O2 oxidant (effectively O2 + equiv), which compete terms To date, among catalysts mild condition, industrially, is expensive production methanol.This observation activity led new utilize oxidant. Supported precious metal nanoparticles been shown be range reactions H2O2, rapid decomposition surfaces limits efficiency. We identified that could minimized by removing support material carrying out reaction colloidal AuPd nanoparticles. efficiency consumption was increased 4 orders magnitude, crucially demonstrated first time incorporated produced 91% selectivity. understanding gained from two provides valuable insight possible routes will presented here context our own area.

Язык: Английский

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Role of H₂O in Catalytic Conversion of C₁ Molecules

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2857 - 2875

Опубликована: Янв. 24, 2024

Due to their role in controlling global climate change, the selective conversion of C

Язык: Английский

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In Situ UV–Vis–NIR Absorption Spectroscopy and Catalysis

Chemical Reviews, Год журнала: 2024, Номер 124(5), С. 2352 - 2418

Опубликована: Фев. 26, 2024

This review highlights

Язык: Английский

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Progress and challenges in nitrous oxide decomposition and valorization

Chemical Society Reviews, Год журнала: 2024, Номер 53(16), С. 8379 - 8423

Опубликована: Янв. 1, 2024

Nitrous oxide (N

Язык: Английский

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Current research progress and perspectives on liquid hydrogen rich molecules in sustainable hydrogen storage

Energy storage materials, Год журнала: 2020, Номер 35, С. 695 - 722

Опубликована: Дек. 11, 2020

Язык: Английский

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Recognition of Water-Induced Effects toward Enhanced Interaction between Catalyst and Reactant in Alcohol Oxidation

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(16), С. 6071 - 6078

Опубликована: Апрель 8, 2021

Pickering emulsion stabilized by solid nanoparticles provides a diverse solvent microenvironment and enables to promote the phase transfer of reaction substrates/products in catalytic reactions, but intrinsic role is still not clear. Herein, using benzyl alcohol (BA) as model reactant, we demonstrate nature water-promoted activity for oxidation over Pd/MgAl-LDO catalyst. Depending on water solvent, observe different reactivities regarding proportion system. Kinetic isotope effects confirm participation positive BA. The promotion are recognized identified vapor pulse adsorption coupled with temperature program desorption. Moreover, behavior BA or benzaldehyde at interface also investigated quasi-in-situ Raman spectroscopy. In addition, mechanism rationally proposed based Langmuir–Hinshelwood mechanism. general applicability further demonstrated supports substrates, which well achieves excellent selectivity compared that pure toluene

Язык: Английский

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