Tailored Pore-confined Single-site Iron(III) Catalyst for Selective CH Oxidation to CHOH or CHCOH Using O

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Nov 12

PMID 39532873

Authors

Manav Chauhan

Bharti Rana

Poorvi Gupta

Rahul Kalita

Chhaya Thadhani

Kuntal Manna

Affiliations

Soon will be listed here.

Abstract

Direct oxidation of methane to valuable oxygenates like alcohols and acetic acid under mild conditions poses a significant challenge due to high C‒H bond dissociation energy, facile overoxidation to CO and CO and the intricacy of C-H activation/C-C coupling. In this work, we develop a multifunctional iron(III) dihydroxyl catalytic species immobilized within a metal-organic framework (MOF) for selective methane oxidation into methanol or acetic acid at different reaction conditions using O. The active-site isolation of monomeric Fe(OH) species at the MOF nodes, their confinement within the porous framework, and their electron-deficient nature facilitate chemoselective C‒H oxidation, yielding methanol or acetic acid with high productivities of and , respectively. Experiments and theoretical calculations suggest that methanol formation occurs via a Fe-Fe-Fe catalytic cycle, whereas CHCOH is produced via hydrocarboxylation of in-situ generated CHOH with CO and H, and direct CH carboxylation with CO.

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