Issue 8, 2023

Theoretical exploration of the origin of selectivity for the oxidative carbonylation reaction catalyzed by a single Pd atom embedded on graphene

Abstract

The vapor-phase carbonylation of methyl nitrite (MN) can selectively give dimethyl carbonate (DMC) or dimethyl oxalate (DMO) when using Pd-based catalysts. Density functional theory calculations were performed to explore the origin of this selectivity and its relationship with the electronic structures of the Pd centers by employing a catalytic model of a single Pd atom embedded on graphene. Through a systematic study, Pd–COOCH3 is identified as a key intermediate which plays two roles in the reaction. The nucleophilicity of the Pd–C bond of Pd–COOCH3 enables carbonylation with CO to give DMO, while the electrophilicity of the π* orbital of the carbonyl species, *COOCH3, allows coupling with MN to afford DMC. This two-fold reactivity could be regulated by the local coordination environments of the Pd centers. Pd centers each embedded on either a graphene defect, N-doped graphene, or oxidized graphene, Pd1@C3, Pd1@N3, and Pd1@O3, respectively, were investigated to understand the effect of the local coordination environment on the reaction. The calculation results show that the electron-donating nature of Pd1@N3 enhances the nucleophilicity of the Pd–C bond and promotes the activity and selectivity toward DMO production, while the electron-withdrawing nature of Pd1@O3 has an inhibitory effect. The current study will find applications as a theoretical guide for the rational design of related catalysts.

Graphical abstract: Theoretical exploration of the origin of selectivity for the oxidative carbonylation reaction catalyzed by a single Pd atom embedded on graphene

Supplementary files

Article information

Article type
Paper
Submitted
18 Jan 2023
Accepted
17 Feb 2023
First published
22 Feb 2023

Catal. Sci. Technol., 2023,13, 2421-2431

Theoretical exploration of the origin of selectivity for the oxidative carbonylation reaction catalyzed by a single Pd atom embedded on graphene

S. Lin, Z. Xu, J. Lin and G. Guo, Catal. Sci. Technol., 2023, 13, 2421 DOI: 10.1039/D3CY00091E

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