General Descriptors for CO2-Assisted Selective C-H/C-C Bond Scission in Ethane

Zhenhua Xie; Xuelong Wang; Xiaobo Chen; Ping Liu; Jingguang G Chen

doi:10.1021/jacs.1c13415

General Descriptors for CO₂-Assisted Selective C-H/C-C Bond Scission in Ethane

J Am Chem Soc. 2022 Mar 9;144(9):4186-4195. doi: 10.1021/jacs.1c13415. Epub 2022 Feb 8.

Authors

Zhenhua Xie^{1

2}, Xuelong Wang¹, Xiaobo Chen³, Ping Liu¹, Jingguang G Chen^{1

2}

Affiliations

¹ Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States.
² Department of Chemical Engineering, Columbia University, New York, New York 10027, United States.
³ Department of Mechanical Engineering, State University of New York at Binghamton, Binghamton, New York 13902, United States.

PMID: 35133131
DOI: 10.1021/jacs.1c13415

Abstract

The selective C-H/C-C bond scission in CO₂-assisted alkane activation represents an opportunity for simultaneously upgrading greenhouse gas CO₂ and light alkanes for the synthesis of value-added syngas (CO and H2), olefins, aromatics, and oxygenates. Here, Pd bimetallic (PdM_x)-derived catalysts were investigated for ethane-CO₂ reactions by combining kinetic analysis, in situ characterization, and density functional theory calculations. Two types of catalyst structures were identified under the reaction conditions, with the PdCo_x alloy surface favoring ethoxy formation, a critical precursor for further C-C bond scission, and the reaction-induced InO_x/Pd interface promoting C-H bond scission. Our results revealed a general strategy to capture the reaction-induced surface configurations and in turn control the selectivity in C-C/C-H bond scission over PdM_x-derived catalysts, featuring the interplay of two general descriptors: formation energy of PdM_x surfaces and their binding energy to oxygen. Our study provides insight into the rational design of selective catalysts for light alkane-CO₂ reactions.