General Descriptors for CO 2 -Assisted Selective C-H/C-C Bond Scission in Ethane.

The selective C-H/C-C bond scission in CO 2 -assisted alkane activation represents an opportunity for simultaneously upgrading greenhouse gas CO 2 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-CO 2 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-CO 2 reactions.