Modifying the Charge‐Density of Tetrahedral Cobalt(II) Centers through Carbon‐Layer Modulation Promotes C‐H Activation in the Propane Dehydrogenation Reaction (PDH)

Abstract The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non‐metal component of carbon as electronic additives to regulate d‐band center has rarely been studied in thermal‐catalysis field. Herein, we report electron‐deficient tetrahedral Co(II) (T d ‐cobalt(II)) centers through carbon‐layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both T d ‐cobalt(II) and metallic‐cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic‐cobalt can cover the inactive metallic‐cobalt and tailor d‐band of active T d ‐cobalt(II) simultaneously. More importantly, the pre‐deposited carbon‐layer is proposed to decrease electron density of T d ‐cobalt(II) and make d‐band center closer to Fermi level, consequently promotes C−H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts.