First‐Principles Design of a Highly Active and Selective V2CO2‐Based Double‐Atom Catalyst for Ethane Dehydrogenation to Ethylene

Abstract The electrocatalytic ethane dehydrogenation to ethylene reaction (EDH) offers an alternative to the traditional steam cracking method for sustainable ethylene production but suffers sluggish kinetics due to the inert C−H bonds. Herein, a novel strategy is proposed for designing efficient double‐atom catalysts (DACs) via first principle calculations. We examined the C−H activation of methane by single‐atom catalysts (SACs) and constructed activity maps using activation energy as the activity descriptor, where methane is the simplest probe molecule to establish trends in C−H activation. Particularly, due to the strong d‐σ* coupling between ethane and Rh atoms, Rh 2 @V 2 CO 2 presents excellent EDH performance with particularly low energy barriers (0.64 eV for the C 2 H 6 * to C 2 H 5 * step and 0.63 eV for the C 2 H 5 * to C 2 H 4 * step). This work not only demonstrates the possibility of developing novel DACs for EDH but also provides a new strategy for designing efficient DACs.