Bifunctional Direct and Oxidative Dehydrogenation of Propane by Balanced Electronic Coupling and Surface States in Pt‐M@Silicalite‐1

ABSTRACT Searching for efficient catalysts that enable both direct and CO 2 ‐oxidative dehydrogenation of propane (DDP and CO 2 ‐ODP) is of fundamental and industrial interests, while a challenge remains on leveraging electronic coupling and acid–base sites for activating both C─H and C═O. Present work develops a strategy of mediating electronic coupling by selecting counter‐part metals in Pt‐based catalysts encapsulated in Silicalite‐1 (S‐1), leading to as far as we know the first demonstration of a single catalyst achieving high efficiency separately in DDP and CO 2 ‐ODP. Strong PtIn electron‐coupling downshifts Pt d‐band center and creates balanced acid–base pairs, weakening propylene adsorption and promoting the activation of C─H and C═O. In contrast, the selection of other metal promoters other than In induces competitive adsorption due to imbalanced acidity/basicity. Optimized PtIn@S‐1 delivers an activity‐stability synergy in both DDP and CO 2 ‐ODP, i.e., a top‐tier propylene yield (54.5%) in DDP, a leading propylene yield (59.7%) in CO 2 ‐ODP, and outstanding stability with ultralow deactivation constants (0.0039 h −1 after 150 h; 0.0048 h −1 after 167 h, respectively), setting a benchmark for bifunctional propane dehydrogenation. We believe this work provides an effective design strategy for integrating complex catalytic functionalities in Pt‐based systems, with implications for low‐carbon olefin production and CO 2 utilization.