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

Searching for efficient catalysts that enable both direct and CO₂-oxidative dehydrogenation of propane (DDP and CO₂-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 CO₂-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 CO₂-ODP, i.e., a top-tier propylene yield (54.5%) in DDP, a leading propylene yield (59.7%) in CO₂-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 CO₂ utilization.