Improving the Selectivity and Stability of Supported Cobalt Catalysts via Static Bi‐Doping and Dynamic Trace CO 2 Co‐Feeding During Propane Dehydrogenation

Abstract Simultaneously enhancing selectivity and stability on supported propane dehydrogenation (PDH) catalysts remains a formidable challenge. Here, we report a combined static and dynamic strategy to address these issues synergistically. Firstly, we demonstrate a feasible sol‐gel method for preparing atomically‐dispersed Bi‐decorated metal nanoparticle catalysts (MBi/Al 2 O 3 , M=Fe, Co, Ni, and Zn). In PDH testing, the total selectivity of by‐products (CH 4 and C 2 H 6 ) significantly decreases to 4 % for CoBi catalysts due to the static Bi‐doping, compared with 16 % for Co‐supported catalysts. Secondly, to enhance catalytic stability, we introduce a dynamic trace CO 2 co‐feeding route. 10CoBi/Al 2 O 3 catalysts exhibit superior durability against coke formation for 330 hours in PDH under a 40 % C 3 H 8 atmosphere followed by pure C 3 H 8 conditions at 600 °C while maintaining propylene selectivity at 96 %. Notably, introducing trace CO 2 leads to a remarkable 6‐fold decrease in the deactivation rate constant ( k d ). Multiple characterizations and density functional theory calculations reveal that charge transfer from atomically‐distributed Bi to Co nanoparticles benefits lowering the energy of C 3 H 6 adsorption thereby suppressing by‐products. Furthermore, the dynamic co‐feeding of trace CO 2 facilitates coke removal, suppressing catalyst deactivation. The static Bi‐doping and dynamic trace CO 2 co‐feeding strategy contributes simultaneously to increased selectivity and stability on supported PDH catalysts.