Metal‐free carbon catalysts represent attractive alternatives to platinum and chromium‐containing systems for the on‐purpose production of propylene, a crucial chemical building block, via non‐oxidative propane dehydrogenation. However, the role of heteroatoms in determining reactivity and stability is poorly understood. Here, the study of a platform of polyaniline‐derived and activated carbons, with distinct porous properties, and heteroatom type, content, and speciation, enables establishing improved structure‐performance relationships. In‐depth characterization reveals that, while several oxygen species potentially catalyze the reaction, carbonyl groups are the main functionality governing the activity. Oxygen loss via propane‐driven water evolution is the main deactivation path. Six‐fold enhanced stability evidenced over carbon catalysts derived from KOH‐post‐treated polyanilines demonstrates the importance of controlling the nanostructure for enhancing longevity.

The Cover Feature shows a high‐speed train, representing non‐oxidative propane dehydrogenation, running on a monorail connected to specific atoms (active sites) on a catalyst surface. In their Full Paper, S. Büchele et al. elucidate the role of distinct nitrogen and oxygen groups (colored spheres) in carbon‐based catalysts and their stability under reaction conditions. While several species potentially catalyze the reaction, carbonyl groups (red spheres) comprise the dominant active site. Catalyst deactivation occurs through propane‐driven oxygen loss and can be alleviated by post‐treatment of the carbon with KOH to boost oxygen content and surface area. More information can be found in the Full Paper by S. Büchele et al.