Selective hydrogenation of 1,3-butadiene catalyzed by a single Pd atom anchored on graphene: the importance of dynamics

. Importantly, the high selectivity towards 1-butene is attributed to the post-transition-state dynamics in the second hydrogenation step, which leads exclusively to the desorption of the product. This dynamical event prevails despite the existence of energetically preferred 1-butene adsorption on Pd, which would eventually lead to complete hydrogenation to butane and be thus inconsistent with experimental observations. This insight underscores the importance of dynamics in heterogeneous catalysis, which has so far been underappreciated.