Weak Interactions Initiate C−H and C−C Bond Dissociation of Ethane on Nbn+ Clusters

Abstract The conversion of ethane into value‐added chemicals under ambient conditions has attracted much attention but the mechanisms remain not fully understood. Here we report a study on the reaction of ethane with thermalized Nb n + clusters based on a multiple‐ion laminar flow tube reactor combined with a triple quadrupole mass spectrometer (MIFT‐TQMS). It is found that ethane reacts with Nb n + clusters to form both products of dehydrogenation and methane‐removal (odd‐carbon products). Combined with density functional theory (DFT) calculations, we studied the reaction mechanisms of the C−C bond activation and C−H bond cleavage on the Nb n + clusters. It is unveiled that hydrogen atom transfer (HAT) initiates the reaction process, giving rise to the formation of Nb−C bonds and an elongated C−C distance in the HNb n + CH 2 CH 3 motif. Subsequent reactions allow for C−C bond activation and a competitive HAT process which is associated with CH 4 removal or H 2 release, resulting in the production of the observed carbides.