▎ 摘　　要

The dehydrogenation of alkane feedstock to produce alkenes is a significant and energy intensive industrial process, generally occurring on metals and metal oxides. Here, we investigate a catalytic mechanism for the dehydrogenation of butane on single-layer, metal-free graphene using a combination of ab initio quantum chemical calculations and adsorption microcalorimetry. Dispersion-corrected Density Functional Theory (DFT) is employed to calculate transition states and energy minima that describe the reaction pathways connecting butane to the two possible products, but-1-ene and but-2-ene. The deprotonations occur with moderate energy barriers in the 0.54 eV-0.69 eV range. A strong agreement is observed between the results of the adsorption energies calculated by DFT (0.40 eV) and the measured differential heat of adsorption of n-butane on a graphitic overlayer. We conclude that the active-site for this catalytic reaction is a metal-free graphene vacancy, created by removing a carbon atom from a single-layer graphene sheet.(c) 2022 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).