Non‐Oxidative Dehydroaromatization of Linear Alkanes on Intermetallic Nanoparticles

Abstract There has been significant interest in developing new catalytic systems to convert linear chain alkanes into olefins and aromatics. In the case of higher alkanes (≥C 6 ), the production of aromatic compounds such as benzene‐toluene‐xylenes is highly desirable. However, as the length of the carbon chain increases, the dehydrogenation process becomes more complex, not only due to the challenges of C−H activation but also the need for selectivity towards the desired products by the possibility of side reactions such as isomerization and cracking. Here, we present a detailed analysis of the dehydroaromatization of n‐hexane, n‐heptane, and n‐octane, using PtSn intermetallic nanoparticles supported on SBA‐15 as the catalyst. Through in situ spectroscopic and kinetic analysis, we have probed the reaction kinetics and catalyst deactivation, and provided a mechanistic understanding of the dehydroaromatization process on the surface of the PtSn intermetallic nanoparticles. Introducing Sn has been shown to be crucial not only for enhancement of catalytic activity, but also for higher aromatics selectivity and stability on stream. Furthermore, the analysis of dehydroaromatization reaction rates of reactant and possible intermediates indicates that the dehydroaromatization of n‐hexane to benzene likely proceeds through initial dehydrogenation steps followed by ring closing.