A site distance dependence of product selectivity in n-hexane dehydrogenation over alumina-supported chromium catalyst

Although CrOx/Al2O3 has been widely applied for light alkanes dehydrogenation, there is insufficient understanding on the dehydrogenation of long-chain alkanes that no solutions to the poor selectivity to mono-olefins and high yield of aromatics. Herein, dehydrogenation of n-hexane was studied on a series of CrOx/γ-Al2O3 catalysts with different densities of Cr sites, and it finds that the dehydrogenation performance is closely related to the distance between Cr sites. With densely populated Cr sites, multiple H atoms of n-hexane are adsorbed on the CrOx/γ-Al2O3 simultaneously (i.e., multi-point adsorption), promoting the formation of n-hexadiene, n-hexatriene and the resultant benzene and/or coke. Therefore, when the Cr loading exceeds the mono-layer coverage (5 wt% Cr loadings), the selectivities to n-hexenes and benzene are kept constant (about 23 wt% and 68 wt%, respectively). While decrease of Cr content in the mono-layer regime leads to a significant decrease in both the distance between Cr sites and the number of adsorbed H atoms, resulting in improved selectivity to n-hexenes. The CrOx@γ-Al2O3 catalyst with 3.6 Cr atoms/nm2 prepared by the equilibrium adsorption method (and the complexation of CrIII and 3,5-dimethylpyridine), exhibits 89 wt% selectivity to n-hexenes (<2 wt% for benzene). This work provides theoretical guidance for the precise design and synthesis of the high-performance CrOx-based catalyst for the dehydrogenation of alkanes, especially for long-chain alkanes.