Oxidative dehydrogenation (ODH) of
cyclohexane over solid metal
oxides is an attractive method for the production of cyclohexene,
but the difficulty in selectivity control for cyclohexene due to overoxidation
is considered to be one big hard nut to crack. The doping of non-metal
elements is expected to tune the inherent electronic properties of
metal oxides, offering a brand new train of thought for improving
the catalytic performance. In this work, an efficient catalyst for
cyclohexane ODH was developed by performing postsynthesis treatments
of chlorine decoration on well-defined facets of cubic CeO2 nanocrystals with different levels of chloride incorporation. The
catalyst obtained can significantly reduce the degrees of cyclohexane
overoxidation while slightly promoting the conversion of cyclohexane
and achieve 47.1% cyclohexene selectivity at a mild reaction temperature
(350 °C). According to the characterization results and theoretical
calculation analysis, the contribution of Cl decoration to the O-terminated
surface reduces the surface defects, leading to a decrease in electrophilic
peroxide species (O2
2–) and an increase
in nucleophilic CeOCl species. The former reduces the complete oxidation
of cyclohexane, while the latter is perceived to facilitate the desorption
of cyclohexene. The selectivity of cyclohexene is implicated in the
surface acidity of the catalyst, and the significantly improved selectivity
is derived from more weak acid sites (especially Lewis acid) and fewer
strong acid sites on the Cl-decorated ceria. The results verify the
great potential of the proposed strategy for application in alkane-selective
ODH and provide guidance for the structural optimization of CeO2-based catalysts.