Sulfur-treated TiO ₂ shows improved alcohol dehydration activity and selectivity

The dehydration of alcohols is an important class of reactions for the development of fossil-free fuel and chemical industries. Acid catalysts are well known to enhance the reactivity of alcohols following two main pathways of either dehydration to olefins or dehydrogenation to ketones/aldehydes. TiO₂ surfaces have been well documented for primary and secondary alcohol dehydration with selectivity ranging from 1-100% towards dehydration products based on process conditions and catalyst structure. In this work we document the effects of various sulfur treatments of TiO₂ surfaces which induce higher activity and, more importantly, higher selectivity for alcohol dehydration than untreated surfaces. The increase in activity and >99% dehydration selectivity is coupled with demonstrated stability for several hours on stream at high conversion. Using temperature programmed reaction studies, XPS and FT-IR spectroscopy, we identify Lewis acidic sites correlated with sulfate species on TiO₂ surfaces as active sites for the reaction.