Defective TiO x overlayers catalyze propane dehydrogenation promoted by base metals.

The industrial catalysts utilized for propane dehydrogenation (PDH) to propylene, an important alternative to petroleum-based cracking processes, either use expensive metals or metal oxides that are environmentally unbenign. We report that a typically less-active oxide, titanium oxide (TiO 2 ), can be combined with earth-abundant metallic nickel (Ni) to form an unconventional Ni@TiO x catalyst for efficient PDH. The catalyst demonstrates a 94% propylene selectivity at 40% propane conversion and superior stability under industrially relevant conditions. Complete encapsulation of Ni nanoparticles was allowed at elevated temperatures (>550°C). A mechanistic study suggested that the defective TiO x overlayer consisting of tetracoordinated Ti sites with oxygen vacancies is catalytically active. Subsurface metallic Ni acts as an electronic promoter to accelerate carbon-hydrogen bond activation and hydrogen (H 2 ) desorption on the TiO x overlayer.