Photocatalytic Oxidative Dehydrogenation of Propane for Selective Propene Production with TiO 2 .

Oxidative dehydrogenation of propane (ODHP) as an exothermic process is a promising method to produce propene (C 3 H 6 ) with lower energy consumption in chemical industry. However, the selectivity of the C 3 H 6 product is always poor because of overoxidation. Herein, the ODHP reaction into C 3 H 6 on a model rutile(R)-TiO 2 (110) surface at low temperature via photocatalysis has been realized successfully. The results illustrate that photocatalytic oxidative dehydrogenation of propane (C 3 H 8 ) into C 3 H 6 can occur efficiently on R-TiO 2 (110) at 90 K via a stepwise manner, in which the initial C-H cleavage occurs via the hole coupled C-H bond cleavage pathway followed by a radical mediated C-H cleavage to the C 3 H 6 product. An exceptional selectivity of ∼90% for C 3 H 6 production is achieved at about 13% propane conversion. The mechanistic model constructed in this study not only advances our understanding of C-H bond activation but also provides a new pathway for highly selective ODHP into C 3 H 6 under mild conditions.