Photocatalytic ethane conversion on rutile TiO₂(110): identifying the role of the ethyl radical

Oxidative dehydrogenation of ethane (C2H6, ODHE) is a promising approach to producing ethene (C2H4) in the chemical industry. However, the ODHE needs to be operated at a high temperature, and realizing the ODHE under mild conditions is still a big challenge. Herein, using photocatalytic ODHE to obtain C2H4 has been achieved successfully on a model rutile(R)-TiO2(110) surface with high selectivity. Initially, the C2H6 reacts with hole trapped O-Ti(-) centers to produce ethyl radicals , which can be precisely detected by a sensitive TOF method, and then the majority of the radicals spontaneously dehydrogenate into C2H4 without another photo-generated hole. In addition, parts of the radicals rebound with diversified surface sites to produce C-2 products via migration along the surface. The mechanistic model built in this work not only advances our knowledge of the C-H bond activation and low temperature C2H6 conversion, but also provides new opportunities for realizing the ODHE with high C2H4 efficiency under mild conditions.