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Abstract

The catalytic properties of sp³-hybridized ultra-dispersed diamond and sp²-hybridized onion-like carbon in the oxidative dehydrogenation of ethylbenzene to styrene were investigated, highlighting the structure sensitivity of the reaction. The sp³-carbon led initially to C–C cleavage and benzene formation, while a switchover of the main reaction pathway into the styrene formation occurred with time on stream due to the formation of surface sp² carbon, required for the selective styrene formation. This was confirmed by the behavior and the high stable styrene selectivity shown by onion-like carbons. High temperature oxygen pre-treatment created catalytically active species at the sp² carbon surface, confirming that a high thermal stability carbon–oxygen complex was the active surface site for forming styrene.