The catalytic properties of sp 3 -hybridized ultra-dispersed diamond and sp 2 -hybridized onion-like carbon in the oxidative dehydrogenation of ethylbenzene to styrene were investigated, highlighting the structure sensitivity of the reaction. The sp 3 -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 sp 2 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 sp 2 carbon surface, confirming that a high thermal stability carbon-oxygen complex was the active surface site for forming styrene.
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