Hybrid Nanocarbon as a Catalyst for Direct Dehydrogenation of Propane: Formation of an Active and Selective Core-Shell sp2/sp3 Nanocomposite Structure

Hybrid nanocarbon, comprised of a diamond core and a graphitic shell with a variable sp(2)-/sp(3)-carbon ratio, is controllably obtained through sequential annealing treatment (550-1300 degrees C) of nanodiamond. The formation of sp(2) carbon increases with annealing temperature and the nanodiamond surface is reconstructed from amorphous into a well-ordered, onion-like carbon structure via an intermediate composite structurea diamond core covered by a defective, curved graphene outer shell. Direct dehydrogenation of propane shows that the sp(2)-/sp(3)-nanocomposite exhibits superior catalytic performance to that of individual nanodiamond and graphitic nanocarbon. The optimum catalytic activity of the diamond/graphene composite depends on the maximum structural defectiveness and high chemical reactivity of the ketone groups. Ketone-type functional groups anchored on the defects/vacancies are active for propene formation; nevertheless, once the oxygen functional groups are desorbed, the defects/vacancies alone might be active sites responsible for the CH bond activation of propane.