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An effective structural doping approach has been described to modify the photoelectrochemical properties of g-C3N4 sheet by the π-π hybridization with graphene.It is found that the g-C3N4 sheet is bound to the graphene with the special site selectivity,favoring the CT-NH configuration.However,their bands near Fermi level have characteristic graphene-like features with a small band gap opening at K,which still presents high carrier mobility and saturation velocity.