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Photocatalytic reduction of CO2 into valuable hydrocarbon fuels using solar energy has attracted increasing attention in recent years due to global warming and energy shortage problems.1 However,the recombination of electron-hole pairs in semiconductor restrict the efficiency of photocatalytic activity.Recently,graphene can also act as electron acceptor and transporter to efficiently hinder recombination of electron-hole pairs.2,3 So a novel in situ simultaneous reduction-hydrolysis technique was developed for fabrication of surface-Ti3+ rich TiO2-graphene hybrid sheets in ethylenediamine solvent.4 The dispersion of TiO2 hinders the collapse and restacking of exfoliated sheets of graphene during reduction process.In contrast with prevenient G-TiO2 nanocomposites,Ti3+ was detected to be dominant on the surface of TiO2 of the present hybrid,which can serve as sites for trapping photo-generated electrons to prevent recombination of electron-hole pairs.The high photocatalytic activity of G-TiO2 hybrid was confirmed by photocatalytic conversion of CO2 to valuable hydrocarbons(CH4 and C2H6)in the presence of water vapor.It is for the first time found an interesting phenomenon that the synergistic effect of the surface-Ti3+ abundant TiO2 and graphene favors the generation of C2H6,and the yield of the C2H6 increases with the content of incorporated graphene.Our work may open a new doorway for new significant application of graphene for selectively catalytic C-C coupling reaction.