Competitive surface-enhanced Raman scattering effects in noble metal nanoparticle-decorated graphene sheets

Herein, noble metal nanoparticle (Au or Ag NP) decorated graphene sheets, fabricated according to a facile one-pot environmentally friendly method, are used as good substrates for the investigation of the combined surface-enhanced Raman scattering (SERS) effect, where both the electromagnetic mechanism and the chemical mechanism effects coexist among the Au or Ag NPs, graphene sheets and the absorbed analytes. Our results show that, in aqueous solution, the SERS effect of both the Au and Ag NPs on the absorbed probe molecules and on graphene is competitive, which varies dependent on the species and the concentration of the absorbed probe molecule. By a detailed comparison of three probe molecules (rhodamine 6G, nile blue A, and 4-aminobenzenethiol) with different coupling abilities to the graphene sheets, we finally attribute this phenomenon to the result of the strong suppressing effect of the macrocyclic probe molecules on the SERS of graphene, induced by charge transfer, as the probe molecules are coupled to the graphene sheets. This competitive effect is a non-ignorable phenomenon when graphene/Au or Ag nanocomposites are used as SERS substrates, and our study may deepen our understanding of the SERS mechanism.