Solvents are known to affect the local surface plasmon resonance of metal nanoparticles; however, how solvents can be used to manipulate the interfacial charge and energy transfer in plasmonic catalysis remains to be explored. Here, using NH3 decomposition on a Ru-doped Cu surface as an example, we report density functional theory (DFT) and delta self-consistent field (SCF) calculations, through which we investigate the effect of different protic solvent molecules on interfacial charge transfer by calculating excitation energy of an electronic transition between the metal and the molecular reactant. We find that the H-bonds between water and NH3 can alter the direct interfacial charge transfer due to the shift of the molecular frontier orbitals with respect to the metal Fermi level. These effects are also observed when the H-bonds are formed between methanol (or phenol) and ammonia. We show that the solvent possessing stronger basicity induces a more pronounced effect on the excitation energy. This work thus provides valuable insights for tuning the excitation energy and controlling different routes to channel the photon energy into plasmonic catalysis.
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