Surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculations were used to investigate the nature of the charge-transfer (CT) process between nitrothiophenol (NTP) isomers and the n-type semiconductor, TiO2. The Raman signals of p-NTP and m-NTP that were chemisorbed onto TiO2 were significantly enhanced with respect to their corresponding neat compounds. In particular, an enhancement factor (EF) of 102–103 was observed for both p-NTP and m-NTP, with m-NTP displaying a larger EF compared to p-NTP. The Raman signal of o-NTP on TiO2 was not detectable, owing to interference from fluorescence emissions. A molecule-to-TiO2 charge-transfer mechanism was responsible for the enhanced Raman signals observed in p-NTP and m-NTP. This transfer was due to a strong coupling between the adsorbate and the metal oxide, which led to an optically driven CT transition from the HOMO of NTP into the conduction band of TiO2. Based on the mesomeric effect, the NO2 group para to the thiol had a stronger electron-withdrawing ability than the NO2 group at the meta position. A less-efficient CT transition from p-NTP to TiO2 in the surface complex resulted in a weaker Raman-signal enhancement for p-NTP compared to m-NTP. The DFT calculation determined that the HOMO and the LUMO of NTP bound to TiO2 were located entirely on the adsorbate and the semiconductor, respectively, thereby supporting the experimental findings that a molecule-to-TiO2 mechanism was the driving force behind the observed SERS effect. 相似文献
Local redox conversion of nitro end groups of a 4‐nitrothiophenol self‐assembled monolayer on gold is achieved by direct‐mode scanning electrochemical microscopy (SECM). Potential pulses are applied to the modified gold surface leading to local reduction of nitro end groups to either hydroxylamine (?0.47 V, see picture) or amino groups (?0.6 V) exclusively beneath the positioned SECM tip.