Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H 2 O with Sub-3-nm Spatial Resolution.

Reproducible chemical and chemical reaction nanoimaging at solid-liquid interfaces remains challenging, particularly when resolutions on the order of a few nanometers are sought. In this work, we demonstrate the latter through liquid-tip-enhanced Raman (TER) measurements that target gold nanoplates functionalized with 4-mercaptobenzonitrile (MBN). In addition to chemical imaging and local optical field nanovisualization with high spatial resolution, we observe the signatures of 4-mercaptobenzoic acid, which forms as a result of plasmon-induced hydrolysis of MBN. Evidently, the solvent leads to distinct plasmon-induced/enhanced chemical reaction pathways that have not been documented. This work shows that such reactions that take place at solid-liquid interfaces can be tracked with a record sub-3-nm spatial resolution via TER spectral nanoimaging in liquids.