Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H2O with Sub-3-nm Spatial Resolution

El-Khoury, Patrick Z.

doi:10.1021/jacs.3c01626

Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H₂O with Sub-3-nm Spatial Resolution

Journal Article · Wed Mar 15 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c01626· OSTI ID:1969033

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Reproducible chemical and chemical reaction nano-imaging at solid-liquid interfaces remains challenging, particularly when resolutions on the order of a few nm are sought after. 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 nano-visualization 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. Here 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 nano-imaging in liquids.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1969033

Report Number(s):: PNNL-SA-182192

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY