Surface-Enhanced Raman Spectroscopy Investigation of the Potential-Dependent Acid–Base Chemistry of Silver-Immobilized 2-Mercaptobenzoic Acid

Ma, Chaoxiong; Harris, Joel M.

doi:10.1021/la1044859

Surface-Enhanced Raman Spectroscopy Investigation of the Potential-Dependent Acid–Base Chemistry of Silver-Immobilized 2-Mercaptobenzoic Acid

Journal Article · Wed Mar 02 00:00:00 EST 2011 · Langmuir

DOI:https://doi.org/10.1021/la1044859· OSTI ID:2480829

Ma, Chaoxiong ^[1]; Harris, Joel M. ^[1]

University of Utah, Salt Lake City, UT (United States)

The acid–base chemistry of 2-mercaptobenzoic acid (2-MBA) immobilized on a polycrystalline silver surface was investigated by surface-enhanced Raman spectroscopy under potential control. The COO^– bending mode of the benzoate form and the C–COOH stretching mode of the benzoic acid form of 2-MBA were used to determine the relative deprotonated and protonated populations of the bound ligand, respectively. In addition, shifts in the symmetric carboxylate stretching mode of 2-MBA reveal interactions between the benzoate group and the silver surface, interactions which could be displaced by acetate and other buffer anions from solution. It was found that the applied potential has a significant effect on the proton dissociation equilibrium of immobilized 2-MBA. This effect arises from the surface potential governing the activity of protons at the interface, which changes the interfacial pH relative to bulk solution. The results are fit to a Poisson–Boltzmann model, corrected for potential distribution across the monolayer and interactions between adjacent immobilized ligands. Furthermore, the results show a significant increase in the intrinsic pK_a of the immobilized ligand compared to 2-MBA in free solution, which is likely due to an increase in electron density on the benzoic acid group that occurs upon binding of the thiol group to the silver surface.

View Accepted Manuscript (DOE)

Research Organization:: University of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG03-93ER14333

OSTI ID:: 2480829

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 7 Vol. 27; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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