The interfacial adsorption, desorption, and exchange behaviors of thiolated ligands on nanotextured Au nanoparticle surfaces exhibit phenomenal site-to-site variations essentially dictated by the local surface curvatures, resulting in heterogeneous thermodynamic and kinetic profiles remarkably more sophisticated than those associated with the self-assembly of organothiol ligand monolayers on the atomically flat surfaces of planar Au substrates. Here we use surface-enhanced Raman scattering as a plasmon-enhanced spectroscopic tool with unique time-resolving and molecular fingerprinting capabilities to quantitatively correlate the interfacial ligand dynamics with detailed molecular structures in real time under a diverse set of ligand adsorption, desorption, and exchange conditions at both equilibrium and non-equilibrium states, which enables us to delineate the effects of nanoscale surface curvature on the binding affinity, cooperativity, structural ordering, and the adsorption/desorption/exchange kinetics of organothiol ligands on colloidal Au nanoparticles. We have also discovered several unconventional coupling reactions between thiophenol derivatives chemisorbed on Au nanoparticle surfaces that otherwise will not occur in the absence of the Au nanoparticles.

Interfacial ligand dynamics and chemistry on highly curved Au nanoparticle surfaces: A plasmon-enhanced spectroscopic study

254th National Meeting (2017)

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