title: Redox-switching in a viologen-type adlayer: an electrochemical shell-isolated nanoparticle enhanced Raman spectroscopy study on Au(111)-(1×1) single crystal electrodes.
abstract: We reported the first application of in situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) to an interfacial redox reaction under electrochemical conditions. We construct gap-mode sandwich structures composed of a thiol-terminated HS-6V6H viologen adlayer immobilized on a single crystal Au(111)-(1×1) electrode and covered by Au(60 nm)@SiO(2) core-shell nanoparticles acting as plasmonic antennas. We observed high-quality, potential-dependent Raman spectra of the three viologen species V(2+), V(+●), and V(0) on a well-defined Au(111) substrate surface and could map their potential-dependent evolution. Comparison with experiments on powder samples revealed an enhancement factor of the nonresonant Raman modes of ∼3 × 10(5), and up to 9 × 10(7) for the resonance modes. The study illustrates the unique capability of SHINERS and its potential in the entire field of electrochemical surface science to explore structures and reaction pathways on well-defined substrate surfaces, such as single crystals, for molecular, (electro-)catalytic, bioelectrochemical systems up to fundamental double layer studies at electrified solid/liquid interfaces.
authors.affiliation: Departement of Chemistry and Biochemistry, Bern University, Freiestrasse 3, 3012 Bern, Switzerland.
authors.forename: Bo
authors.initials: B
authors.lastname: Liu
authors.forename: Alfred
authors.initials: A
authors.lastname: Blaszczyk
authors.forename: Marcel
authors.initials: M
authors.lastname: Mayor
authors.forename: Thomas
authors.initials: T
authors.lastname: Wandlowski
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D004563:Electrochemistry; D004566:Electrodes; D006046:Gold / Q000737:chemistry*; D053758:Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D013059:Spectrum Analysis, Raman; D013499:Surface Properties; D014755:Viologens / Q000737:chemistry*
chemical_list: D014755:Viologens; D015082:2,2'-Dipyridyl; D006046:Gold