Uncovering strong ?-metal interactions on Ag and Au nanosurfaces under ambient conditions via in-situ surface-enhanced Raman spectroscopy

•Surface-enhanced Raman spectroscopy reveals that aromatic hydrocarbons adsorb spontaneously to Au and Ag colloids•Density functional theory co-adsorb alongside capping ligands•The ?-metal interaction is prohibited by surface oxidation of the nanosurfaces•Recognizing on IB metals paves way for new nanotechnologies The interactions between aryl molecules are ubiquitous in nanotechnology have direct consequences formation applications metal nanomaterials. current consensus with nanomaterials negligible presence solvents ligands. As a result, work based under ambient conditions has hardly been pursued. Here, combining surface-enhanced density modeling, we show significant Ag/Au nanosurfaces do fact exist these conditions. Rationalizing this effect immediately led design plasmonic sensors greatly improved sensitivity. This expected broader significance areas across chemistry because it completely alters which understood. nanoparticles nanotechnology. Currently, well appreciated VIIIB but not metals. demonstrate probing molecular specificity using (SERS), strongly from solution onto surfaces nanoparticles, provided there no oxidation. Theoretical modeling shows adsorption driven dispersive ligands present initially nanosurface. Finding evidence long-neglected implications various applications. demonstrated SERS sensing an drug molecule whose structure would typically suggest be weakly adsorbing, indeed detected conventional colloids due oxidation, found particles. IntroductionStrong attractive recognized serves as foundation important industrial production fuels chemicals typical examples including hydrocracking biomass gasification Pt nanocatalysts.1Ghadami Yazdi M.G. Moud P.H. Marks K. Piskorz W. Öström H. Hansson T. Kotarba A. Engvall Göthelid M. Naphthalene Ni (111): experimental theoretical insights into adsorption, dehydrogenation, carbon passivation.J. Phys. Chem. 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Moreover, MeLLFs interface, lets use even subtle changes both environments (see Figure S2 “experimental procedures” section details).Figure 1B, spectrum i obtained formed standard citrate-reduced stabilized particles, dominated bands 701 1,533 cm?1, bulk dichloromethane (DCM) citrate derivatives colloids, respectively. ii-iii, when naphthalene (NA) introduced MeLLF, clearly bands, prominently 1,378 characteristic NA.7Du Scholar,17Ye iii iv, NA unchanged MeLLF replaced ultrapure DCM, observed corresponded only contributed unabsorbed sitting physically within hot-spots. took place rapidly observation intensity close its final value first measurement (50 s accumulation time, see S3). very so overnight (Figure S4).Currently, widely accepted literature hydrocarbons, NA, Consequently, require functionalized hydrophobic modifiers, exhibit favorable intermolecular similarly hydrocarbons.21Carron Scholar,24Vasilyuk Scholar,28Olson Scholar,30Mosier-Boss Scholar,32Costa Scholar,50Gu H.-X. Hu D.-W. Y.-T. bare film system.Analyst. 141: 4359-4365Crossref Therefore, whether forces, contrast experiments either performed. 1B v, comparable, regardless taking DCM. metal. reinforced affected polarities hexane (vi) chloroform (vii), phase.NA special case, generated MeLLFs, 2A 2B . band positions notable shifts compared acquired same details), interacting nanosurface.51Liu G.-K. Wu D.-Y. Duan J.-F. Yao J.-L. R.-A. Effect intrinsic behavior molecules: group metals.J. 110: 17498-17506Crossref (28) addition frequency shifts, clear relative intensities observed, phenanthrene. out-of-plane vibrations 422SERS (not Raman), 492SERS (497Raman), 587SERS 898SERS (896Raman) cm?1 much more enhanced than in-plane 823SERS (831Raman) 1,031SERS (1,039Raman) cm?1.52Cyvin Neerland Brunvoll Cyvin B.N. Condensed aromatics. XII. Phenanthrene.Spectrosc. 1981; 14: 37-45Crossref (17) surface-selection rules dictate modes large tensor component normal surface, parallel field polarization, smaller components.53Le Ru E.C. Meyer S.A. Artur Etchegoin P.G. Grand Lang Maurel Experimental demonstration selection flat surfaces.Chem. 3903-3905Crossref (87) suggests flatly nanosurface.Figure 2An atomistic picture ligand-protected surfacesShow full caption(A B) (i) (ii) phenanthrene, respectively.(C) Schematic illustration model Cl? capped predicted DFT. Free species Cl?, Na+, unadsorbed system calculations, w