Vibrational relaxation of cyanide at the metal/electrolyte interface

Abstract

Articles you may be interested inVibrational lifetimes of cyanide and carbon monoxide on noble and transition metal surfaces Multidimensional density operator propagations in open systems: Model studies on vibrational relaxations and surface sticking processes Effect of a static electric field on the vibrational and electronic properties of a compressed CO adlayer on Pt (110) in nonaqueous electrolyte as probed by infrared reflection-absorption spectroscopy and infrared-visible sumfrequency generation spectroscopyThe vibrational lifetime of the CN stretching mode has been measured at a Pt͑111͒, polycrystalline Au and polycrystalline Ag electrochemical interface with sum-frequency generation ͑SFG͒. The lifetimes on Pt͑111͒ and Au are potential dependent and range from 3 to 8 ps and 10 to 19 ps, respectively, with the longer lifetimes occurring at more positive potentials. Results for the Ag surface show solvent dependent lifetimes of Ϸ28 ps in a 0.1 M solution of NaClO 4 in H 2 O and Ϸ60 ps when the solvent is changed to D 2 O. The results on all of these metals are surprising because of the comparatively short ͑1.5-3.0 ps͒ lifetimes predicted and measured for isoelectronic CO. The lifetimes on Ag are remarkable because of their similarity to those of freely-solvated CN Ϫ ions. We discuss our results in the context of a charge transfer to the substrate and also consider an image dipole mechanism.

An in situ SFG and SERS investigation into the electrodeposition of Au from and solutions

“…The vibrational relaxation of CN À on polycrystalline Au in 0.1M NaClO 4 , KCN 0.025 M was studied by picosecond SFG in [12,13]. Vibrational decay curves exhibit a simple exponential behaviour, which was interpreted with a strongly potential-dependent T 1 , ranging from 10 to 19 ps; longer lifetimes were found on shifting the potential to more positive values.…”

Time-dependent in situ SERS study of CN− adsorbed on gold

“…Some dynamic SFG work has been reported on the Au/ CN À system. The vibrational relaxation of CN À on polycrystalline Au in 0.1 M NaClO 4 , KCN 0.025 M was studied by picosecond SFG in [12,13]. Vibrational decay curves exhibit a simple exponential behaviour, which was interpreted with a strong potential dependence T 1 , ranging from 10 to 19 ps; longer lifetimes were found on shifting the potential to more positive values.…”

Structure and bonding mechanism of cyanide adsorbed on Pt(111)

“…Its chemistry is of fundamental interest for large-scale industrial processes such as the Andrussov process [2] for the synthesis of HCN and in the context of catalytic automotive converters. Experimentally, adsorption of CN has been studied on several metals as Ni [3,4], Pd [5][6][7], Pt [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22], Rh [23][24][25][26], Ru [27,28], Cu [29][30][31][32] or Au [33][34][35], either in electrochemical cells and in vacuum medium. However, and contrarily to analogue species as CO or NO, no energetic data for CN adsorbed on platinum is known, only the vibrational frequency has been reported.…”