A Capacitance and Infrared Study of the Electrical Double Layer Structure at Single Crystal Gold Electrodes in Acetonitrile

The electrical double layer at Au(100) and Au(111) electrodes in acetonitrile containing tetraethylammoniumperchlorate (TEAP) was studied by means of differential capacitance and in-situ FTIR spectroscopy measurements. For both surfaces, a preponderant capacitance maximum was observed at a positive charge of about 8 μC cm -2 . Two types of acetonitrile molecules were identified in the interfacial infrared spectra. One of these concerns adsorbed acetonitrile with a strongly blue shifted vCN mode at 2337 cm -1 . The potential dependence of the spectra provides a clear evidence for dielectric saturation of the solvent and specific adsorption of the ions at large electrode charges. The spectra also indicate that the maximum ability of the solvent to reorientate in the interfacial field is in an adsorption geometry with the molecular axis inclined with respect to the surface. The data are discussed in context of the current models of the double layer, and compared with the related literature data obtained in an aqueous electrolyte.

[1]  M. J. Weaver,et al.  Some Electrochemical Consequences of Potential-Induced Surface Reconstruction on Au(100): Double-Layer Nonuniformity and Electrode Kinetics , 1994 .

[2]  R. Guidelli,et al.  A model for the effect of roughness of single-crystal electrodes on Parsons-Zobel plots , 1993 .

[3]  K. Baberschke,et al.  Alkali-metal-induced bond length contraction of acetonitrile (CH3CN) on Au(100) , 1993 .

[4]  W. Fawcett,et al.  Attenuated total reflection fourier-transform infrared spectroscopic study of ion–solvent and ion–ion interactions in alkali-metal perchlorate–acetonitrile solutions , 1993 .

[5]  W. Fawcett,et al.  A study of the adsorption of acetonitrile on a gold electrode from aqueous solutions using in situ vibrational spectroscopy , 1992 .

[6]  Yuyuan Tian,et al.  Kinetics of a potential induced 23 × 3 to 1 × 1 transition of Au(111) studied by in situ scanning tunneling microscopy , 1992 .

[7]  M. J. Weaver,et al.  Initial surface structure of flame-annealed Au(100) in aqueous solution: Consistency between in-situ scanning tunneling microscopy and electrochemical results , 1992 .

[8]  P. Ross,et al.  The effect of surface reconstruction on the capacitance of Au(100) surfaces , 1992 .

[9]  S. Lamperski.  A Monte Carlo study of intermolecular electrostatic interactions at the electrode/electrolyte interface , 1991 .

[10]  K. Christmann,et al.  The interaction of nitriles with a potassium-promoted gold(100) surface , 1991 .

[11]  M. J. Weaver,et al.  Atomic relaxation at ordered electrode surfaces probed by scanning tunneling microscopy: Au(111) in aqueous solution compared with ultrahigh‐vacuum environments , 1991 .

[12]  K. Christmann,et al.  Structural information pertaining to non-aqueous electrified interfaces: 2-D solvation of potassium with nitriles on the Au(100) surface , 1991 .

[13]  P. Rossky.  Structure and Dynamics of Water at Interfaces , 1991 .

[14]  S. Trasatti.  Structure of the metal/electrolyte solution interface: new data for theory , 1991 .

[15]  M. Sottomayor,et al.  The temperature dependence of double layer properties of gold faces in perchloric acid , 1990 .

[16]  G. Marowsky,et al.  An in situ study of reconstructed gold electrode surfaces by second harmonic generation. , 1989 .

[17]  Maria Luisa Foresti,et al.  A Monte Carlo simulation of water molecules near a charged wall , 1989 .

[18]  K. Christmann,et al.  Interaction of acetonitrile and benzonitrile with the gold (100) surface , 1989 .

[19]  Russier,et al.  Calculation of the electronic work function of Cu and Ag from an extended jellium model. , 1989, Physical review. B, Condensed matter.

[20]  J. Schneider,et al.  Potential-induced surface reconstruction of Au(100) , 1988 .

[21]  H. Angerstein-Kozlowska,et al.  Elementary steps of electrochemical oxidation of single-crystal planes of Au Part II. A chemical and structural basis of oxidation of the (111) plane , 1987 .

[22]  Z. Borkowska,et al.  Electrochemical study of the polycrystalline gold electrode in dimethylsulphoxide , 1987 .

[23]  A. Hamelin,et al.  A modification of the last step of surface preparation for gold and silver single crystal faces , 1987 .

[24]  M. R. Philpott,et al.  Vibrational and electronic properties of cyanide adsorbed on metal electrodes , 1987 .

[25]  M. Carlà,et al.  A comparison between the quasi-chemical approximation and the monte carlo method for the study of monolayer models of solvent dipoles☆ , 1986 .

[26]  Z. Borkowska,et al.  A double layer study of the (210) and (111) faces of gold in aqueous NaBF4 SOLUTIONS , 1985 .

[27]  J. Toennies,et al.  Observation of a soliton reconstruction of Au(111) by high-resolution helium-atom diffraction. , 1985, Physical review letters.

[28]  H. Baumgärtel,et al.  The influence of alkanes and benzene derivatives on the double-layer properties of mercury/nonaqueous CH3CN electrolytes , 1985 .

[29]  H. Baumgärtel,et al.  The influence of cations on the interface between the mercury electrode and non-aqueous CH3CN , 1985 .

[30]  Gerd K. Binnig,et al.  Real-space observation of the reconstruction of Au(100) , 1984 .

[31]  D. Henderson,et al.  The interphase between jellium and a hard sphere electrolyte. A model for the electric double layer , 1984 .

[32]  W. Schmickler.  A Monte Carlo study of point dipole models for solvent molecules in the inner layer , 1983 .

[33]  J. W. Halley,et al.  A new model of the differential capacitance of the double layer , 1983 .

[34]  J. Goodisman,et al.  The metal in the polarisable interface coupling with the solvent phase , 1983 .

[35]  A. Bewick,et al.  Vibrational spectroscopy of the electrode—solution interface: Part III. Use of fourier transform spectroscopy for observing double layer reorganization , 1982 .

[36]  M. D. Levi,et al.  Metal-solvent interaction and ion adsorption: Influence of solvent and metal nature , 1982 .

[37]  R. Durand,et al.  Preparation of monocrystalline Pt microelectrodes and electrochemical study of the plane surfaces cut in the direction of the {111} and {110} planes , 1980 .

[38]  J. Coetzee,et al.  Solute-solvent interactions. VII. Proton magnetic resonance and infrared study of ion solvation in dipolar aprotic solvents , 1972 .

[39]  J. Davies.  The Raman spectra of the guest molecules formic acid, methanol, and acetonitrile in β-quinol clathrates , 1971 .

[40]  G. Janz,et al.  Raman spectra of silver nitrate in water-acetonitrile mixtures , 1970 .

[41]  R. Manne.  Molecular Orbitals and Inner‐Electron‐Shell Chemical Shifts for Sulfur and Chlorine Oxy‐anions , 1967 .

[42]  K. Purcell.  An Investigation into the Source of C[UNK]N Vibrational Frequency Shifts , 1967 .

[43]  K. Purcell,et al.  Studies of the Bonding in Acetonitrile Adducts1 , 1966 .

[44]  G. Janz,et al.  Nonaqueous silver nitrate solutions. Raman spectral studies in acetonitrile , 1965 .

[45]  J. Coetzee,et al.  Evaluation of Single Ion Conductivities in Acetonitrile, Nitromethane, and Nitrobenzene Using Tetraisoamylammonium Tetraisoamylboride as Reference Electrolyte , 1965 .

[46]  M. Kubota,et al.  Molecular Addition Compounds of Tin(IV) Chloride. II. Frequency and Intensity of the Infrared Nitrile Absorption in Benzonitrile Complexes , 1961 .

[47]  A. M. Saum.  Intermolecular association in organic nitriles; the CN dipole‐pair bond , 1960 .