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Electrochemical impedance spectroscopy, photoelectron spectroscopy, and Kelvin probe measurements on various TiO 2 single-crystal surfaces show that the position of the Fermi level and the conduction band minimum depend significantly on the sample environment (vacuum, air, water vapor, and aqueous or aprotic electrolyte solutions). In most cases, the conduction-band minimum increases in the series: anatase < rutile < brookite. The offset between anatase and rutile indicates a type II staggered alignment if the environment is vacuum, air, water vapor, or aprotic electrolyte solution, but a type IV aligned configuration is found in an aqueous electrolyte solution. The photoelectron spectra in water vapor reveal a strong upshift of the conduction band, which is nearly reversible in the early stages of water/titania interactions. Our results rationalize various earlier contradictions and highlight the need for proper analytical techniques and experimental conditions for investigation of the band energetics, which is relevant to practical applications of titania materials.

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A crystallic silver amalgam was found to be a suitable working electrode material for voltammetric determination of electrochemically reducible organic nitro-compounds. Optimum conditions for crystal growth were found, the crystal surface was investigated by atomic force microscopy in tapping mode and single crystals were used for the preparation of quasi-cylindrical single crystal silver amalgam electrode (CAgAE). An electrochemical behavior of this alternative electrode material was investigated in aqueous media by direct current voltammetry, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and adsorptive stripping voltammetry (AdSV) using 4-nitrophenol as a model compound. Applicable potential windows of the CAgAE were found comparable with those obtained at a hanging mercury drop electrode, providing high hydrogen overpotential, and polished silver solid amalgam electrode. Thanks to the smooth single crystal electrode surface, the effect of the passivation is not too pronounced, direct DPV determination of 100 μmol l(-1) of 4-nitrophenol at CAgAEs in 0.2 mol l(-1) acetate buffer pH 4.8 provides a RSD around 1.5% (n = 15). DPV calibration curves of 4-nitrophenol are linear in the whole concentration range 1-100 μmol l(-1) with a limit of quantification of 1.5 μmol l(-1). The attempt to increase sensitivity by application of AdSV was not successful. The mechanism of 4-nitrophenol reduction at CAgAE was investigated by CV.