Layer-by-layer deposition of open-pore mesoporous TiO 2- Nafion® film electrodes

The formation of variable thickness TiO2 nanoparticle-Nafion® composite films with open pores is demonstrated via a layer-by-layer deposition process. Films of about 6 nm diameter TiO2 nanoparticles grow in the presence of Nafion® by “clustering” of nanoparticles into bigger aggregates, and the resulting hierarchical structure thickens with about 25 nm per deposition cycle. Film growth is characterized by electron microscopy, atomic force microscopy, and quartz crystal microbalance techniques. Simultaneous small-angle X-ray scattering and wide-angle X-ray scattering measurements for films before and after calcination demonstrate the effect of Nafion® binder causing aggregation. Electrochemical methods are employed to characterize the electrical conductivity and diffusivity of charge through the TiO2-Nafion® composite films. Characteristic electrochemical responses are observed for cationic redox systems (diheptylviologen2+/+, Ru(NH3)3+/2+6, and ferrocenylmethyl-trimethylammonium2+/+) immobilized into the TiO2-Nafion® nanocomposite material. Charge conduction is dependent on the type of redox system and is proposed to occur either via direct conduction through the TiO2 backbone (at sufficiently negative potentials) or via redox-center-based diffusion/electron hopping (at more positive potentials)

An in situ electrochemical quartz crystal microbalance study of polycrystalline gold electrodes in nitric acid solution

The dissolution and redeposition processes of Au in HNO3 solution at pH 1 and 0 were investigated as a function of sweep rate by in situ EQCM experiments. The results demonstrate that, at pH 1 and vless than or equal to10 mV s(-1), An dissolves through a 3 e(-) oxidation at E > +1.0 V versus saturated calomel electrode (SCE), a process that, at vgreater than or equal to10 mV s(-1), is kinetically hindered with respect to upd of OH surface sublattices and subsequent 2-D-phase oxide formation. The inhibition arises from the presence of a close packed layer of nitrate oxyanions at the gold surface, although the layer is disrupted and the inhibition removed by the Au dissolution and reprecipitation processes that occur during potential cycling at low v. (C) 2002 Elsevier Science B.V. All rights reserved