Single crystals of TiO2 anatase containing 0.22% of Al and traces of V, Zr, Nb, and La were grown by chemical transport reactions employing TeCl4 as the transporting agent. Electrodes having the (101) face exposed doped by reduction with hydrogen were employed. The electrochemical and photoelectrochemical behavior of a single crystal of anatase were scrutinized for the first time. Properties were compared to those of single-crystal rutile having the (001) face exposed. Impedance analysis established that the flatband potential of anatase (101) is shifted negatively by 0.2 V with regards to that of rutile (001). Interfacial capacitance measurements under forward bias indicate smaller density of surface states on anatase. Photoelectrochemical oxidation of water occurs on both rutile and anatase with incident photon-to-current conversion efficiencies close to unity at λ = 300 nm. From the comparison of U fb and E g, it follows that anatase (101) and rutile (001) electrodes differ mainly in the position of the conduction band edge. The complete photoelectrolysis of water to H2 and O2 is thermodynamically possible on anatase only. Photosensitized electron injection from adsorbed cis-Ru[L2(SCN)2] (L = 2,2‘-bipyridyl-4,4‘-dicarboxylic acid) proceeds with similar efficiency on both types of electrodes. However, light-induced charge separation on the single-crystal electrodes is about three times less efficient compared with nanoscopic anatase films. Anatase (101) is strikingly more active for electrochemical insertion of Li+ than rutile (001). The diffusion coefficients for Li+ insertion and extraction were estimated to be 2 × 10-13 and 6 × 10-13 cm2/s, respectively.

Phase-pure TiO2(B) with microfibrous morphology was prepared via a newly developed method from amorphous TiO2. Cyclic voltammetry evidences that Li-insertion into TiO2(B) is governed by a pseudocapacitive faradaic process, whose rate is not limited by solid-state diffusion of Li+ in a broad interval of scan rates. This unusual behavior was discussed in terms of the crystal structure of the TiO2(B) host, having freely accessible parallel channels for Li+-transport perpendicular to the (010) face. The characteristic Li-insertion electrochemistry of TiO2(B) allows re-interpretation of several previous reports, which did not consider explicitly this relation or the presence of TiO2(B) in various TiO2 materials of different origin.

Commercial graphene nanoplatelets in the form of optically transparent thin films on F-doped SnO(2) (FTO) exhibited high electrocatalytic activity toward I(3)(-)/I(-) redox couple, particularly in electrolyte based on ionic liquid (Z952). The charge-transfer resistance, R(CT), was smaller by a factor of 5-6 in ionic liquid, compared to values in traditional electrolyte based on methoxypropionitrile solution (Z946). Optical spectra and electrochemical impedance confirm that the film's absorbance scales linearly with R(CT)(-1). Electrocatalytic properties of graphene nanoplatelets for the I(3)(-)/I(-) redox reaction are proportional to the concentration of active sites (edge defects and oxidic groups), independent of the electrolyte medium. Dye-sensitized solar cell (DSC) was assembled with this material as a cathode. Semitransparent (>85%) film of graphene nanoplatelets presented no barrier to drain photocurrents at 1 Sun illumination and potentials between 0 and ca. 0.3 V, but an order of magnitude decrease of R(CT) is still needed to improve the behavior of DSC near the open circuit potential and, consequently, the fill factor. We predict that the graphene composite is a strong candidate for replacing both Pt and FTO in cathodes for DSC.