Electrochemical properties of Li+ ion insertion in nanoporous TiO2 (anatase) electrodes were studied by voltammetry. Linear and cyclic potential scans were recorded as a function of electrolyte concentration, film thickness, and temperature. The currents were directly proportional to the inner electrode area of the electrodes. The reduction of Ti4+ and oxidation of Ti3+ are sluggish and follows irreversible kinetics. The standard rate constant was (3.5 ± 0.5) × 10-10 cm/s. The transfer coefficient was close to 0.5, indicating that the potential drop appears mainly across the Helmholtz layer. The capacitive currents govern largely the shape of the i − v curves, except within a region near the peak potential where diffusion-limited insertion and extraction of Li+ ions in the anatase lattice are dominating. The diffusion coefficient at 25 °C in the nanoporous structure was approximately 2 × 10-17 cm2/s for insertion and 4 × 10-17 cm2/s for extraction. The activation energy was 0.4 eV for insertion and 0.5 eV for extraction. The maximum obtained mole fraction of Li+ in Li x TiO2 was x = 0.47.

The ability to generate homogeneous particulate thin films of highly oriented and highly porous microparticles of a post transition metal oxide onto polycrystalline and single-crystalline substrates, at low cost, by a template-free, aqueous low-temperature coating process is demonstrated by the fabrication of a large three-dimensional array of perpendicularly oriented hexagonal microtubes of crystalline zincite ZnO from an aqueous solution of zinc nitrate and methenamine.

Nanostructured NiO film was prepared by depositing nickel hydroxide slurry on conducting glass and sintering at 500 °C to a thickness of about 1 µm. The photocurrent-voltage (IV) characteristics of the plain nanostructured NiO electrode recorded potentiostatically in a standard three-electrode setup upon UV illumination demonstrate p-type behavior, while the IV characteristics of a dye-sensitized nanostructured NiO electrode coated with erythrosin B show cathodic photocurrent under visible light illumination. The highest incident photon-to-current conversion efficiencies of tetrakis(4-carboxyphenyl)porphyrin (TPPC) and erythrosin B-coated NiO films were 0.24% and 3.44%, respectively. In sandwich solar cells with a platinized conducting glass as counter electrode exposed to light from a sun simulator (light intensity: 68 mW/cm 2 ), a short-circuit cathodic photocurrent density (I SC ) of 0.079 mA/cm 2 and an open-circuit voltage (V OC ) of 98.5 mV for TPPC-coated NiO electrode were achieved. Similarly, I SC ) 0.232 mA/cm 2 and V OC ) 82.8 mV were registered when the NiO electrode was coated with erythrosin B. The cathodic photocurrent is explained by hole injection from dye molecule to the valence band of the p-NiO electrode.

Nanocrystalline particles of ZnO and TiO 2 of approximately equal size (∼15 nm) were used to prepare mesoporous electrodes for dye-sensitized solar cells. Electron transport in the solar cells was studied using intensity-modulated photocurrent spectroscopy and revealed very similar results for ZnO and TiO 2 . Apparent activation energies for electron transport in nanostructured ZnO of e0.1 eV were calculated from the temperature dependence of transport times under short-circuit conditions. The lifetime of electrons in the nanostructured semiconductors was evaluated from open-circuit voltage decay and intensity-modulated photovoltage spectroscopy. Significantly longer lifetimes were obtained with ZnO. Despite the reduced recombination, ZnO-based solar cells performed worse than TiO 2 cells, which was attributed to a lower electron injection efficiency from excited dye molecules and/or a lower dye regeneration efficiency. The internal voltage in the nanostructured ZnO film under short-circuit conditions was about 0.23 V lower than the opencircuit potential at the same light intensity. Results may be explained using a multiple trapping model, but as electrons are usually only shallowly trapped in ZnO, an alternative view is presented. If there is significant doping of the ZnO, resulting band bending in the nanocrystals will form energy barriers for electron transport and recombination that can explain the observed properties.

Four Zn(II)-tetra(carboxyphenyl)porphyrins in solution and bound to metal oxide (TiO2, ZnO, and ZrO2) nanoparticle films were studied to determine the effect of the spacer length and anchoring group position (para or meta) on their binding geometry and photoelectrochemical and photophysical properties. The properties of three types of anchoring groups (COOH and COONHEt3) for four Zn(II)-porphyrins (Zn(II)-5,10,15,20-tetra(4-carboxyphenyl)porphyrin (p-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-carboxyphenyl)porphyrin (m-ZnTCPP), Zn(II)-5,10,15,20-tetra(3-(4-carboxyphenyl)phenyl)porphyrin (m-ZnTCP2P), and Zn(II)-5,10,15,20-tetra(3-ethynyl(4-carboxyphenyl)phenyl)porphyrin (m-ZnTC(PEP)P)) were compared. In m-ZnTCPP, m-ZnTCP2P, and m-ZnTC(PEP)P the four anchoring groups are in the meta position on the meso-phenyl rings of the porphyrin macrocycle, thus favoring a planar binding mode to the metal oxide surfaces. The three meta-substituted porphyrin salts have rigid spacer units of increasing length (phenyl (P), biphenyl (P2), and diphenylethynyl (PEP)) between the porphyrin ring and the carboxy anchoring groups, thus raising the macrocycle from the metal oxide surface. All porphyrins studied here, when bound to TiO2 and ZnO, exhibited quenching of the fluorescence emission, consistent with electron injection into the conduction band of the semiconductor. Steady-state UV-vis and fluorescence studies of p-ZnTCPP on insulating ZrO2 showed evidence of aggregation and exciton coupling. This was not observed in any of the meta-substituted porphyrins. The photoelectrochemical properties (IPCE, Voc, and Isc) of the porphyrins bound to TiO2 films in solar cells have been measured and rationalized with respect to the sensitizer binding geometry and distance from the surface.