During the past five years, we have developed in our laboratory a new type of solar cell that is based on a photoelectrochemical process. The light absorption is performed by a monolayer of dye (i.e., a Ruthenium complex) that is adsorbed chemically at the surface of a semiconductor (i.e., titanium oxide (TiO2)). When excited by a photon, the dye has the ability to transfer an electron to the semiconductor. The electric field that is inside the material allows extraction of the electron, and the positive charge is transferred from the dye to a redox mediator that is present in solution. A respectable photovoltaic efficiency (i.e., 10%) is obtained by the use of mesoporous, nanostructured films of anatase particles. We will show how the TiO2 electrode microstructure influences the photovoltaic response of the cell. More specifically, we will focus on how processing parameters such as precursor chemistry, temperature for hydrothermal growth, binder addition, and sintering conditions influence the film porosity, pore‐size distribution, light scattering, and electron percolation and consequently affect the solar‐cell efficiency.
In recent decades, significant advances in drug‐delivery systems have enabled more effective drug administration. To deliver drugs to specific organs, a range of organic systems (e.g., micelles, liposomes, and polymeric nanoparticles) have been designed. They suffer from limitations, including poor thermal and chemical stability, and rapid elimination by the immune system. In contrast, silica particles offer a biocompatible, stable, and “stealthy” alternative. Bioactive molecules can be easily encapsulated within silica particles by combining sol–gel polymerization with either spray‐drying or emulsion chemistry. Spray‐drying faces challenges, including low yield, surface segregation, and size limitations. In contrast, sol–gel emulsions enable the production of nanoparticles with homogeneous drug distribution, and permit ambient temperature processing, necessary for handling biologicals. Independent control of the size and release rate can be readily achieved. Preliminary in‐vivo experiments reveal enhanced blood stability of the nanoparticles, which, coupled with sustained release of anti‐tumor agents, show good potential for cancer treatment.
A monolayer of a phosphonated triarylamine adsorbed on nanocrystalline TiO2, ZrO2, or Al2O3 film deposited on conducting glass displays reversible electrochemical and electrochromic behavior although the redox potential of the electroactive molecules (0.80 V vs NHE) lies in the forbidden band of the semiconducting or insulating oxides. The mechanism of charge transport was found to involve hole injection from the conducting support followed by lateral electron hopping within the monolayer. The apparent diffusion coefficient ranged from 2.8 × 10(-12) m(2) s(-1) in the neat 1-ethyl-2-methylimidazolium bis(trifluoromethylsulfonyl)imide (EtMeIm(+)Tf2N(-)) to 1.1 × 10(-11) m(2) s(-1) in acetonitrile + 2 M EtMeIm(+)Tf2N(-). A percolation threshold for electronic conductivity was found at a surface coverage corresponding to 50% of a full monolayer.
Nanocrystalline titanium dioxide colloids have been synthesized using a sol-gel technique followed by growth under hydrothermal conditions in a basic environment at temperatures between 190 and 270 °C. Thin films have been made from aqueous suspensions of these colloids. X-ray analysis showed the colloids to be primarily the anatase crystal phase. Scanning electron microscopy (SEM) revealed a predominantly rodlike particle morphology after growth at lower temperatures and the formation of principally truncated tetragonal or tetrahydral bipyramidal nanocrystallites following growth at higher temperatures. The rodlike particles self-organize into regular cubic arrays with the long axis of the rods aligned perpendicular to the film surface. This self-organization is dependent upon the base used in colloidal synthesis and also upon the dielectric constant of the medium used during film formation.
Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray powder diffraction (XRD) studies on nanocrystalline TiO2 powders and thin films are presented. The size, shape (mostly exposed faces), and ordering of the TiO2 anatase particles in the nanocrystalline films are discussed. The use of the topochemical approach, which considers the properties of (nanocrystalline) solids in terms of crystallographic features of (nano)crystals is suggested. The surface area of sensitizer [bis(4,4‘-dicarboxy-2,2‘-bipyridine)bis(thiocyanato)]ruthenium(II) [abbreviated as (cis-Ru(dcbpy)2(NCS)2] on the semiconductor surface for the different types of anchoring is estimated on the basis of single-crystal X-ray diffraction studies of the esterified form of the complex.
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