Assembly of CeO2-TiO2 nanoparticles prepared in room temperature ionic liquid on graphene nanosheets for photocatalytic degradation of pollutants.

CeO(2)-TiO(2) nanoparticles were prepared by the sol-gel process using 2-hydroxylethylammonium formate as room-temperature ionic liquid and calcined at different temperatures (500-700°C). CeO(2)-TiO(2)-graphene nanocomposites were prepared by hydrothermal reaction of graphene oxide with CeO(2)-TiO(2) nanoparticles in aqueous solution of ethanol. The photocatalysts were characterized by X-ray diffraction, BET surface area, diffuse reflectance spectroscopy, scanning electron microscopy, and Fourier transformed infrared techniques. The results demonstrate that the room-temperature ionic liquid inhibits the anatase-rutile phase transformation. This effect was promoted by addition of CeO(2) to TiO(2). The addition of graphene to CeO(2)-TiO(2) nanoparticles enhances electron transport and therefore impedes the charge recombination of excited TiO(2). The photodegradation results of the pollutants in aqueous medium under UV irradiation revealed that CeO(2)-TiO(2)-graphene nanocomposites exhibit much higher photocatalytic activity than CeO(2)-TiO(2) and pure TiO(2). The photocatalytic activity of CeO(2)-TiO(2)-graphene nanocomposites decreases with additional increasing of the graphene content. Moreover, comparison of the photocatalytic activities of CeO(2)-TiO(2)-graphene with the other CeO(2)-TiO(2)-carbon demonstrates that CeO(2)-TiO(2)-graphene nanocomposites have the highest photocatalytic activity due to their unique structure and electronic properties. Chemical oxygen demand for solutions of the pollutants gave a good idea about mineralization of them.

Transition metal ions effect on the properties and photocatalytic activity of nanocrystalline TiO2 prepared in an ionic liquid.

TiO(2) and transition metal (Cr, Mn, Fe, Co, Ni, Cu, and Zn) doped TiO(2) nanoparticles were synthesized by the sol-gel method using 2-hydroxylethylammonium formate as an ionic liquid. All the prepared samples were calcined at 500 degrees C and characterized by X-ray diffraction (XRD), BET surface area determination, energy dispersive X-ray (EDX) analysis, diffuse reflectance spectroscopy (DRS), and Fourier transformed infrared (FT-IR) techniques. The studies revealed that transition metal (TM) doped nanoparticles have smaller crystalline size and higher surface area than pure TiO(2). Dopant ions in the TiO(2) structure caused significant absorption shift into the visible region. The results of photodegradation of Acid Blue92 (AB92) in aqueous medium under UV light showed that photocatalytic activity of TiO(2) nanoparticles was significantly enhanced by the presence of some transition metal ions. Chemical Oxygen Demand (COD) of dye solutions were done at regular intervals gave a good idea about mineralization of dye.

DNA adsorption measured with ultra-thin film organic field effect transistors.

Organic ultra-thin film field effect transistors (FET) are operated as label-free sensors of deoxyribonucleic acid (DNA) adsorption. Linearized plasmid DNA molecules (4361 base pairs) are deposited from a solution on two monolayers thick pentacene FET. The amount of adsorbed DNA is measured by AFM and correlated to the concentration of the solution. Electrical characteristics on the dried DNA/pentacene FETs were studied as a function of DNA concentration in the solution. Shift of the pinch-off voltage across a wide range of DNA concentration, from very diluted to highly concentrated, is observed. It can be ascribed to additional positive charges in the semiconductor induced by DNA at a rate of one charge for every 200 base pairs. The sensitivity 74 ng/cm(2), corresponding to 650 ng/ml, is limited by the distribution of FET parameters upon repeated cycles, and is subjected to substantial improvement upon standardization. Our work demonstrates the possibility to develop label-free transducers suitable to operate in regimes of high molecular entanglement.

Solution-processed ambipolar organic field-effect transistors and inverters.

There is ample evidence that organic field-effect transistors have reached a stage where they can be industrialized, analogous to standard metal oxide semiconductor (MOS) transistors. Monocrystalline silicon technology is largely based on complementary MOS (CMOS) structures that use both n-type and p-type transistor channels. This complementary technology has enabled the construction of digital circuits, which operate with a high robustness, low power dissipation and a good noise margin. For the design of efficient organic integrated circuits, there is an urgent need for complementary technology, where both n-type and p-type transistor operation is realized in a single layer, while maintaining the attractiveness of easy solution processing. We demonstrate, by using solution-processed field-effect transistors, that hole transport and electron transport are both generic properties of organic semiconductors. This ambipolar transport is observed in polymers based on interpenetrating networks as well as in narrow bandgap organic semiconductors. We combine the organic ambipolar transistors into functional CMOS-like inverters.

Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.

The energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient absorption spectra measured in solution and in films allows disentangling of the contributions arising from intrachain and from interchain energy-migration phenomena. Intrachain processes dominate in solution where photoexcitation of the polyindenofluorene units induces a rather slow energy transfer to the perylene end moieties. In films, close contacts between chains favors interchain transport of the excited singlet species (from the conjugated bridge of one chain to the perylene unit of a neighboring one); this process is characterized by a 1-order-of-magnitude increase in transfer rate with respect to solution. This description is supported fully by the results of quantum-chemical calculations that go beyond the usual point-dipole model approximation and account for geometric relaxation phenomena in the excited state before energy migration. The calculations indicate a two-step mechanism for intrachain energy transfer with hopping along the conjugated chains as the rate-limiting step; the higher efficiency of the interchain transfer process is mainly due to larger electronic coupling matrix elements between closely lying chains.

Polyfluorenes with polyphenylene dendron side chains: toward non-aggregating, light-emitting polymers.

A polyfluorene 12 has been prepared in which bulky polyphenylene dendrimer substituents suppress formation of long wavelength emitting aggregates, thus giving a polymer with pure blue emission. Absorption- and emission spectra and molecular modeling confirm that the bulky dendrimer side chains do not cause extra torsion between the fluorene units. New polyfluorenes with 9,9-diaryl substituents have been prepared to determine the minimum size of substituent necessary for aggregation suppression. An LED using 12 has been demonstrated to produce blue emission with onset voltages below 4 V.