Elena Lestini

Plasmonic Enhancement of Dye Sensitized Solar Cells via a Tailored Size-Distribution of Chemically Functionalized Gold Nanoparticles

A substantial and stable increase of the current density Jsc of ruthenium (Ru) dye sensitized solar cells (DSC) of up to 16.18% and of the power efficiency of up to 25.5% is demonstrated in this article via plasmonic enhancement. The key aspect of this work is the use of a tailored bimodal size distribution of functionalized gold nanoparticles (AuNPs) that have been chemically immobilized onto the mesoporous titanium dioxide (TiO2) layer via short, stable dithiodibutyric acid linkers. The size distribution of the AuNPs is a result of theoretical calculations that aimed at the perfection of the absorption characteristics of the complete solar cell system over a wide range of wavelengths. The functionalization of the AuNPs serves to bind them at a close but defined distance to TiO2-particles and additionally to chemically protect them against potential corrosion by the electrolyte. Simulations of near field (enhanced absorption) and far field (scattering) contributions have been used to tailor a complex AuNPs bimodal size distribution that had subsequently demonstrated experimentally a close to optimum improvement of the absorbance over a wide wavelength range (500–675 nm) and therefore an impressive DSC efficiency enhancement. Finally, the modified DSCs are exhibiting pronounced longevity and stable performance as confirmed via long time measurements. In summary, the presented systems show increased performance compared to non plasmonic enhanced cells with otherwise identical composition, and are demonstrating a previously unpublished longevity for iodide electrolyte/AuNPs combinations.

Electron Transfer and Switching in Rigid [2]Rotaxanes Adsorbed on TiO2 Nanoparticles

Bistable [2]rotaxanes have been attached through a bulky tripodal linker to the surface of titanium dioxide nanoparticles and studied by cyclic voltammetry and spectroelectrochemical methods. The axle component in the [2]rotaxane contains two viologen sites, V(1) and V(2), interconnected by a rigid terphenylene bridge. In their parent dication states, V(1)(2+) and V(2)(2+) can both accommodate a crown ether ring, C, but are not equivalent in terms of their affinity towards C and have different electrochemical reduction potentials. The geometry and size of the tripodal linker help to maintain a perpendicular [2]rotaxane orientation at the surface and to avoid unwanted side-to-side interactions. When the rigid [2]rotaxane or its corresponding axle are adsorbed on a TiO(2) nanoparticle, viologen V(2)(2+) is reduced at significantly more negative potentials (-0.3 V) than in flexible analogues that contain aliphatic bridges between V(1) and V(2). These overpotentials are analysed in terms of electron-transfer rates and a donor-bridge-acceptor (D-B-A) formalism, in which D is the doubly reduced viologen, V(1)(0), adjacent to the TiO(2) surface (TiO(2)-V(1)(0)), B is the terphenylene bridge and A is viologen V(2)(2+). We have also found that, in contrast with earlier findings in solution, no molecular shuttling occurs in rigid [2]rotaxane adsorbed at the surface. The observations were explained by the relative position of the viologen stations within the electrical double layer, screening of V(2)(2+) by the counterions and high capacity of the medium, which reduces the mobility of the crown ether. The results are useful in transposing of solution-based molecular switches to the interface or in the design and understanding of the properties of systems comprising electroactive and/or interlocked molecules adsorbed at the nanostructured TiO(2) surface.

Alternative Mild Route to the Synthesis of 4-Methylenecyclohex-2-enone, a Key Moiety of the Anticancer Compounds Ottelione A and B

GRAPHICAL ABSTRACT

Linear self-assembly and grafting of gold nanorods into arrayed micrometer-long nanowires on a silicon wafer via a combined top-down/bottom-up approach

Macroscopically long wire-like arrangements of gold nanoparticles were obtained by controlled evaporation and partial coalescence of an aqueous colloidal solution of capped CTAB-Au nanorods onto a functionalised 3-mercaptopropyl trimethoxysilane (MPTMS) silicon substrate, using a removable, silicon wafer with a hydrophobic surface that serves as a “handrail” for the initial nanorods’ linear self-assembly. The wire-like structures display a quasi-continuous pattern by thermal annealing of the gold nanorods when the solvent (i.e. water) is evaporated at temperatures rising from 20°C to 140°C. Formation of both single and self-replicating parallel 1D-superstructures consisting of two or even three wires is observed and explained under such conditions.