Effective piezoelectric response of substrate-integrated ZnO nanowire array devices on galvanized steel.

Harvesting waste energy through electromechanical coupling in practical devices requires combining device design with the development of synthetic strategies for large-area controlled fabrication of active piezoelectric materials. Here, we show a facile route to the large-area fabrication of ZnO nanostructured arrays using commodity galvanized steel as the Zn precursor as well as the substrate. The ZnO nanowires are further integrated within a device construct and the effective piezoelectric response is deduced based on a novel experimental approach involving induction of stress in the nanowires through pressure wave propagation along with phase-selective lock-in detection of the induced current. The robust methodology for measurement of the effective piezoelectric coefficient developed here allows for interrogation of piezoelectric functionality for the entire substrate under bending-type deformation of the ZnO nanowires.

A substrate-integrated and scalable templated approach based on rusted steel for the fabrication of polypyrrole nanotube arrays.

We report here a facile, generalizable, and entirely scalable approach for the fabrication of vertically aligned arrays of Fe(2)O(3)/polypyrrole core-shell nanostructures and polypyrrole nanotubes. Our "all electrochemical" approach is based on the fabrication of α-Fe(2)O(3) nanowire arrays by the simple heat treatment of commodity low carbon steel substrates, followed by electropolymerization of conformal polypyrrole sheaths around the nanowires. Subsequently, electrochemical etching of the nanowires yields large-area vertically aligned polypyrrole nanotube arrays on the steel substrate. The developed methodology is generalizable to functionalized pyrrole monomers and represents a significant practical advance of relevance to the technological implementation of conjugated polymer nanostructures in electrochromics, electrochemical energy storage, and sensing.

Matter of age: growing anisotropic gold nanocrystals in organic media.

We investigated the influence of the reduction state of gold ions on the growth of gold nanocrystals in N,N-dimethyl formamide (DMF). While freshly prepared solutions of AuCl3 produce spherical nanocrystals, aged precursor solutions containing mainly Au+ ions and Au(0) atoms lead to various branched nanoparticles. Furthermore, we show that also the amount of the reducing and stabilisation agent tetra-n-octylammonium formate (TOAF) plays a decisive role on the shape of the nanocrystals, allowing us to grow triangular and cubic nanoparticles.

Ion- and atom-leaching mechanisms from palladium nanoparticles in cross-coupling reactions.

Leaching of palladium species from Pd nanoparticles under C--C coupling conditions was observed for both Heck and Suzuki reactions by using a special membrane reactor. The membrane allows the passage of palladium atoms and ions, but not of species larger than 5 nm. Three possible mechanistic scenarios for palladium leaching were investigated with the aim of identifying the true catalytic species. Firstly, we examined whether or not palladium(0) atoms could leach from clusters under non-oxidising conditions. By using our membrane reactor, we proved that this indeed happens. We then investigated whether or not small palladium(0) clusters could in fact be the active catalytic species by analysing the reaction composition and the palladium species that diffused through the membrane. Neither TEM nor ICP analysis supported this scenario. Finally, we tested whether or not palladium(II) ions could be leached in the presence of PhI by oxidative addition and the formation of [Pd(II)ArI] complexes. Using mass spectrometry, UV-visible spectroscopy and 13C NMR spectroscopy, we observed and monitored the formation and diffusion of these complexes, which showed that the first and the third mechanistic scenarios were both possible, and were likely to occur simultaneously. Based on these findings, we maintain that palladium nanoparticles are not the true catalysts in C--C coupling reactions. Instead, catalysis is carried out by either palladium(0) atoms or palladium(II) ions that leach into solution.

A simple method for measuring the size of metal nanoclusters in solution.

The connection between quantum size effects and the surface plasmon resonance of metal nanoclusters is introduced and the pros and cons of in situ and ex situ cluster analysis methods are outlined. A new method for estimating the size of nanoclusters is presented. This method combines core/shell cluster synthesis, UV-visible spectroscopy, and Mie theory. The core/shell approach enables the estimation of metal cluster sizes directly from the UV-visible spectra, even for transition metal nanoclusters such as Pd that have no distinct surface-plasmon peak in UV-visible region. Pd/Au and Au/Pd core/shell clusters as well as Au-Pd alloy clusters are synthesized and used as test cases for simulations and spectroscopic measurements. The results of the simulations and UV-visible spectroscopy experiments are validated with transmission electron microscopy.

In-situ UV-visible study of Pd nanocluster formation in solution.

The formation of Pd nanoclusters in solution is studied. This system has two types of light-absorbing species: Pd ions which absorb light via electronic transitions and Pd clusters and aggregates which absorb light via valence-conduction transitions and also scatter light due to their nanometric dimensions. Here we monitor these dynamic changes using UV-visible spectroscopy. The reduction and clustering concentration profiles are extracted from the raw data using a combination of net analyte signal (NAS) and principal component analysis (PCA) methods. PdCl2, Pd(OAc)2 and Pd(NO3)2 are used as Pd2+ precursors and various tetra-n-octylammonium carboxylates are applied as reducing and stabilising agents. This in situ approach enables the quantification of both the reduction of the Pd2+ ions and the growth of the Pd clusters. Kinetic models that account for ion reduction, cluster growth and aggregation are presented and the influence of the counteranions and the reducing agents on these processes is discussed.