Ni(II)-doped CuWO4 photoanodes with enhanced photoelectrocatalytic activity.

CuWO4 has emerged in the last years as a ternary metal oxide material for photoanodes application in photoelectrochemical cells, thanks to its relatively narrow band gap, high stability and selectivity toward the oxygen evolution reaction, though largely limited by its poor charge separation efficiency. Aiming at overcoming this limitation, we investigate here the effects that Cu(II) ion substitution has on the photoelectrocatalytic (PEC) performance of copper tungstate. Optically transparent CuWO4 thin-film photoanodes, prepared via spin coating and containing different amounts of Ni(II) ions, were fully characterized via UV-Vis spectroscopy, XRD and SEM analyses, and their PEC performance was tested via linear sweep voltammetry, incident photon to current efficiency and internal quantum efficiency analyses. From tests performed in the presence of a hole scavenger-containing electrolyte, the charge injection and separation efficiencies of the electrodes were also calculated. Pure-phase crystalline and/or heterojunction materials were obtained with higher PEC performance compared to pure CuWO4, mainly due to a significantly enhanced charge separation efficiency in the bulk of the material.

Sculpturing patterns of plasmonic silver nanoprisms by means of photocatalytic lithography.

The controlled shaping of nanoparticles' morphology is one of the pillars of nanotechnology. Here, we demonstrate that photocatalytic lithography, a technique already proved to be useful in materials science, can act as a dry etching technique for noble metal nanoparticles. Triangular silver nanoprisms are self-assembled on titanium dioxide films and photocatalytically shaped into discoidal particles upon irradiation with near-UV light. The obtained patterned surfaces show a dramatically different surface-enhanced Raman scattering response, suggesting the utility of our approach for the development of sensors. The photocatalytic nature of the particle shaping is demonstrated and a plausible mechanism drawn by performing photocatalysis in different configurations (direct and remote) and by irradiating in different solvents.

Improved Photoelectrochemical Performance of WO3/BiVO4 Heterojunction Photoanodes via WO3 Nanostructuring.

WO3/BiVO4 heterojunction photoanodes can be efficiently employed in photoelectrochemical (PEC) cells for the conversion of water into molecular oxygen, the kinetic bottleneck of water splitting. Composite WO3/BiVO4 photoelectrodes possessing a nanoflake-like morphology have been synthesized through a multistep process and their PEC performance was investigated in comparison to that of WO3/BiVO4 photoelectrodes displaying a planar surface morphology and similar absorption properties and thickness. PEC tests, also in the presence of a sacrificial hole scavenger, electrochemical impedance analysis under simulated solar irradiation, and incident photon to current efficiency measurements highlighted that charge transport and charge recombination issues affecting the performance of the planar composite can be successfully overcome by nanostructuring the WO3 underlayer in nanoflake-like WO3/BiVO4 heterojunction electrodes.

Photoanodes based on nanostructured WO3 for water splitting.

Anodically grown WO(3) photoelectrodes prepared in an N-methylformamide (NMF) electrolyte have been investigated with the aim of exploring the effects induced by anodization time and water concentration in the electrochemical bath on the properties of the resulting photoanodes. An n-type WO(3) semiconductor is one of the most promising photoanodes for hydrogen production from water splitting and the electrochemical anodization of tungsten allows very good photoelectrodes, which are characterized by a low charge-transfer resistance and an increased spectral response in the visible region, to be obtained. These photoanodes were investigated by a combination of steady state and transient photoelectrochemical techniques and a correlation between photocurrent produced, morphology, and charge transport has been evaluated.

Polymer-Assisted Single-Step Slot-Die Coating of Flexible Perovskite Solar Cells at Mild Temperature from Dimethyl Sulfoxide.

The industrialization of perovskite solar cells relies on solving intrinsic-to-material issues. To reach record efficiencies perovskite deposition needs to be finely adjusted by multi-step processes, in a humidity free glove-box environment and by means of hardly scalable techniques often associated with toxic solvents and anti-solvent dripping/bath. Herein, the use of polymeric material is proposed to deposit perovskite layers with easy processability. To the scope, a starch-polymer/perovskite composite is developed to suit slot-die coating technique requirement, allowing the deposition of hybrid halide perovskite material in a single straightforward step without the use of toxic solvents, and in uncontrolled humid environment (RH up to 70 %). The starch-polymer increases the viscosity of the perovskite precursor solutions and delays the perovskite crystallization that results in the formation of perovskite films at mild temperature (60 °C) with good morphology. These innovative inks enables the fabrication of flexible solar cells with p-i-n configuration featured by a power conversion efficiency higher than 3 %. . Overall, this approach can be exploited in the future to massively reduce perovskite manufacturing costs related to keeping the entire fabrication line at high-temperature and under nitrogen or dry conditions.

Solvent-free phenyl-C61-butyric acid methyl ester (PCBM) from clathrates: insights for organic photovoltaics from crystal structures and molecular dynamics.

The first solvent-free crystal structure of PCBM, an organic semiconductor widely used in solvent-free nanocrystalline films in plastic solar cells, is reported and its relevance to structure-property relationships discussed. The PCBM structure, obtained from o-dichlorobenzene solvates by solvent abstraction, was solved using powder diffraction, demonstrating this possibility for functionalized fullerenes.

Loading silica with metals (palladium or platinum) under mild conditions by using well-defined molecular precursors.

The loading of pre-treated amorphous silica with platinum or palladium was carried out by using the molecular precursors Pt2(micro-Cl)2Cl2(CO)2, or Pd2(micro-Cl)2Cl2(CO)2, respectively, which contain the required amount of coordinated CO to carry out the formation of the metal particles upon contact with moisture. The reactivity of the well-soluble mononuclear platinum complex cis-PtCl2(CO)2 with stoichiometric amounts of water was investigated either under N2 or CO. The metal nanoparticles produced on the silica matrix have been characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The catalytic performance of the silica-supported metals thus produced was evaluated in the hydrogenation of cyclohexene.