Purely Visible-Light-Induced Photochromism in Ag-TiO2 Nanoheterostructures.

We report titania nanoheterostructures decorated with silver, exhibiting tuneable photochromic properties for the first time when stimulated only by visible white light (domestic indoor lamp), with no UV wavelengths. Photochromic materials show reversible color changes under light exposure. However, all inorganic photochromic nanoparticles (NPs) require UV light to operate. Conventionally, multicolor photochromism in Ag-TiO2 films involves a change in color to brownish-gray during UV-light irradiation (i.e., reduction of Ag+ to Ag0) and a (re)bleaching (i.e., (re)oxidation of Ag0 to colorless Ag+) upon visible-light exposure. In this work, on the contrary, we demonstrate visible-light-induced photochromism (ranging from yellow to violet) of 1-10 mol % Ag-modified titania NPs using both spectroscopic and colorimetric CIEL*a*b* analyses. This is not a bleaching of the UV-induced color but a change in color itself under exposure to visible light, and it is shown to be a completely different mechanism-driven by the interfacial charge transfer of an electron from the valence band of TiO2 to that of the AgxO clusters that surround the titania-to the usual UV-triggered photochromism reported in titania-based materials. The quantity of Ag or irradiation time dictated the magnitude and degree of tuneability of the color change, from pale yellow to dark blue, with a rapid change visible only after a few seconds, and the intensity and red shift of surface plasmon resonance induced under visible light also increased. This effect was reversible after annealing in the dark at 100 °C/15 min. Photocatalytic activity under visible light was also assessed against the abatement of nitrogen oxide pollutants, for interior use, therefore showing the coexistence of photochromism and photocatalysis-both triggered by the same wavelength-in the same material, making it a multifunctional material. Moreover, we also demonstrate and explain why X-ray photoelectron spectroscopy is an unreliable technique with such materials.

High-quality PVD graphene growth by fullerene decomposition on Cu foils.

We present a new protocol to grow large-area, high-quality single-layer graphene on Cu foils at relatively low temperatures. We use C60 molecules evaporated in ultra high vacuum conditions as carbon source. This clean environment results in a strong reduction of oxygen-containing groups as depicted by X-ray photoelectron spectroscopy (XPS). Unzipping of C60 is thermally promoted by annealing the substrate at 800ºC during evaporation. The graphene layer extends over areas larger than the Cu crystallite size, although it is changing its orientation with respect to the surface in the wrinkles and grain boundaries, producing a modulated ring in the low energy electron diffraction (LEED) pattern. This protocol is a self-limiting process leading exclusively to one single graphene layer. Raman spectroscopy confirms the high quality of the grown graphene. This layer exhibits an unperturbed Dirac-cone with a clear n-doping of 0.77 eV, which is caused by the interaction between graphene and substrate. Density functional theory (DFT) calculations show that this interaction can be induced by a coupling between graphene and substrate at specific points of the structure leading to a local sp3 configuration, which also contribute to the D-band in the Raman spectra.

Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces.

We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion.

Investigation of temperature and frequency dependence of the dielectric properties of multiferroic (La0.8Ca0.2)0.4Bi0.6FeO3 nanoparticles for energy storage application.

In this work we synthesized the multifunctional (La0.8Ca0.2)0.4Bi0.6FeO3 material using a sol-gel process. Structural and morphologic investigations reveal a Pnma perovskite structure at room temperature with spherical and polygonal nanoparticles. A detailed study of the temperature dependence of the dielectric and electrical properties of the studied material proves a typical FE-PE transition with a colossal value of real permittivity at 350 K that allows the use of this material in energy storage devices. Thus, the investigation of the frequency dependence of the ac conductivity proves a correlated barrier hopping (CBH) conduction mechanism to be dominant in the temperature ranges of 150-170 K; the two observed Jonscher's power law exponents, s 1 and s 2 between 180 K and 270 K correspond to the observed dispersions in the ac conductivity spectra in this temperature region, unlike in the temperature range of 250-320 K, the small polaron tunnel (NSPT) was considered the appropriate conduction model.

The growth and improved magnetoelectric response of strain-modified Aurivillius SrBi4.25La0.75Ti4FeO18 thin films.

In this study, we grew 5-layered SrBi4.25La0.75Ti4FeO18 (SBLFT) polycrystalline thin films (80-330 nm thick) via pulsed-laser deposition to study their ferroelectric and magnetoelectric response. Structural/microstructural analysis confirmed the formation of orthorhombic SBLFT with good crystallinity and randomly oriented Aurivillius phases. Detailed scanning transmission electron microscopy analysis of 120 nm film revealed a predominantly five-layered structure with the coexistence of four-layer stacking. Such stacking defects are found to be pertinent to the high structural flexibility of Bi-rich Aurivillius phases, alleviated by lattice strain. Raman spectral features at ambient temperatures depict the signature of the orthorhombic-tetragonal phase transition. SBLFT films have a strong ferroelectric nature (remanent polarization 2Pr of 35 µC cm-2) with a fatigue endurance up to 1010 cycles and strongly improved, switchable magnetization as opposed to its antiferromagnetic bulk counterpart. The scaling behavior of dynamic hysteresis reveals that ferroelectric domain reversal has good stability and low energy consumption. We observed the presence of SBLFT nanoregions (1-5 nm), distributed across the film, with Bi and Fe-rich compositions and oxygen vacancies that contribute to the weak ferromagnetic behavior mediated by the Dzyaloshinskii-Moriya interactions. Subtle changes in the structural strain and lattice distortions of thin films with varied thicknesses led to distinct ferroic properties. Stronger ferroelectric polarization of 80 nm and 120 nm films compared to that of thicker ones can be due to structural strain and the possible rearrangement of BO6 octahedra. The observation of the improved magnetoelectric coefficient of 50 mV cm-1 Oe-1 for 120 nm film, as compared to that of several Aurivillius oxides, indicates that the structural strain modification in SBLFT is beneficial for the fatigue-free magnetic field switching of ferroelectric polarization. The structural strain of the unit cell as well as the presence of Bi- and ferromagnetic Fe-rich nanoregions was found to be responsible for the improved multiferroic behaviour of the SBLFT films.