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B-site Fe-doped (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 was synthesized by a facile chemical route to study the effect of doping on its physical properties. Detailed analysis of X-ray diffraction and Raman spectroscopy data revealed an increased lattice strain and thereby deviation from the morphotropic phase boundary with the progressive doping of Fe from 1 to 5 mol%. Such structural changes have resulted in the weakening of the energy band gap as well as deterioration of the ferroelectric polar nature which was evidenced by a shift of tetragonal to cubic transitions towards room temperature and hard doping effects in ferroelectric hysteresis. The doped samples exhibited room temperature ferromagnetism. Combined Mossbauer and X-ray photoelectron spectroscopic studies suggest that oxygen vacancies and defect complexes induced by Fe doping play a major role in magnetic properties. Local piezoresponse measurements illustrated imprint characteristics of ferroelectric domains in undoped and doped samples at the nanoscale. Room temperature magnetoelectric (ME) measurements revealed that 1 mol% Fe doped sample, having higher ferroelectric polarization and moderate magnetization, exhibits a strong ME response with a coefficient of 12.8 mV cm−1 Oe−1. The present study on Fe-doping effects on the structure and related ME properties of this important lead-free material is useful to tailor multiferroic applications in electronics. [ABSTRACT FROM AUTHOR]

Tungsten, silver, and tungsten/silver co-doped titaniananopowders were synthesised via an aqueous sol-gel method. The dried gels were thermally treated at 2 different temperatures, and the occurrence of the amorphous phase was assessed, using the combined Rietveld-RIR method, on the X-ray powder diffraction data. Systematic studies of the crystal structure and of the optical properties of the powders - made with diffuse reflectance spectroscopy (DRS) - were performed. The energy band gap was calculated using the differential reflectance method; their morphology was investigated using field emission scanning electron microscopy and transmission electron microscopy analyses (FE-SEM and TEM, respectively). The photocatalytic activity of the samples was assessed in liquid-solid phase, under UVA-light and visible-light irradiation, monitoring the degradation of an organic dye. The influence of the phase composition, optical properties, dimensions, and specific surface area of the powders on the photocatalytic activity was thoroughly discussed. [ABSTRACT FROM AUTHOR]

Abstract: A series of TiO2–SiO2 mixtures – having the following stoichiometry Ti1−x Si x O2, with x =0, 0.1, 0.3 and 0.5 atoms per formula unit – were prepared by using precursor oxides and fired at three temperatures (900, 1000 and 1200°C). The modifications in the structure and, consequently, on the photocatalytic activity, induced by the addition of SiO2 into the TiO2 powder, were thoroughly investigated by using various analytical techniques: X-ray powder diffraction, electron microscopy (FE-SEM and TEM), XPS, FT-IR, DRS and BET analysis. The results underlined as essentially no solid solution occurs between the two crystalline end-members. Nevertheless, silica addition caused a retarding effect on anatase-to-rutile phase transformation and on the crystallite growth. The photocatalytic activity of the powders was assessed in gas phase and the results were explained by taking into account the anatase and rutile relative amounts in the samples, their crystallite size, the surface hydroxyl groups adsorbed on the photocatalysts and the surface area of the mixtures. [Copyright &y& Elsevier]

The growing world energy consumption, with reliance on conventional energy sources and the associated environmental pollution, are considered the most serious threats faced by mankind. Heterogeneous photocatalysis has become one of the most frequently investigated technologies, due to its dual functionality, i.e., environmental remediation and converting solar energy into chemical energy, especially molecular hydrogen. H2 burns cleanly and has the highest gravimetric gross calorific value among all fuels. However, the use of a suitable electron donor, in what so-called "photocatalytic reforming", is required to achieve acceptable efficiency. This oxidation half-reaction can be exploited to oxidize the dissolved organic pollutants, thus, simultaneously improving the water quality. Such pollutants would replace other potentially costly electron donors, achieving the dual-functionality purpose. Since the aromatic compounds are widely spread in the environment, they are considered attractive targets to apply this technology. In this review, different aspects are highlighted, including the employing of different polymorphs of pristine titanium dioxide as photocatalysts in the photocatalytic processes, also improving the photocatalytic activity of TiO2 by loading different types of metal co-catalysts, especially platinum nanoparticles, and comparing the effect of various loading methods of such metal co-catalysts. Finally, the photocatalytic reforming of aromatic compounds employing TiO2-based semiconductors is presented. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (g-C3N4), possessing high thermal and chemical stability, non-toxicity, facile synthesis, and low band gap energy is a promising candidate for photocatalytic applications. In this study, bulk and exfoliated g-C3N4 were synthesised from different precursors (melamine and urea). Moreover, the surface of bulk g-C3N4 and exfoliated g-C3N4 was modified with graphene (0.5 wt% and 1 wt%) aiming to obtain a prolonged carrier lifetime. The effect of g-C3N4 synthesis from various precursors and the influence of graphene content on the photocatalytic activity during the degradation of a water–methanol mixture under UVC irradiation were examined, in comparison to commercial P25. Hydrogen, methane and carbon monoxide were the decomposition products; hydrogen was the main product of decomposition, whereas CH4 and CO resulting from the reduction of CO2 were generated in a significantly smaller amount. All the produced photocatalysts, whether pure or modified with graphene, exhibited higher activity than the commercial photocatalyst P25. [ABSTRACT FROM AUTHOR]

Abstract: Anatase-structured TiO2 films were deposited on a commercial fluorinated polymer (FEP) with a treated surface, by means of a sol–gel dip-coating technique. Two different curing temperatures were investigated and the film microstructures were characterized by X-ray diffraction, atomic force microscopy and scanning electron microscopy analyses. The prepared samples presented very high performances in terms of photocatalytic activities, analyzed by the degradation of an organic dye in a liquid medium, and of bactericidal activities, tested on Staphylococcus aureus (S. aureus, a Gram positive bacterium) and Escherichia coli (E. coli, a Gram negative bacterium). [Copyright &y& Elsevier]

Abstract: Karrooite, MgTi2O5, is a promising ceramic pigment due to its high refractoriness and refractive indices, as well as its ability to host transition metal ions in two crystallographically distinct octahedral sites. The colouring performance was investigated combining X-ray powder diffraction with UV–vis–NIR spectroscopy on karrooite doped with V, Cr, Mn, Fe, Co or Ni (M) according to the formula Mg1− x Ti2− xM 2 x O5, with x=0.02 and 0.05. Transition metals solubility in the karrooite lattice is not complete and a second phase is always present (geikielite or rutile). Structural data proved that incorporation of different chromophore ions into the karrooite structure affects unit cell parameters, bond length distances and angles, site occupancies and therefore cation order–disorder. Optical spectra exhibit broad absorbance bands of Co(II), Cr(IV), Fe(III), Mn(II), Mn(III), Ni(II), V(IV) with distinct contributions by cations in the M 1 and M 2 sites. Karrooite pigments have colours ranging from orange to brown-tan (Cr, Fe, Mn, V) to green (Co) and yellow (Ni) that are stable in low-temperature (<1050°C) ceramic glazes and glassy coatings. [Copyright &y& Elsevier]

Heavy pnictogen chalcohalides are often termed lead-free, perovskite-inspired materials. Despite theoretical predictions, incontrovertible experimental demonstrations of heavy pnictogen chalcohalides adopting a perovskite structure are lacking. Here we report our attempts to prepare CsBiSCl 2 adopting a perovskite structure as colloidal nanocrystals. Synthesis of nanoscale materials can indeed rely on fast, nonequilibrium reactions and on large, eventually thermodynamically favorable surface energies, leading to the possibility of stabilizing kinetically trapped or metastable phases. However, we obtained no CsBiSCl 2 , but a mixture of nanocrystals of secondary phases, namely Cs 3 BiCl 6 submicrometric polyhedra, Bi 2 S 3 nanoscopic rods, and Cs 3 Bi 2 Cl 9 nanoscopic dots, whose low polydispersity enabled an effective separation via size/shape selective precipitation. This work confirms that heavy pnictogen chalcohalides are hardly prone to adopting a perovskite structure. Nevertheless, chemistry at the nanoscale offers multiple possibilities for overcoming phase segregation and pursuing the synthesis of prospective mixed anion compound semiconductors.

MoS 2 is a two-dimensional layered transition metal dichalcogenide with unique electronic and optical properties. The fabrication of ultrathin MoS 2 is vitally important, since interlayer interactions in its ultrathin varieties will become thickness-dependent, providing thickness-governed tunability and diverse applications of those properties. Unlike with a number of studies that have reported detailed information on direct bandgap emission from MoS 2 monolayers, reliable experimental evidence for thickness-induced evolution or transformation of the indirect bandgap remains scarce. Here, the sulfurization of MoO 3 thin films with nominal thicknesses of 30 nm, 5 nm and 3 nm was performed. All sulfurized samples were examined at room temperature with spectroscopic ellipsometry and photoluminescence spectroscopy to obtain information about their dielectric function and edge emission spectra. This investigation unveiled an indirect-to-indirect crossover between the transitions, associated with two different Λ and K valleys of the MoS 2 conduction band, by thinning its thickness down to a few layers.

Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO 2 ) is extremely attractive as a transparent conducting material for applications in low-emission window coatings and solar cells, as well as in lithium-ion batteries and gas sensors. It is also an important catalyst and catalyst support for oxidation reactions. Here, we describe a novel nonaqueous sol-gel synthesis approach to produce tin oxide nanoparticles (NPs) with a low NP size dispersion. The success of this method lies in the nonhydrolytic pathway that involves the reaction between tin chloride and an oxygen donor, 1-hexanol, without the need for a surfactant or subsequent thermal treatment. This one-pot procedure is carried out at relatively low temperatures in the 160-260 °C range, compatible with coating processes on flexible plastic supports. The NP size distribution, shape, and dislocation density were studied by powder X-ray powder diffraction analyzed using the method of whole powder pattern modeling, as well as high-resolution transmission electron microscopy. The SnO 2 NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state 13 C and 1 H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of 13 C, 1 H, and 119 Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The 13 C SSNMR, FTIR, and Raman data showed the presence of organic species derived from the 1-hexanol reactant remaining within the samples. The optical absorption, studied using UV-visible spectroscopy, indicated that the band gap ( E g ) shifted systematically to lower energy with decreasing NP sizes. This unusual result could be due to mechanical strains present within the smallest NPs perhaps associated with the organic ligands decorating the NP surface. As the size increased, we observed a correlation with an increased density of screw dislocations present within the NPs that could indicate relaxation of the stress. We suggest that this could provide a useful method for band gap control within SnO 2 NPs in the absence of chemical dopants., Competing Interests: The authors declare no competing financial interest.