Prospective Chalcohalide Perovskites: Pursuing (and Failing) the Synthesis of CsBiSCl2 Nanocrystals.

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 CsBiSCl2 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 CsBiSCl2, but a mixture of nanocrystals of secondary phases, namely Cs3BiCl6 submicrometric polyhedra, Bi2S3 nanoscopic rods, and Cs3Bi2Cl9 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.

Molybdenum precursor delivery approaches in atomic layer deposition of α-MoO3.

In this research work, we present a study on time-sequenced plasma-enhanced atomic layer deposition (PE-ALD) processes towards the achievement of high-quality α-MoO3 thin films which are suitable for exfoliation. In particular, a conventional precursor injection method along with a boosted precursor delivery approach are discussed and analysed. In the latter, the proposed gas supply mechanism ensures a large number of deposited Mo atoms per unit of time, which, along with a proper thermal energy, leads to high-quality and oriented orthorhombic α-MoO3 films. The proposed boosted approach is also compared with post growth annealing steps, resulting in more effective achievement of a highly oriented orthorhombic α-MoO3 phase and less time consumption.

Two-Channel Indirect-Gap Photoluminescence and Competition between the Conduction Band Valleys in Few-Layer MoS2.

MoS2 is a two-dimensional layered transition metal dichalcogenide with unique electronic and optical properties. The fabrication of ultrathin MoS2 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 MoS2 monolayers, reliable experimental evidence for thickness-induced evolution or transformation of the indirect bandgap remains scarce. Here, the sulfurization of MoO3 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 MoS2 conduction band, by thinning its thickness down to a few layers.

Pseudocapacitive behaviour in sol-gel derived electrochromic titania nanostructures.

Nanostructured thin films are widely investigated for application in multifunctional devices thanks to their peculiar optoelectronic properties. In this work anatase TiO2 nanoparticles (average diameter 10 nm) synthesised by a green aqueous sol-gel route are exploited to fabricate optically active electrodes for pseudocapacitive-electrochromic devices. In our approach, highly transparent and homogeneous thin films having a good electronic coupling between nanoparticles are prepared. These electrodes present a spongy-like nanostructure in which the dimension of native nanoparticles is preserved, resulting in a huge surface area. Cyclic voltammetry studies reveal that there are significant contributions to the total stored charge from both intercalation capacitance and pseudocapacitance, with a remarkable 50% of the total charge deriving from this second effect. Fast and reversible colouration occurs, with an optical modulation of ∼60% in the range of 315-1660 nm, and a colouration efficiency of 25.1 cm2 C-1 at 550 nm. This combination of pseudocapacitance and electrochromism makes the sol-gel derived titania thin films promising candidates for multifunctional 'smart windows'.

Films of chitosan and natural modified hydroxyapatite as effective UV-protecting, biocompatible and antibacterial wound dressings.

Chitosan is a natural polysaccharide widely used in biomedicine, for instance for wound dressing. Hydroxyapatite is a very bioactive calcium phosphate which, if modified with an appropriate element (iron Fe), can also have UV-absorbing properties. In this work, we report the study of films of chitosan incorporated with iron-modified hydroxyapatite of natural origin (from cod fish bones); this combination led to an innovative chitosan-based material with excellent and advanced functional properties. The films showed very high UV absorption (Ultraviolet Protection Factor (UPF) value higher than 50). This is the first time that a chitosan-based material has shown such high UV protection properties. The films also showed to be non-cytotoxic, and possessed antimicrobial activity towards both Gram-positive and negative strains. Their mechanical properties, optimised with an experimental design approach, confirmed their potential use as multifunctional wound dressing, capable of reducing bacterial infections and, at the same time, protecting from UV light.

Waste-Based Pigments for Application in Ceramic Glazes and Stoneware Bodies.

The use of wastes, some of them hazards, as raw materials of ceramic pigments has been a way to diminish their environmental impact, to economically valorize them, and to face the depletion of virgin raw materials. In this work were prepared pigments having in their composition only industrial wastes: Cr/Ni electroplating (ES), and sludges from the cutting of natural stones-marble (MS) and granite (GS). The prepared mixtures were calcined at three temperatures (1100, 1200, and 1300 °C) and the obtained powders were characterized by XRD and UV-vis. Their coloring strength and thermal stability were assessed by adding them to different ceramic substrates: glazes (transparent bright and opaque matte) and a stoneware paste. The CIEL*a*b* coordinates of the fired materials were measured. The developed pigments are thermally stable and exhibit good tinting power, originating nicely colored and defect-free ceramic materials.

Exploring Tantalum as a Potential Dopant to Promote the Thermoelectric Performance of Zinc Oxide.

Zinc oxide (ZnO) has being recognised as a potentially interesting thermoelectric material, allowing flexible tuning of the electrical properties by donor doping. This work focuses on the assessment of tantalum doping effects on the relevant structural, microstructural, optical and thermoelectric properties of ZnO. Processing of the samples with a nominal composition Zn1-xTaxO by conventional solid-state route results in limited solubility of Ta in the wurtzite structure. Electronic doping is accompanied by the formation of other defects and dislocations as a compensation mechanism and simultaneous segregation of ZnTa2O6 at the grain boundaries. Highly defective structure and partial blocking of the grain boundaries suppress the electrical transport, while the evolution of Seebeck coefficient and band gap suggest that the charge carrier concentration continuously increases from x = 0 to 0.008. Thermal conductivity is almost not affected by the tantalum content. The highest ZT~0.07 at 1175 K observed for Zn0.998Ta0.002O is mainly provided by high Seebeck coefficient (-464 V/K) along with a moderate electrical conductivity of ~13 S/cm. The results suggest that tantalum may represent a suitable dopant for thermoelectric zinc oxide, but this requires the application of specific processing methods and compositional design to enhance the solubility of Ta in wurtzite lattice.

Hydrothermal Synthesis of Rare-Earth Modified Titania: Influence on Phase Composition, Optical Properties, and Photocatalytic Activity.

In order to expand the use of titania indoor as well as to increase its overall performance, narrowing the band gap is one of the possibilities to achieve this. Modifying with rare earths (REs) has been relatively unexplored, especially the modification of rutile with rare earth cations. The aim of this study was to find the influence of the modification of TiO2 with rare earths on its structural, optical, morphological, and photocatalytic properties. Titania was synthesized using TiOSO4 as the source of titanium via hydrothermal synthesis procedure at low temperature (200 °C) and modified with selected rare earth elements, namely, Ce, La, and Gd. Structural properties of samples were determined by X-ray powder diffraction (XRD), and the phase ratio was calculated using the Rietveld method. Optical properties were analyzed by ultraviolet and visible light (UV-Vis) spectroscopy. Field emission scanning electron microscope (FE-SEM) was used to determine the morphological properties of samples and to estimate the size of primary crystals. X-ray photoelectron spectroscopy (XPS) was used to determine the chemical bonding properties of samples. Photocatalytic activity of the prepared photocatalysts as well as the titania available on the market (P25) was measured in three different setups, assessing volatile organic compound (VOC) degradation, NOx abatement, and water purification. It was found out that modification with rare earth elements slows down the transformation of anatase and brookite to rutile. Whereas the unmodified sample was composed of only rutile, La- and Gd-modified samples contained anatase and rutile, and Ce-modified samples consisted of anatase, brookite, and rutile. Modification with rare earth metals has turned out to be detrimental to photocatalytic activity. In all cases, pure TiO2 outperformed the modified samples. Cerium-modified TiO2 was the least active sample, despite having a light absorption tail up to 585 nm wavelength. La- and Gd-modified samples did not show a significant shift in light absorption when compared to the pure TiO2 sample. The reason for the lower activity of modified samples was attributed to a greater Ti3+/Ti4+ ratio and a large amount of hydroxyl oxygen found in pure TiO2. All the modified samples had a smaller Ti3+/Ti4+ ratio and less hydroxyl oxygen.

Solid-Gas Phase Photo-Catalytic Behaviour of Rutile and TiOn (1 < n < 2) Sub-Oxide Phases for Self-Cleaning Applications.

The solid-gas phase photo-catalytic activities of rutile TiO2 and TiOn (1 < n < 2) sub-oxide phases have been evaluated. Varying concentrations of Ti3+ defects were introduced into the rutile polymorph of titanium dioxide through carbo-thermal reduction at temperatures ranging from 350 °C to 1300 °C. The resulting sub-oxides formed were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, impedance spectroscopy and UV-visible diffuse reflectance spectroscopy. The presence of Ti3+ in rutile exposed to high reduction temperatures was confirmed by X-ray diffraction. In addition, a Ti3+-Ti4+ system was demonstrated to enhance the photo-catalytic properties of rutile for the degradation of the air pollutants NO2 and CO2 under UV irradiation of wavelengths (λ) 376⁻387 nm and 381⁻392 nm. The optimum reduction temperature for photo-catalytic activity was within the range 350⁻400 °C and attributed to improved charge-separation. The materials that were subject to carbo-thermal reduction at temperatures of 350 °C and 400 °C exhibited electrical conductivities over one hundred times higher compared to the non-reduced rutile. The results highlight that sub-oxide phases form an important alternative approach to doping with other elements to improve the photo-catalytic performance of TiO2. Such materials are important for applications such as self-cleaning where particles can be incorporated into surface coatings.

One-Step Synthesis, Structure, and Band Gap Properties of SnO2 Nanoparticles Made by a Low Temperature Nonaqueous Sol-Gel Technique.

Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO2) 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 SnO2 NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state 13C and 1H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of 13C, 1H, and 119Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The 13C 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 SnO2 NPs in the absence of chemical dopants.

Hybrid Noble-Metals/Metal-Oxide Bifunctional Nano-Heterostructure Displaying Outperforming Gas-Sensing and Photochromic Performances.

As nanomaterials are dominating 21st century's scene, multiple functionality in a single (nano)structure is becoming very appealing. Inspired by the Land of the Rising Sun, we designed a bifunctional (gas-sensor/photochromic) nanomaterial, made with TiO2 whose surface was simultaneously decorated with copper and silver (the Cu/Ag molar ratio being 3:1). This nanomaterial outperformed previous state-of-the-art TiO2-based sensors for the detection of acetone, as well as the Cu-TiO2-based photochromic material. It indeed possessed splendid sensitivity toward acetone (detection limit of 100 ppb, 5 times lower than previous state-of-the-art TiO2-based acetone sensors), as well as reduced response/recovery times at very low working temperature, 150 °C, for acetone sensing. Still, the same material showed itself to be able to (reversibly) change in color when stimulated by both UV-A and, most remarkably, visible light. Indeed, the visible-light photochromic performance was almost 3 times faster compared to the standard Cu-TiO2 photochromic material-that is, 4.0 min versus 10.8 min, respectively. It was eventually proposed that the photochromic behavior was triggered by different mechanisms, depending on the light source used.

Erratum: One-Step Synthesis, Structure, and Band Gap Properties of SnO2 Nanoparticles Made by a Low Temperature Nonaqueous Sol-Gel Technique.

[This corrects the article DOI: 10.1021/acsomega.8b02122.].

Smallest Bimetallic CoPt3 Superparamagnetic Nanoparticles.

We present for the first time a nonaqueous sol-gel route to produce ultrasmall (<2 nm) magnetic bimetallic CoPt3 nanoparticles (NPs). The one-pot procedure is carried out at low temperature (180 °C) using benzyl alcohol, acting as both reducing agent and solvent. The highly monodisperse CoPt3 NPs were investigated with innovative advanced X-ray methods (whole powder pattern modeling), HR-STEM, XPS, and SQUID magnetometry. XPS showed Co was mostly in metallic form, but with a very small amount of CoO on the NP surface. The spherical NPs had an ultrasmall diameter of 1.6 nm and could self-assemble in aligned linear chains, or nanobelts, of single NPs. They are superparamagnetic, with blocking temperature of ∼20 K and coercivity at 10 K of 27.9 kA m-1 (∼350 Oe). However, there is evidence of a second magnetic phase (probably CoO) in the ZFC magnetization curve, which enhances their magnetization values, without significantly affecting their superparamagnetism.

Alkali Niobate and Tantalate Perovskites as Alternative Photocatalysts.

Alkali tantalates and niobates are listed as important photocatalysts for the development of renewable energy technologies and environmental remediation. Herein, the photocatalytic degradation of methylene blue dye in aqueous solution by using highly crystalline particles with perovskite-like structures, LiTaO3 , LiNbO3 , NaTaO3 , NaNbO3 , KNbO3 , and KTaO3 , is investigated. It is demonstrated that ferroelectric KNbO3 is the most efficient photocatalyst of those tested because it combines an electronic band structure that can respond successfully to UVA light with a relatively high surface energy that enhances the catalytic properties. Additionally, the built-in electric field due to internal polarization of ferroelectric particles may contribute to the unique properties of this functional photocatalyst. This work provides an ideal platform for the rational design of more efficient ferroelectric-based photocatalytic devices.

Dielectrical Properties of CeO2 Nanoparticles at Different Temperatures.

A template-free precipitation method was used as a simple and low cost method for preparation of CeO2 nanoparticles. The structure and morphology of the prepared nanoparticle samples were studied in detail using X-ray diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM) measurements. The whole powder pattern modelling (WPPM) method was applied on XRD data to accurately measure the crystalline domain size and their size distribution. The average crystalline domain diameter was found to be 5.2 nm, with a very narrow size distribution. UV-visible absorbance spectrum was used to calculate the optical energy band gap of the prepared CeO2 nanoparticles. The FT-IR spectrum of prepared CeO2 nanoparticles showed absorption bands at 400 cm(-1) to 450 cm(-1) regime, which correspond to CeO2 stretching vibration. The dielectric constant (εr) and dielectric loss (tan δ) values of sintered CeO2 compact consolidated from prepared nanoparticles were measured at different temperatures in the range from 298 K (room temperature) to 623 K, and at different frequencies from 1 kHz to 1 MHz.