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

American Chemical Society. 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 SnO2NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state13C and1H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of13C,1H, and119Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The13C 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 (Eg) 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 SnO2NPs in the absence of chemical dopants

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

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Shell pressure on the core of MnO/Mn3O4 core/shell nanoparticles

Here we show that spontaneous oxidation of MnO nanoparticles into MnO/Mn3O4 core/shell nanoparticles has the effect of a local pressure, decreasing the MnO cell parameter and increasing strain, resulting in the increase of the MnO antiferromagnetic/paramagnetic transition temperature T-N. These effects are more severe in smaller nanoparticles

Synthesis of cobalt aluminate nanopigments by a non-aqueous sol-gel route

Here we report the chemical synthesis of cobalt aluminum oxide (CoAl2O4) nanoparticles by a non-aqueous sol-gel route. The one-pot procedure is carried out at mild temperatures (in the 150 to 300 °C range), and consists of the reaction between cobalt acetate and aluminium isopropoxide in benzyl alcohol. The resulting CoAl2O4 nanoparticles show an unusually low average size, between 2.5 and 6.2 nm, which can be controlled by the synthesis temperature. The colorimetric properties of the nanoparticles are also determined by the synthesis temperature and the characteristic blue color of CoAl2O4 pigments is achieved in samples prepared at T ¿ 200 °C. The nanoparticles are antiferromagnetically ordered below ~27 K with an uncompensated configuration. The uncompensated moment shows the typical features of strongly interacting superparamagnetic nanoparticles and spin-glass systems.M.K. thanks Fundação para a Ciência e a Tecnologia (FCT) for grant no. SFRH/BPD/74477/2010. N.J.O.S. thanks FCT for Ciencia 2008 program. Partial funding from FCT under the program COMPETE – FEDER (PTDC/FIS/105416/2008) and Pest-C/CTM/LA0011/2011 is acknowledged. The Aveiro-Zaragoza collaboration has been supported by the Integrated Spanish-Portuguese Action PT2009-0131.Peer Reviewe

Non-aqueous sol-gel synthesis through a low-temperature solvothermal process of anatase showing visible-light photocatalytic activity

A novel, facile method based on a non-aqueous sol-gel solvothermal process has been developed to synthesise spherical TiO2 nanoparticles (NPs) in one pot. The reaction between titanium(iv) tert-butoxide (Ti[OC(CH3)3]4) and benzyl alcohol was a simple process, which resulted in the formation of highly crystalline titania NPs with a small size of only 6 nm, and with a correspondingly high surface area. The chemical formation mechanism of the metal oxide NPs has been proposed, and the degree of surface hydroxyls (-OH groups) has been examined. The products of the synthesis were characterised by X-ray powder diffraction (XRPD) using the advanced whole powder pattern modelling (WPPM) method, high-resolution transmission electron microscopy (HR-TEM), thermo-gravimetric analysis (TGA), UV-visible diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FT-IR), and nuclear magnetic resonance (NMR) spectroscopy. The photocatalytic activity (PCA) was evaluated in both the liquid-solid phase, by monitoring the degradation of an organic dye (methylene blue (MB)) under UV-light irradiation, and in the gas-solid phase, by following the degradation of 2-propanol under UV- and visible-light exposures. The synthesized titania powders not only exhibited excellent photocatalysis in the liquid-solid phase (under UV irradiation), but also possessed a superior PCA in the gas-solid phase under a visible-light exposure. The effects on the PCA of the very small crystalline domain size, surface composition and the presence of organic molecules due to the synthesis process of the TiO2 NPs were shown to account for this behaviour

High dielectric constant and capacitance in ultrasmall (2.5 nm) SrHfO3 perovskite nanoparticles produced in a low temperature non-aqueous sol-gel route

Strontium hafnium oxide (SrHfO3) has great potential as a high-k gate dielectric material, for use in memories, capacitors, CMOS and MOSFETs. We report for the first time the dielectric properties (relative permittivity and capacitance) of SrHfO3 nanoparticles (NPs), as opposed to thin films or sintered bulk ceramics. These monodisperse, ultra-small, perovskite-type SrHfO3 nanocrystals were synthesised through a non-aqueous sol-gel process under solvothermal conditions (at only 220 °C) using benzyl alcohol as a solvent, and with no other capping agents or surfactants. Advanced X-ray diffraction methods (whole powder pattern modelling, WPPM), CS-corrected high-resolution scanning transmission electron microscopy (HRSTEM), dielectric spectroscopy, and optical (UV-vis, Raman) and photoluminescent spectroscopy were used to fully characterise the NPs. These SrHfO3 NPs are the smallest reported and highly monodisperse, with a mean diameter of 2.5 nm, a mode of 2.0 nm and a small size distribution. The formation mechanism of the NPs was determined using NMR and GC-MS analysis of the species involved. Our SrHfO3 nanoparticles had a dielectric constant of 17, which is on par with literature data for bulk and thin film samples, and they also had a relatively large capacitance of 9.5 nF cm-2. As such, they would be suitable for applications as gate dielectrics for capacitors and in metal-oxide semiconductor field-effect transistor (MOSFET) technology

Novel nanosynthesis of In2O3 and its application as a resistive gas sensor for sevoflurane anesthetic

A novel non-aqueous sol-gel route for synthesizing pure indium oxide (In2O3) nanoparticles (NPs) using indium acetylacetonate and n-butylamine as the reactive solvent, under solvothermal conditions, is herein proposed. The samples were characterized by an advanced X-ray method, whole powder pattern modeling (WPPM) and high-resolution transmission electron microscopy (HR-TEM), showing the exclusive presence of pure In2O3. Diffuse reflectance spectroscopy (DRS) was used to determine the optical band gap (Eg) of the sample. Moreover, these investigations also revealed that the In2O3 nanoparticles are quasi-spherical in shape, with a diameter of around 7 nm as prepared and 9.5 nm after thermal treatment at 250°C. In2O3 NPs worked as highly sensitive sensing interfaces to provide resistance changes during exposure to sevoflurane, a volatile anesthetic agent used in surgical wards. The developed sensor demonstrated a good response and fast response/recovery time towards very low concentrations of sevoflurane in air, suggesting a very attractive application as a real-time monitoring analyzer in a hospital environment