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.

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.

Production of ultra-deep sulfur-free diesels using a sustainable catalytic system based on UiO-66(Zr).

The porous metal-organic framework UiO-66(Zr) obtained via non modulated synthesis, has revealed to be a notable heterogeneous catalyst, enabling extremely fast and very efficient desulfurization of a multicomponent model diesel and also a real diesel fuel.

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.

Optical properties of lanthanide-doped lamellar nanohybrids.

In this article a detailed study of the optical properties of lanthanide doped lamellar nanohybrids synthesized by the "benzyl alcohol route" is presented. The synthetic approach results in the formation of a highly ordered lamellar nanocomposite consisting of yttrium or gadolinium oxide crystalline layers with a confined thickness of about 0.6 nm, separated from each other by organic layers of intercalated benzoate molecules. When the inorganic layers are doped with optically-active lanthanide ions they show outstanding emission properties in the green (Tb(3+)), red (Eu(3+)) and near infrared (Nd(3+)). The local environment of the emitting ions and the energy transfer processes involving the phenyl ring of the benzoate complexes and the lanthanide ions are presented, as well as radiance and lifetime measurements. The radiance values are comparable and in some cases even larger than those of standard phosphors, proving that these nanohybrids can compete, from an emission efficiency point of view, with commercial phosphors. Furthermore, in these nanohybrids it is possible by simply changing the excitation wavelength, to tune the emission colour chromaticity without loosing the radiance.