SnO2/TiO2 Thin Film n-n Heterostructures of Improved Sensitivity to NO2.

Thin-film n-n nanoheterostructures of SnO2/TiO2, highly sensitive to NO2, were obtained in a two-step process: (i) magnetron sputtering, MS followed by (ii) Langmuir-Blodgett, L-B, technique. Thick (200 nm) SnO2 base layers were deposited by MS and subsequently overcoated with a thin and discontinuous TiO2 film by means of L-B. Rutile nanopowder spread over the ethanol/chloroform/water formed a suspension, which was used as a source in L-B method. The morphology, crystallographic and electronic properties of the prepared sensors were studied by scanning electron microscopy, SEM, X-ray diffraction, XRD in glancing incidence geometry, GID, X-ray photoemission spectroscopy, XPS, and uv-vis-nir spectrophotometry, respectively. It was found that amorphous SnO2 films responded to relatively low concentrations of NO2 of about 200 ppb. A change of more than two orders of magnitude in the electrical resistivity upon exposure to NO2 was further enhanced in SnO2/TiO2 n-n nanoheterostructures. The best sensor responses RNO2/R0 were obtained at the lowest operating temperatures of about 120 °C, which is typical for nanomaterials. Response (recovery) times to 400 ppb NO2 were determined as a function of the operating temperature and indicated a significant decrease from 62 (42) s at 123 °C to 12 (19) s at 385 °C A much smaller sensitivity to H2 was observed, which might be advantageous for selective detection of nitrogen oxides. The influence of humidity on the NO2 response was demonstrated to be significantly below 150 °C and systematically decreased upon increase in the operating temperature up to 400 °C.

WO3/CeO2/TiO2 Catalysts for Selective Catalytic Reduction of NO(x) by NH3: Effect of the Synthesis Method.

WO3/CeO2/TiO2, CeO2/TiO2 and WO3/TiO2 catalysts were prepared by wet impregnation. CeO2/TiO2 and WO3/TiO2 showed activity towards the selective catalytic reduction (SCR) of NO(x) by NH3, which was significantly improved by subsequent impregnation of CeO/TiO2 with WO3. Catalytic performance, NH3 oxidation and NH3 temperature programmed desorption of wet-impregnated WO3/CeO2/TiO2 were compared to those of a flame-made counterpart. The flame-made catalyst exhibits a peculiar arrangement of W-Ce-Ti-oxides that makes it very active for NH3-SCR. Catalysts prepared by wet impregnation with the aim to mimic the structure of the flame-made catalyst were not able to fully reproduce its activity. The differences in the catalytic performance between the investigated catalysts were related to their structural properties and the different interaction of the catalyst components.

Scavenger-Supported Photocatalytic Evidence of an Extended Type I Electronic Structure of the TiO2@Fe2O3 Interface.

Heterostructures of TiO2@Fe2O3 with a specific electronic structure and morphology enable us to control the interfacial charge transport necessary for their efficient photocatalytic performance. In spite of the extensive research, there still remains a profound ambiguity as far as the band alignment at the interface of TiO2@Fe2O3 is concerned. In this work, the extended type I heterojunction between anatase TiO2 nanocrystals and α-Fe2O3 hematite nanograins is proposed. Experimental evidence supporting this conclusion is based on direct measurements such as optical spectroscopy, X-ray photoemission spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), and the results of indirect studies of photocatalytic decomposition of rhodamine B (RhB) with selected scavengers of various active species of OH•, h•, e-, and •O2-. The presence of small 6-8 nm Fe2O3 crystallites at the surface of TiO2 has been confirmed in HRTEM images. Irregular 15-50 nm needle-like hematite grains could be observed in scanning electron micrographs. Substitutional incorporation of Fe3+ ions into the TiO2 crystal lattice is predicted by a 0.16% decrease in lattice parameter a and a 0.08% change of c, as well as by a shift of the Raman Eg(1) peak from 143 cm-1 in pure TiO2 to 149 cm-1 in Fe2O3-modified TiO2. Analysis of O 1s XPS spectra corroborates this conclusion, indicating the formation of oxygen vacancies at the surface of titanium(IV) oxide. The presence of the Fe3+ impurity level in the forbidden band gap of TiO2 is revealed by the 2.80 eV optical transition. The size effect is responsible for the absorption feature appearing at 2.48 eV. Increased photocatalytic activity within the visible range suggests that the electron transfer involves high energy levels of Fe2O3. Well-programed experiments with scavengers allow us to eliminate the less probable mechanisms of RhB photodecomposition and propose a band diagram of the TiO2@Fe2O3 heterojunction.

The Effect of Electrophoretic Deposition Parameters on the Microstructure and Adhesion of Zein Coatings to Titanium Substrates.

Zein coatings were obtained by electrophoretic deposition (EPD) on commercially pure titanium substrates in an as-received state and after various chemical treatments. The properties of the zein solution, zeta potential and conductivity, at varying pH values were investigated. It was found that the zein content and the ratio of water to ethanol of the solution used for EPD, as well as the process voltage value and time, significantly influence the morphology of coatings. The deposits obtained from the solution containing 150 g/L and 200 g/L of zein and 10 vol % of water and 90 vol % of ethanol, about 4-5 µm thick, were dense and homogeneous. The effect of chemical treatment of the Ti substrate surface prior to EPD on coating adhesion to the substrate was determined. The coatings showed the highest adhesion to the as-received and anodized substrates due to the presence of a thick TiO2 layer on their surfaces and the presence of specific surface features. Coated titanium substrates showed slightly lower electrochemical corrosion resistance than the uncoated one in Ringer's solution. The coatings showed a well-developed surface topography compared to the as-received substrate, and they demonstrated hydrophilic nature. The present results provide new insights for the further development of zein-based composite coatings for biomedical engineering applications.

Template-Assisted Iron Nanowire Formation at Different Electrolyte Temperatures.

We studied the morphology, structure, and magnetic properties of Fe nanowires that were electrodeposited as a function of the electrolyte temperature. The nucleation mechanism followed instantaneous growth. At low temperatures, we observed an increase of the total charge reduced into the templates, thus suggesting a significant increase in the degree of pore filling. Scanning electron microscopy images revealed smooth nanowires without any characteristic features that would differentiate their morphology as a function of the electrolyte temperature. X-ray photoelectron spectroscopy studies indicated the presence of a polycarbonate coating that covered the nanowires and protected them against oxidation. The X-ray diffraction measurements showed peaks coming from the polycrystalline Fe bcc structure without any traces of the oxide phases. The crystallite size decreased with an increasing electrolyte temperature. The transmission electron microscopy measurements proved the fine-crystalline structure and revealed elongated crystallite shapes with a columnar arrangement along the nanowire. Mössbauer studies indicated a deviation in the magnetization vector from the normal direction, which agrees with the SQUID measurements. An increase in the electrolyte temperature caused a rise in the out of the membrane plane coercivity. The studies showed the oxidation resistance of the Fe nanowires deposited at elevated electrolyte temperatures.

Influence of W Addition on Microstructure and Resistance to Brittle Cracking of TiB2 Coatings Deposited by DCMS.

The aim of this work was to determine the influence of the tungsten addition to TiB2 coatings on their microstructure and brittle cracking resistance. Four coatings of different compositions (0, 7, 15, and 20 at.% of W) were deposited by magnetron sputtering from TiB2 and W targets. The coatings were investigated by the following methods: X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). All coatings had a homogeneous columnar structure with decreasing column width as the tungsten content increased. XRD and XPS analysis showed the presence of TiB2 and nonstoichiometric TiBx phases with an excess or deficiency of boron depending on composition. The crystalline size decreased from 27 nm to 10 nm with increasing W content. The brittle cracking resistance improved with increasing content of TiBx phase with deficiency of B and decreasing crystalline size.

An unprecedented copper(I,II)-octacyanotungstate(V) 2-D network: crystal structure and magnetism of [CuII(tren)]{CuI[W(V)(CN)8]} . 1.5H2O.

A novel two-dimensional cyanide-bridged polymer [CuII(tren)]{CuI[W(V)(CN)8]} . 1.5H2O (tren = tris(2-aminoethyl)amine) formed via the simultaneous in situ metal-ligand redox reaction of [Cu(tren)(OH2)]2+ and self-assembly with [W(V)(CN)8]3- consists of a {CuI[W(V)(CN)8]} square grid built of CuI centres of tetrahedral geometry coordinatively saturated by CN bridges and [W(V)(CN)8]3- capped by [CuII(tren)]2+ moieties; it exhibits ferromagnetic coupling J1 = +5.8(1) cm(-1) within the CuII-W(V) dinuclear subunits and weak antiferromagnetic coupling J2 = -0.03(1) cm(-1) between them through diamagnetic CuI spacers.