Gas Sensing Properties of Metal Oxide Nanostructured Heterojunctions

Engineering: 2nd Place (The Ohio State University Denman Undergraduate Research Forum)Titanium dioxide (TiO2) has demonstrated great potential for resistive-type gas sensors used to detect hydrocarbons and volatile organic compounds (VOC). Two parameters which affect the sensitivity of gas sensors is the surface area of the sensing material and interfacial potentials. This experiment is exploring the VOC selectivity and gas-sensing ability of TiO2 aerogel, the highest surface area TiO2 – based material, and metal oxide powders (MOX) containing single crystalline TiO2 nanorods. Nanorods are high surface area structures which alter the potential at surface interfaces. The nanorod structures are hydrothermally grown directly onto the powders with the use of a microwave synthesis system. These hybrid powders are then used to fabricate sensors which are tested in ethanol and acetone saturated air. Thus far, commercial grade TiO2, SnO2, NiO, and CoO powders and TiO2 aerogel have been used for sensor fabrication. Initial results indicate that the response of aerogel-based sensors is highly dependent upon the quality of the aerogel. Preliminary tests have also shown that the presence of nanorods appreciably increases the response of the sensors to ethanol and acetone saturated air. The SnO2 hybrid (containing nanorods) and CoO hybrid sensors show promise for be selective towards ethanol. Selectivity towards ethanol or acetone would allow the sensor to be used as a tool for preemptive diagnoses of diseases, such as diabetes. It has been found that patients with certain diseases possess elevated concentrations of specific VOC’s in their breath. There has only been limited success in developing a sensor which is sensitive to either acetone or ethanol, two of the main VOC’s used for diagnosis. The relationship between a sensor’s response, selectivity, and surface interface composition is being analyzed. Future work includes analyzing the relationship between temperature and response and fabricating sensors made of mixed MOX powders, instead of hydrothermal compositing.The Ohio State University, Department of Materials Science and EngineeringAcademic Major: Materials Science and Engineerin

Structure and morphology of ACEL ZnS:Cu,Cl phosphor powder etched by hydrochloric acid

© The Electrochemical Society, Inc. 2009. All rights reserved. Except as provided under U.S. copyright law, this work may not be reproduced, resold, distributed, or modified without the express permission of The Electrochemical Society (ECS). The archival version is available at the link below.Despite many researches over the last half century, the mechanism of ac powder electroluminescence remains to be fully elucidated and, to this end, a better understanding of the relatively complex structure of alternate current electroluminescence (ACEL) phosphors is required. Consequently, the structure and morphology of ZnS:Cu,Cl phosphor powders have been investigated herein by means of scanning electron microscopy (SEM) on hydrochloric acid-etched samples and X-ray powder diffraction. The latter technique confirmed that, as a result of two-stage firing during their synthesis, the phosphors were converted from the high temperature hexagonal (wurtzite) structure to the low temperature cubic (sphalerite) polymorph having a high density of planar stacking faults. Optical microscopy revealed that the crystal habit of the phosphor had the appearance of the hexagonal polymorph, which can be explained by the sphalerite pseudomorphing of the earlier wurtzite after undergoing the hexagonal to cubic phase transformation during the synthesis. SEM micrographs of the hydrochloric-etched phosphor particles revealed etch pits, a high density of planar stacking faults along the cubic [111] axis, and the pyramids on the (111) face. These observations were consistent with unidirectional crystal growth originating from the face showing the pyramids.EPSRC, DTI, and the Technology Strategy Board-led Technology Program

Redetermination of despujolsite, Ca3Mn4+(SO4)2(OH)6·3H2O

The crystal structure of despujolsite [tricalcium manganese bis­(sulfate) hexahydroxide tri­hydrate], the Ca/Mn member of the fleischerite group, ideally Ca3Mn4+(SO4)2(OH)6·3H2O, was previously determined based on X-ray diffraction intensity data from photographs, without H-atom positions located [Gaudefroy et al. (1968 ▶). Bull. Soc. Fr. Minéral. Crystallogr. 91, 43–50]. The current study redetermines the structure of despujolsite from a natural specimen, with all H atoms located and with higher precision. The structure of despujolsite is characterized by layers of CaO8 polyhedra (m.. symmetry) inter­connected by Mn(OH)6 octa­hedra (32. symmetry) and SO4 tetra­hedra (3.. symmetry) along [001]. The average Ca—O, Mn—O and S—O bond lengths are 2.489, 1.915, and 1.472 Å, respectively. There are two distinct hydrogen bonds that stabilize the structural set-up. This work represents the first description of hydrogen bonds in the fleischerite group of minerals

Lithio­marsturite, LiCa2Mn2Si5O14(OH)

Lithio­marsturite, ideally LiCa2Mn2Si5O14(OH), is a member of the pectolite–pyroxene series of pyroxenoids (hydro­pyroxenoids) and belongs to the rhodonite group. A previous structure determination of this mineral based on triclinic symmetry in space group P by Peacor et al. [Am. Mineral. (1990), 75, 409–414] converged with R = 0.18 without reporting any information on atomic coordinates and displacement param­eters. The current study redetermines its structure from a natural specimen from the type locality (Foote mine, North Carolina) based on single-crystal X-ray diffraction data. The crystal structure of lithio­marsturite is characterized by ribbons of edge-sharing CaO6 and two types of MnO6 octa­hedra as well as chains of corner-sharing SiO4 tetra­hedra, both extending along [110]. The octa­hedral ribbons are inter­connected by the rather irregular CaO8 and LiO6 polyhedra through sharing corners and edges, forming layers parallel to (1), which are linked together by the silicate chains. Whereas the coordination environments of the Mn and Li cations can be compared to those of the corresponding cations in nambulite, the bonding situations of the Ca cations are more similar to those in babingtonite. In contrast to the hydrogen-bonding scheme in babingtonite, which has one O atom as the hydrogen-bond donor and a second O atom as the hydrogen-bond acceptor, our study shows that the situation is reversed in lithio­marsturite for the same two O atoms, as a consequence of the differences in the bonding environments around O atoms in the two minerals

Lotharmeyerite, Ca(Zn,Mn)2(AsO4)2(H2O,OH)2

Lotharmeyerite, calcium bis­(zinc/manganese) bis­(arsenate) bis­(hydroxide/hydrate), Ca(Zn,Mn3+)2(AsO4)2(H2O,OH)2, is a member of the natrochalcite group of minerals, which are characterized by the general formula AM 2(XO4)2(H2O,OH)2, where A may be occupied by Pb2+, Ca2+, Na+, and Bi3+, M by Fe3+, Mn3+, Cu2+, Zn2+, Co2+, Ni2+, Al3+, and Mg2+, and X by PV, AsV, VV, and SVI. The minerals in the group display either monoclinic or triclinic symmetry, depending on the ordering of chemical components in the M site. Based on single-crystal X-ray diffraction data of a sample from the type locality, Mapimi, Durango, Mexico, this study presents the first structure determination of lotharmeyerite. Lotharmeyerite is isostructural with natrochalcite and tsumcorite. The structure is composed of rutile-type chains of edge-shared MO6 octa­hedra (site symmetry ) extending along [010], which are inter­connected by XO4 tetra­hedra (site symmetry 2) and hydrogen bonds to form [M 2(XO4)2(OH,H2O)2] sheets parallel to (001). These sheets are linked by the larger A cations (site symmetry 2/m), as well as by hydrogen bonds. Bond-valence sums for the M cation, calculated with the parameters for Mn3+ and Mn2+ are 2.72 and 2.94 v.u., respectively, consistent with the occupation of the M site by Mn3+. Two distinct hydrogen bonds are present, one with O⋯O = 2.610 (4) Å and the other O⋯O = 2.595 (3) Å. One of the H-atom positions is disordered over two sites with 50% occupancy, in agreement with observations for other natrochalcite-type minerals, such as natrochalcite and tsumcorite

Trapping the δ isomer of the polyoxometalate-based Keggin cluster with a tripodal ligand

We report the synthesis, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyanion. A family of δ-Keggin polyoxoanions of the general formula, (TEA)HpNaq [H2M12(XO4)O33(TEA)].rH2O where p, q, r = [2,3,8] for 1 and [4,1,4] for 2 were isolated by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster leading to the entrapment and stabilization of the elusive polyanhionic δ Keggin archetype. The δ-Keggin species were characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited multi-electron transfer and reversible photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations accompanied with colour changes under ligh

Structural and compositional tuning of layered subnitrides ; new complex nitride halides

New quaternary bimetallic nitride halides and the first examples of quintinary nitride mixed halides have been synthesised in the phase system Ca - Sr - N - Cl - Br. The variation in structure with composition has been investigated by powder X- ray and powder neutron diffraction techniques. All compounds crystallise in the R-3m spacegroup, with the anti-alpha-NaFeO2 structure. The layered compounds exhibit unprecedented coexistent disorder of both cations and anions in which only nitride solely occupies a discrete crystallographic position. [N(Ca,Sr)(2)](+) layers alternate with halide ions (Cl, Br)(-), which fill the octahedral voids between the positively charged sheets. A dual cationic-anionic substitution approach allows all aspects of the anisotropic structure to be controlled, including the thickness of the ionic layers and the [N(Ca,Sr)(2)](+) interlayer spacing