Novel electrocatalytic sensors

Basic principles employed for previously developed oxygen and SO{sub 2} sensors have been applied to other chemical sensor needs. Oxide electrodes used for oxygen sensors also possess novel catalytic properties that have been utilized for CO detection through the use of electrocatalysts on solid electrolyte membranes. These oxides offer the ability to catalyze reactions selectively for oxidation and/or reduction of analyte gas species. A combination of a catalytic and noncatalytic electrode deposited on a solid electrolyte was used to sense the reactive species by locally changing the oxygen concentration on the electrode surfaces. Multiple species can be sensed on a single substrate through the use of different electrocatalysts. A related concept is to control the catalytic properties of these materials by controlling the oxygen stoichiometry using an electrochemical pump. Presence of a gas species was sensed by changes in the electronic conductivity of the semiconducting electrode layer

Effects of Calcination Temperature and Acid-Base Properties on Mixed Potential Ammonia Sensors Modified by Metal Oxides

Mixed potential sensors were fabriated using yttria-stabilized zirconia (YSZ) as a solid electrolyte and a mixture of Au and various metal oxides as a sensing electrode. The effects of calcination temperature ranging from 600 to 1,000 °C and acid-base properties of the metal oxides on the sensing properties were examined. The selective sensing of ammonia was achieved by modification of the sensing electrode using MoO3, Bi2O3 and V2O5, while the use of WO3, Nb2O5 and MgO was not effective. The melting points of the former group were below 820 °C, while those of the latter group were higher than 1,000 °C. Among the former group, the selective sensing of ammonia was strongly dependent on the calcination temperature, which was optimum around melting point of the corresponding metal oxides. The good spreading of the metal oxides on the electrode is suggested to be one of the important factors. In the former group, the relative response of ammonia to propene was in the order of MoO3 > Bi2O3 > V2O5, which agreed well with the acidity of the metal oxides. The importance of the acidic properties of metal oxides for ammonia sensing was clarified

The development of a fullerene based hydrogen storage system

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The project objective was to evaluate hydrogen uptake by fullerene substrates and to probe the potential of the hydrogen/fullerene system for hydrogen fuel storage. As part of this project, the authors have completed and tested a fully automated, computer controlled system for measuring hydrogen uptake that is capable of handling both a vacuum of 1 x 10{sup -6} torr and pressures greater than 200 bars. The authors have first established conditions for significant uptake of hydrogen by fullerenes. Subsequently, hydrogenation and dehydrogenation of pure and catalyst-doped C60 was further studied to probe suitability for hydrogen storage applications. C60 {center_dot} H18.7 was prepared at 100 bar H2 and 400 C, corresponding to hydrogen uptake of 2.6 wt%. Dehydrogenation of C60 {center_dot} H18.7 was studied using thermogravimetric and powder x-ray diffraction analysis. The C60 {center_dot} H18.7 molecule was found to be stable up to 430 C in Ar, at which point the release of hydrogen took place simultaneously with the collapse of the fullerene structure. X-ray diffraction analysis performed on C60 {center_dot} H18.7 samples dehydrogenated at 454 C, 475 C, and 600 C showed an increasing volume fraction of amorphous material due to randomly oriented, single-layer graphine sheets. Evolved gas analysis using gas chromatography and mass spectroscopy confirmed the presence of both H{sub 2} and methane upon dehydrogenation, indicating decomposition of the fullerene. The remaining carbon could not be re-hydrogenated. These results provide the first complete evidence for the irreversible nature of fullerene hydrogenation and for limitations imposed on the hydrogenation/dehydrogenation cycle by the limited thermal stability of the molecular crystal of fullerene

Optimization of carbon-supported platinum cathode catalysts for DMFC operation.

In this paper, we describe performance and optimization of carbon-supported cathode catalysts at low platinum loading. We find that at a loading below 0.6 mg cm-2 carbon-supported platinum outperforms platinum black as a DMFC cathode catalyst. A catalyst with a 1:1 volume ratio of the dry NafionTM to the electronically conducting phase (platinum plus carbon support) provides the best performance in oxygen reduction reaction. Thanks to improved catalyst utilization, carbon-supported catalysts with a platinum content varying from 40 wt% to 80 wt% deliver very good DMFC performance, even at relatively modest precious metal loadings investigated in this work

Electronic and magnetic phase diagrams of Kitaev quantum spin liquid candidate Na2_2Co2_2TeO6_6

The 3$d^7$ Co$^{2+}$-based insulating magnet \NCTO{} has recently been reported to have strong Kitaev interactions on a honeycomb lattice, and is thus being considered as a Kitaev quantum spin liquid candidate. However, due to the existence of other types of interactions, a spontaneous long-range magnetic order occurs. This order is suppressed by applied magnetic fields leading to a succession of phases and ultimately saturation of the magnetic moments. The precise phase diagram, the nature of the phases, and the possibility that one of the field-induced phases is a Kitaev quantum spin liquid phase are still a matter of debate. Here we measured an extensive set of physical properties to build the complete temperature-field phase diagrams to magnetic saturation at 10 T for magnetic fields along the $a$- and $a^*$-axes, and a partial phase diagram up to 60 T along $c$. We probe the phases using magnetization, specific heat, magnetocaloric effect, magnetostriction, dielectric constant, and electric polarization, which is a symmetry-sensitive probe. With these measurements we identify all the previously incomplete phase boundaries and find new high-field phase boundaries. We find strong magnetoelectric coupling in the dielectric constant and moderate magnetostrictive coupling at several phase boundaries. Furthermore, we detect the symmetry of the magnetic order using electrical polarization measurements under magnetic fields. Based on our analysis, the absence of electric polarization under zero or finite magnetic field in any of the phases or after...Comment: LA-UR-22-3257

Effects of magnetization on hole localization and MnO{sub 6} octahedra disorder in hole-doped lanthanum manganese perovskites

The authors review the distortions of the MnO{sub 6} octahedra reduced by magnetization in hole-doped lanthanum manganese perovskites. The systems they consider include the colossal magnetoresistance (CMR) samples La{sub 1{minus}x}Ca{sub x}MnO{sub 3} (x = 0.21, 0.25, 0.30), La{sub 0.76}Ba{sub 0.33}MnO{sub 3}, and a poorer quality La{sub 0.76}Pb{sub 0.33}MnO{sub 3} sample. They also report preliminary work on three samples of oxygen-doped LaMnO{sub 3+{delta}} and a lanthanum-deficient La{sub 0.9}MnO{sub 3} sample. They find the same exponential relationship between the removal of the distortion and the sample magnetization in the Ba- and Pb-doped CMR samples as was found previously for the Ca doped samples. The MnO{sub 6} distortion in the oxygen-doped materials is found to slightly reduce below the magnetic transition, although much less so than in the CMR samples. Above T{sub C}, the antiferromagnetic LaMnO{sub 3.006} sample shows a softer temperature dependence of the Mn-O bond length distribution broadening. Surprisingly, even this sample shows deviations from thermal (Debye) behavior near T{sub N}, possibly due to FM coupling within MnO planes

The Evolution of High Temperature Gas Sensors.

Gas sensor technology based on high temperature solid electrolytes is maturing rapidly. Recent advances in metal oxide catalysis and thin film materials science has enabled the design of new electrochemical sensors. We have demonstrated prototype amperometric oxygen sensors, nernstian potentiometric oxygen sensors that operate in high sulfur environments, and hydrocarbon and carbon monoxide sensing mixed potentials sensors. Many of these devices exhibit part per million sensitivities, response times on the order of seconds and excellent long-term stability

Measurement of the local Jahn-Teller distortion in LaMnO_3.006

The atomic pair distribution function (PDF) of stoichiometric LaMnO_3 has been measured. This has been fit with a structural model to extract the local Jahn-Teller distortion for an ideal Mn(3+)O_6 octahedron. These results are compared to Rietveld refinements of the same data which give the average structure. Since the local structure is being measured in the PDF there is no assumption of long-range orbital order and the real, local, Jahn-Teller distortion is measured directly. We find good agreement both with published crystallographic results and our own Rietveld refinements suggesting that in an accurately stoichiometric material there is long range orbital order as expected. The local Jahn-Teller distortion has 2 short, 2 medium and 2 long bonds.Comment: 5 pages, 3 postscript figures, minor change