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At least 127 records · Page 7

CO 2 -assisted ethane oxidative dehydrogenation over MoO x catalysts supported on reducible CeO 2 –TiO 2

Supported MoO x on mixed CeO 2 –TiO 2 was investigated for the oxidative dehydrogenation of ethane (ODHE) using CO 2 as a mild oxidant. Raman spectroscopic characterization of the synthesized catalysts under dehydrated conditions suggested that surface MoO x species prefer to anchor on the crystalline domains of TiO 2 . Upon increasing the amount of CeO 2 in the mixed oxide support, significant spectral changes were observed, especially in the ~900–950 cm –1 region where Mo–O–M bonds are expected. The catalytic behaviors of Mo as opposed to pure support materials were distinct. As the ceria content in the support increased, MoO x catalysts promoted oxidative dehydrogenation pathways via the Mars–van Krevelen mechanism, while pure supports appeared to favor ethane direct dehydrogenation. Investigation of structure–function relationships via in situ Raman spectroscopic efforts revealed that adding ceria not only changed the redox properties of the support but also improved those of the deposited amorphous MoO x species. We also show that upon incorporation of ceria into the support, CO 2 directly participates in the reoxidation of the dispersed MoO x species during catalysis. Here, this effect was distinct from the participation of CO 2 in the reverse water gas shift reaction. Operando Raman spectra revealed that the presence of CO 2 prolonged the existence of the 930 cm –1 feature which appears to correlate well with the relative contribution of the oxidative versus non-oxidative pathway in ethane dehydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-equilibrium deposition of phase pure Cu{sub 2}O thin films at reduced growth temperature

Cuprous oxide (Cu{sub 2}O) is actively studied as a prototypical material for energy conversion and electronic applications. Here we reduce the growth temperature of phase pure Cu{sub 2}O thin films to 300 °C by intentionally controlling solely the kinetic parameter (total chamber pressure, P{sub tot}) at fixed thermodynamic condition (0.25 mTorr pO{sub 2}). A strong non-monotonic effect of P{sub tot} on Cu-O phase formation is found using high-throughput combinatorial-pulsed laser deposition. This discovery creates new opportunities for the growth of Cu{sub 2}O devices with low thermal budget and illustrates the importance of kinetic effects for the synthesis of metastable materials with useful properties.

36 MATERIALS SCIENCE↗

The impact of carbon sp{sup 2} fraction of reduced graphene oxide on the performance of reduced graphene oxide contacted organic transistors

One of the major bottlenecks in fabricating high performance organic field effect transistors (OFETs) is a large interfacial contact barrier between metal electrodes and organic semiconductors (OSCs) which makes the charge injection inefficient. Recently, reduced graphene oxide (RGO) has been suggested as an alternative electrode material for OFETs. RGO has tunable electronic properties and its conductivity can be varied by several orders of magnitude by varying the carbon sp{sup 2} fraction. However, whether the sp{sup 2} fraction of RGO in the electrode affects the performance of the fabricated OFETs is yet to be investigated. In this study, we demonstrate that the performance of OFETs with pentacene as OSC and RGO as electrode can be continuously improved by increasing the carbon sp{sup 2} fraction of RGO. When compared to control palladium electrodes, the mobility of the OFETs shows an improvement of ∼200% for 61% sp{sup 2} fraction RGO, which further improves to ∼500% for 80% RGO electrode. Similar improvements were also observed in current on-off ratio, on-current, and transconductance. Our study suggests that, in addition to π-π interaction at RGO/pentacene interface, the tunable electronic properties of RGO electrode have a significant role in OFETs performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a reduced model of formation reactions in Zr-Al nanolaminates

A computational model of anaerobic reactions in metallic multilayered systems with an equimolar composition of zirconium and aluminum is developed. The reduced reaction formalism of M. Salloum and O. M. Knio, Combust. Flame 157(2): 288–295 (2010) is adopted. Attention is focused on quantifying intermixing rates based on experimental measurements of uniform ignition as well as measurements of self-propagating front velocities. Estimates of atomic diffusivity are first obtained based on a regression analysis. A more elaborate Bayesian inference formalism is then applied in order to assess the impact of uncertainties in the measurements, potential discrepancies between predictions and observations, as well as the sensitivity of predictions to inferred parameters. Intermixing rates are correlated in terms of a composite Arrhenius law, which exhibits a discontinuity around the Al melting temperature. Analysis of the predictions indicates that Arrhenius parameters inferred for the low-temperature branch lie within a tight range, whereas the parameters of the high-temperature branch are characterized by higher uncertainty. The latter is affected by scatter in the experimental measurements, and the limited range of bilayers where observations are available. For both branches, the predictions exhibit higher sensitivity to the activation energy than the pre-exponent, whose posteriors are highly correlated.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A strategy for reducing stagnation phase hydrodynamic instability growth in inertial confinement fusion implosions

Encouraging progress is being made in demonstrating control of ablation front hydrodynamic instability growth in inertial confinement fusion implosion experiments on the National Ignition Facility [E. I. Moses, R. N. Boyd, B. A. Remington, C. J. Keane, and R. Al-Ayat, Phys. Plasmas 16, 041006 (2009)]. Even once ablation front stabilities are controlled, however, instability during the stagnation phase of the implosion can still quench ignition. A scheme is proposed to reduce the growth of stagnation phase instabilities through the reverse of the “adiabat shaping” mechanism proposed to control ablation front growth. Two-dimensional radiation hydrodynamics simulations confirm that improved stagnation phase stability should be possible without compromising fuel compression.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Financial incentives for reducing proliferation risks

This article submitted for publication to the Bulletin of Atomic Scientists explains the possible financial incentives for financial institutions and large integrators to reduce nuclear proliferation risks by including anti-proliferation measures in their due diligence and requiring their suppliers to meet heightened compliance standards. Because manufacturers of dual-use nuclear goods are diverse and numerous outreach is difficult. However, financial institutions and large integrators work with nearly all dual-use manufacturers, making financial institutions and integrators well-positioned to increase awareness of proliferation and trafficking risks throughout the nuclear supply chain

anti-proliferation↗

Reducing microgrid availability to reduce costs for coastal Puerto Rican communities

Renewable microgrids are sustainable, resilient solutions to mitigate and adapt to climate change. Making electric loads nearly 100% available (i.e., power remains on) during outages increases cost. Near 100% availability is required when human life or high-cost assets are involved, but availability can be reduced for less consequential loads leading to lower costs. This study analyses costs for photo-voltaic and lithium-ion battery microgrids with availability ranging from 0–99%. We develop a methodology to analyse three Puerto Rican coastal communities. Here, we consider power outage effects for hurricanes, earthquakes, and everyday outages. The results show cost versus availability from 0–99%. There is 27–31% cost reduction at 80% availability in comparison to 99% availability. A regression model of microgrid availability versus three ratios: 1) the annual generation to demand ratio, 2) storage to interruption energy ratio, and 3) peak storage to load ratio produced a coefficient of determination of 0.99949 with 70% of the data used for training and 30% for testing. The results can therefore be extended to other coastal Puerto Rican communities of varying sizes that have ratios within the ranges analysed in this study. This can empower decision makers to rapidly analyse designs that have availabilities well below 100%.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Ability of TiO 2 (110) Surface to Be Fully Hydroxylated and Fully Reduced

Many TiO 2 applications (e.g., in heterogeneous catalysis) involve contact with ambient atmosphere and/or water. The resulting hydroxylation can significantly alter its surface properties. While behavior of single, isolated OH species on the model metal oxide surface of rutile TiO 2 (110) is relatively well understood, much less is known regarding highly-hydroxylated surfaces and/or whether TiO 2 (110) could be fully-hydroxylated under ultra-high vacuum conditions. Here we report in situ formation of a well-ordered, fully-hydroxylated TiO 2 (110)-(1 x 1) surface using an enhanced photochemical approach, key parts of which are pre-dosing of water and multi-step dissociative adsorption and subsequent photolysis of the carboxylic (trimethyl acetic) acid. Combining scanning tunneling microscopy, ultra-violet photoelectron spectroscopy and density functional theory results, we show that the attained “super OH” surface is also fully-reduced, as a result of the photochemical trapping of electrons at the OH groups.

Environmental Molecular Sciences Laboratory↗

Modified Process Reduces Porosity when Soldering in Reduced Gravity Environments

A modified process yields lower levels of internal porosity for solder joints produced in reduced-gravity environments. The process incorporates both alternative materials and a modified procedure. The process provides the necessary cleaning action to enable effective bonding of the applied solder alloy with the materials to be joined. The modified process incorporates a commercially available liquid flux that is applied to the solder joint before heating with the soldering iron. It is subsequently heated with the soldering iron to activate the cleaning action of the flux and to evaporate most of the flux, followed by application of solder alloy in the form of commercially available solid solder wire (containing no flux). Continued heating ensures adequate flow of the solder alloy around and onto the materials to be joined. The final step is withdrawal of the soldering iron to allow alloy solidification and cooling of the solder joint.

Watson, Kevin↗