Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “OXIDATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,243 records · Page 69

Non-precious metal electrocatalysts with high activity for hydrogen oxidation reaction in alkaline electrolytes

A ternary metallic CoNiMo catalyst is electrochemically deposited on a polycrystalline gold (Au) disk electrode using pulse voltammetry, and characterized for hydrogen oxidation reaction (HOR) activity by temperature-controlled rotating disk electrode measurements in 0.1 M potassium hydroxide (KOH). The catalyst exhibits the highest HOR activity among all non-precious metal catalysts (e.g., 20 fold higher than Ni). At a sufficient loading, the CoNiMo catalyst is expected to outperform Pt and thus provides a promising low cost pathway for alkaline or alkaline membrane fuel cells. Density functional theory (DFT) calculations and parallel H-2-temperature programmed desorption (TPD) experiments on structurally much simpler model alloy systems show a trend that CoNiMo has a hydrogen binding energy (HBE) similar to Pt and much lower than Ni, suggesting that the formation of multi-metallic bonds modifies the HBE of Ni and is likely a significant contributing factor for the enhanced HOR activity.

Sheng, WC↗

Partial oxidation of light alkanes by periodate and chloride salts

We present that the efficient and selective partial oxidation of light alkanes using potassium periodate and potassium chloride is reported. Yields of methane functionalization in trifluoroacetic acid reach >40% with high selectivity for methyl trifluoroacetate. Periodate and chloride also functionalize ethane and propane in good yields (>20%).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing flame ionization detector (FID) sensitivity using post-column oxidation–methanation

The flame ionization detector (FID) is a robust tool in gas chromatography (GC) due to its sensitivity and linear response in the detection of common organic compounds. However, FID response to oxygenated or highly functionalized organic molecules is low, or in some cases non-existent, making it difficult or impossible to detect and quantify some organic compounds. In this work, the combination of a GC/FID system with a catalytic microreactor, which performs post-column combustion–methanation to convert organic compounds to methane, is shown to be an effective approach for quantifying low-response organic compounds. Molecules that were previously undetectable by conventional FID, including carbon monoxide and carbon dioxide, respond with the same high response of methane in the FID. Low-response molecules, including formaldehyde, formic acid, formamide, and ten other oxygenates also demonstrated enhanced detector response equivalent to that of methane in the FID. Here, the linear response of the FID to these molecules and the equivalent sensitivity to methane indicate that accurate quantification is possible without the usual calibration-corrections (e.g., response factors or correction factors) to the FID response.

99 GENERAL AND MISCELLANEOUS↗

Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers

Here, incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE–PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ~ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g . Over the temperature range 30–90 °C, the values of χ were determined to be very large (~2–2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE–PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ~ 2 nm -1 ) for relatively small polymer chains. Finally, our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

36 MATERIALS SCIENCE↗

Intermetallic Pd3Pb Nanowire Networks Boost Ethanol Oxidation and Oxygen Reduction Reaction with Significantly Improved Methanol Tolerance

Intermetallic nanocrystals are currently receiving extensive attentions due to their well- defined crystal structures, highly ordered atomic distribution and superior structural stability that endow them with optimized catalytic activities, stabilities and high selectivity as electrocatalysts for fuel cells. Here, for the first time, we reported the facile synthesis of intermetallic Pd3Pb nanowire networks (IM-Pd3Pb NNs) with a one-step wet-chemical strategy at a relatively low temperature (i.e. 170 °C) in 1 h. The as-prepared IM-Pd3Pb NNs exhibited superior bifunctional catalytic performances toward oxygen reduction reaction (ORR) and ethanol oxidation reaction (EtOR) compared to commercial Pt/C and Pd black, respectively. Significantly, IM-Pd3Pb NNs also showed excellent methanol- and CO-tolerant ability as ORR cathode and EtOR anode electrocatalysts, respectively. The electrochemical active surface area and mass activity of IM-Pd3Pb NNs are about 3.4 times and 2 times higher than Pd black toward EtOR, respectively. As the Pt-free bifunctional electrocatalysts, 3D IM-Pd3Pb architectures with exceptional catalytic performances hold great promise in various applica-tions of energy conversion and storage devices, sensors, electronics, optics and so on.

Shi, Qiurong↗

Facile incorporation of technetium into magnetite, magnesioferrite, and hematite by formation of ferrous nitrate in situ : precursors to iron oxide nuclear waste forms

The fission product, 99 Tc, presents significant challenges to the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate (TcO 4 – ), the stable Tc species in aerobic environments. Here, the migration of 99 Tc from disposal sites can potentially be prevented by incorporating it into durable waste forms based on environmentally stable minerals.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Conditions for stable operation of solid oxide electrolysis cells: oxygen electrode effects

Solid oxide electrolysis cells (SOECs) convert renewable electricity to fuels with efficiency substantially higher than other electrolysis technologies. However, questions remain regarding degradation mechanisms that limit SOEC long-term stability. One of the key degradation mechanisms is oxygen electrode delamination; although prior studies have improved the understanding of this mechanism, it is still difficult to predict how degradation depends on SOEC materials and operating conditions, i.e., temperature, voltage, and current density. Here we present a study aimed at developing a quantitative understanding of oxygen electrode delamination. Experimentally, a life test study of symmetric and full cells with yttria-stabilized zirconia (YSZ) electrolytes and Gd-doped ceria (GDC) barrier layers was done with three different perovskite oxygen electrode materials. Fracture was observed at the perovskite–GDC interface above a critical current density and below a critical operating temperature. A theory is presented that combines a calculation of the effective oxygen pressure across the electrolyte with an estimation of the pressure required for fracture. Fracture is correctly predicted for a critical oxygen partial pressure of ~7200 atm and an associated electrode overpotential of ~0.2 V, occurring at the electrode/GDC interface because of the relatively low perovskite fracture toughness. As a result, damage at the GDC/YSZ interface was also observed in some cases and explained by a peak in the oxygen pressure at this interface.

30 DIRECT ENERGY CONVERSION↗

Lithium vanadium oxide (Li 1.1 V 3 O 8 ) thick porous electrodes with high rate capacity: utilization and evolution upon extended cycling elucidated via operando energy dispersive X-ray diffraction and continuum simulation

The phase distribution of lithiated LVO in thick (~500 μm) porous electrodes (TPEs) designed to facilitate both ion and electron transport was determined using synchrotron-based operando energy dispersive X-ray diffraction (EDXRD). Probing 3 positions in the TPE while cycling at a 1C rate revealed a homogeneous phase transition across the thickness of the electrode at the 1st and 95th cycles. Additionally, continuum modelling indicated uniform lithiation across the TPE in agreement with the EDXRD results and ascribed decreasing accessible active material to be the cause of loss in delivered capacity between the 1st and 95th cycles. The model was supported by the observation of significant particle fracture by SEM consistent with loss of electrical contact. Overall, the combination of operando EDXRD, continuum modeling, and ex situ measurements enabled a deeper understanding of lithium vanadium oxide transport properties under high rate extended cycling within a thick highly porous electrode architecture.

25 ENERGY STORAGE↗