Investigation of battery active nickel oxides Fourth quarterly report
Electrochemical analysis of battery active sintered nickel oxides - oxidation state, stand and temperature effect, and charge retention
SINTERING↗
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Results for “oxide activation”
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.
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Sources and sinks for atmospheric H2 - A current analysis with projections for the influence of anthropogenic activity
Oxidation of CH4 provides the major source for atmospheric H2, which is removed mainly by reaction with OH. Biological activity at earth's surface appears to represent at most a minor sink for H2. Anthropogenic activity is a significant source for both H2 and CO in the present atmosphere and may be expected to exert a growing influence in the future. Models are presented which suggest a rise in the mixing ratio of H2 from its present value of 5.6 ten-millionths to about 1.8 millionths by the year 2100. The mixing ratio of CO should grow from 9.7 hundred-millionths to 2.3 ten-millionths over the same time period, and there should be a rise in CH4 by about a factor of 1.5 associated with anthropogenically induced reductions in tropospheric OH.
Penner, J. E.↗
Soil oxidoreductase zymography: Visualizing spatial distributions of peroxidase and phenol oxidase activities at the root-soil interface
Decomposition of organic material in the rhizosphere – the most dynamic microbial habitat in soil – involves arrays of oxidoreductase and hydrolytic enzymes. Spatial distributions of various hydrolytic activities in soil have already been explored by zymographic techniques. However, the distribution of oxidative activity in the rhizosphere remains to be studied. Thus, we extended a Time-Lapse Zymography technique, using Amplex Red® reagent, to visualize and quantify distributions of phenol oxidase and peroxidase activities in the rhizosphere of Zea mays L. growing in a Haplic Phaeozem and the non-rhizospheric soil. The gross oxidative activity was greatest at the root surfaces, and fell to background soil levels 1.26 and 0.73 mm from seminal (>1 mm diameter) and lateral (<0.5 mm diameter) roots, respectively. The rhizosphere extent relative to the root radius was 59% broader around lateral than around seminal roots. The greatest activities, up to 30 nmol cm –2 min –1 , were peroxidase-dominated and closely associated with roots. Here, the results confirm the utility of the approach for studying spatio-temporal distributions of oxidative activities in soil. However, actual activity of oxidoreductases in the field will be strongly controlled by fluctuating environmental conditions such as soil aeration and the gradient of reactive oxygen species, which need to be considered especially in anoxic soils.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Investigation of battery active nickel oxides Final report
Identification and characterization of battery active compound structures formed on nickel oxide electrode during charging and discharging
BATTERY↗
Nanostructured, Targeted Layered Metal Oxides as Active and Selective Heterogeneous Electrocatalysts for Oxygen Evolution
Oxygen evolution reaction (OER) is an important chemical transformation that governs the performance of technologically relevant energy conversion and storage processes, such as electrochemical water splitting in electrolyzers and metal-air batteries. This reaction involves the evolution of oxygen gas from (i) oxygen ions formed from water splitting at high temperatures, (ii) oxygen containing species (i.e., OH, OOH) formed from water splitting at low temperatures, and (iii) metal-oxide discharge products (M x O 2 ) in metal-air batteries. One of the main challenges with OER is that it is catalyzed at low temperatures by noble metal-based electrocatalysts, which are expensive (making this process economically unviable), or at high temperatures by metal-oxide based electrocatalysts that are inefficient and lead to high overpotential losses. Our preliminary results, as well as other results in the literature, show that non-noble metal-based oxide electrocatalysts with layered structures, known as nickelate oxides, exhibit promising OER activity. Nickelate oxides (A 2 MO 4+δ ) belong to the Ruddlesden-Popper series composed of alternating perovskite-like and rocksalt-like layers. They are promising OER electrocatalysts due to their high oxygen transport/exchange properties compared to the state-of-the-art perovskite-type oxides. Unfortunately, these materials are fairly unexplored and little is known about the properties that govern their OER activity. Our preliminary studies, where we combine density functional theory (DFT) calculations, selective synthesis and characterization, show that engineering their nanocrystalline structure can significantly impact their catalytic activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ni/CeO 2 Nanocatalysts with Optimized CeO 2 Support Morphologies for CH 4 Oxidation
Catalytic oxidation of CH 4 over nonprecious Ni/CeO 2 catalysts has attracted wide attention. Controlling the morphology of a CeO 2 support can enhance the CH 4 oxidation activity without changing the catalyst composition. Here, in this paper, a series of 2 wt % Ni/CeO 2 nanocatalysts with different CeO 2 support morphologies (nanoparticles (P), rods (R), cubes (C)) and synthetic procedures (precipitation, sol-gel (SG)) were evaluated for their CH 4 oxidation performance. The redox properties of CeO 2 supports and corresponding Ni loaded catalysts were characterized by H 2 -temperature-programmed reduction and oxygen storage capacity (OSC) measurements. The relationship among the CeO 2 morphologies, surface areas, redox properties, and CH4 oxidation activity for both CeO 2 supports and Ni/CeO 2 catalysts was established. The findings suggest that CeO 2 -R has a greater amount of surface oxygen vacancies as well as an improved OSC and CH4 oxidation activity compared to CeO 2 -P and CeO 2 -C supports. The same CH 4 oxidation activity pattern was observed for the Ni containing catalysts (Ni/CeO 2 -R > Ni/CeO 2 -P > Ni/CeO 2 -C). Increasing the CeO 2 surface area by using a sol-gel synthesis method (CeO 2 -SG) improved the amount of surface oxygen vacancies and CH 4 oxidation performance of CeO 2 -SG and Ni/CeO 2 -SG compared to CeO 2 -R and Ni/CeO 2 -R, respectively. Finally, all studied Ni/CeO 2 nanocatalysts showed improved hydrothermal stability compared to conventional Pd/Al 2 O 3 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water
A special membrane electrode assembly to measure operando X-ray absorption spectra and resonant photoemission spectra of mesoporous templated iridium oxide films is used. These films are calcined to different temperatures to mediate the catalyst activity. By combining operando resonant photoemission measurements of different films with ab initio simulations these are able to unambiguously distinguish µ 2 -O (bridging oxygen) and µ 1 -O (terminal oxygen) in the near-surface regions of the catalysts. The intrinsic activity of iridium oxide scales with the formation of µ1-O (terminal oxygen) is found. Importantly, it is shown that the peroxo species do not accumulate under reaction conditions. Rather, the formation of µ 1 -O species, which are active in O-O bond formation during the OER, is the most oxidized oxygen species observed, which is consistent with an O-O rate-limiting step. Thus, the oxygen species taking part in the electrochemical oxidation of water on iridium electrodes are more involved and complex than previously stated. This result highlights the importance of employing theory together with true and complementary operando measurements capable of probing different aspects of catalysts surfaces during operation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effects of high-temperature CeO 2 calcination on the activity of Pt/CeO 2 catalysts for oxidation of unburned hydrocarbon fuels
High temperature (800 °C) pre-calcination of CeO 2 support decreases the surface defects and improves the mobility of surface lattice oxygen. As a result, the supported Pt clusters have higher oxygen coverage and superior HC oxidation activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Iron-activated persulfate oxidation degrades aqueous Perfluorooctanoic acid (PFOA) at ambient temperature
Perfluorooctanoic acid (PFOA, C 8 HF 15 O 2 ) is an industrial surfactant that is highly resistant to natural breakdown processes such as those mediated by heat, hydrolysis, photolysis, and biodegradation. Many efforts have been developed to breakdown PFOA to less harmful species due to its widespread human exposure and potential toxicity. However, these methods require high temperature or specialized equipment with serious disadvantages of high energy cost for long-term use. For this paper, we investigated the effectiveness of PFOA degradation by ferrous iron-activated persulfate oxidation (IAPO) under various aqueous geochemical conditions. Approximately 64% of PFOA (initial concentration = 1.64 μmol L –1 ) was degraded after 4 h under illuminated anoxic conditions at ambient temperature. This degradation rate and magnitude support the potential use of IAPO as a novel inexpensive and environmentally friendly method to remediate PFOA in soil and groundwater.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oxidation kinetics of SPS-densified U 3 Si 2 fuels—Microstructure impact
Here, U 3 Si 2 is a potential candidate for accident tolerant fuels because of its high uranium density and excellent thermal conductivity in comparison to UO 2 . However, U 3 Si 2 suffers from oxidation, steam corrosion, and subsequent disintegration/pulverization. The detailed investigation of kinetics that incorporates fundamental treatment of oxidation of U 3 Si 2 is scarcely reported, and the oxidation mechanisms have not been fully elucidated. In this paper, the oxidation behavior of microcrystalline (mc - ) and nanocrystalline (nc - ) U 3 Si 2 have been systematically investigated using a thermogravimetric analysis (TGA) apparatus through a series of isothermal and non-isothermal kinetic studies. The isothermal kinetic study with a model-fitting approach indicates oxidation activation energy of 85 kJ/mol for dense mc - U 3 Si 2 and 96.4 kJ/mol for nc - U 3 Si 2 pellets, while the isoconversional approach leads to an activation energy in the range of 70–85 kJ/mol for mc - U 3 Si 2 and 75–86 kJ/mol for nc - U 3 Si 2 with three most common model-free methods, including Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa, and Friedman methods. The derivation of oxidation activation energies using both isothermal and isoconversional methods highlights the approach to evaluate the oxidation resistance of nuclear materials using TGA quantitatively and makes it possible to compare among various nuclear fuels.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
The Influence of SiC on the Ablation Response of Advanced Refractory Composite Materials
In continuing our studies of advanced refractory composite materials we have recently completed an arc-jet test series of a diverse group of ceramics and ceramic matrix composites. The compositions range from continuous fiber reinforced ceramics to monoliths. Many of these materials contain SiC and one objective of this test series was to identify the influence of SiC oxidation mechanisms on material performance. Hence the arc heater was operated at two conditions; one in which the passive oxidation of SiC would be dominant and the other where the active oxidation of SiC would be dominant. It is shown here that the active oxidation mechanism of SiC does not dominate material performance when it is present at levels equal to or below 20 volume percent.
Bull, Jeffrey D.↗
Computational and experimental evidence for Sb( v ) metal mediated C–H activation and oxidative functionalization of arenes
Quantum-chemical calculations and experiments demonstrated that inorganic Sb V complexes can directly activate aromatic sp 2 C–H bonds and induce oxidative functionalization to form aryl esters.
Koppaka, Anjaneyulu [Department of Chemistry and B↗
Reduction of bacterial dissemination. germicidal activity of ethylene oxide. reduction of bacterial contamination on surfaces third quarterly summary report of progress
Bacteria dissemination reduction, ethylene oxide germicidal activity, and bacteria contamination reduction on surfaces
ETHYLENE OXIDE↗
Reaction paths of methane activation and oxidation of surface intermediates over NiO on Ceria-Zirconia catalysts studied by In-situ FTIR spectroscopy
Methane activation over NiO/Ce 0.82 Zr 0.18 O 2 catalysts synthesized by combustion synthesis is studied by in-situ IR spectroscopy and correlated to the properties and oxygen speciation of the catalyst. Through XRD, H 2 -TPR, and pyridine adsorption followed by FTIR spectroscopy, the reducibility and Lewis acidity of the catalysts are assessed. In-situ FTIR spectroscopy is used to monitor the methane activation on catalyst surfaces. Complex IR features of methane-derived surface species are observed and are attributed to the formation of surface alkyl/alkoxy, aldehyde, formate/carbonate, and aromatic species. A data analysis algorithm is developed to evaluate the evolution of different surface species over time. The formation of formate and carbonate species is driven by adsorbed surface oxygen, while less reactive oxygen species associated with NiO allow for the production of aromatics and alkoxy intermediates. Finally, by tuning the reducibility and Lewis acidity of the catalyst, the selectivity to alkoxy intermediates can be improved.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oxygen Atom Transfer as an Alternative Pathway for Oxygen–Oxygen Bond Formation
Fundamental understanding of catalytic mechanisms of water oxidation is a prerequisite for the design and development of efficient and rugged water oxidation catalysts. In this work, a detailed mechanistic study of the water oxidation mechanism of the [Ru II (npm)(4-pic) 2 (H 2 O)] 2+ (npm = 4-t-butyl-2,6-di(1',8'-naphthyrid-2'-yl)-pyridine, pic = 4-picoline) complex, [Ru II –OH 2 ] 2+ , reveals oxygen atom transfer from highly reactive ruthenium oxo intermediates to noncoordinating nitrogen atoms of the ligand as a novel route for oxygen evolution via storage of oxidizing equivalents as N-oxide groups on the ligand framework. Theoretical calculations show that the initial complex, [RuII–OH 2 ] 2+ , is transformed to a di-N-oxide [Ru II –OH 2 ,(-NO) 2 ] 2+ complex upon oxidation via facile OAT steps from Ru V =O species and that [Ru V =O,(-NO) 2 ] 3+ represents the most likely reactive species for the critical O–O bond formation. Furthermore, a new stepwise mechanism for oxygen evolution is introduced, which proceeds via coupling of Ru–O and N–O moieties producing a peroxide intermediate, [Ru V –OO–N,(-NO)] 3+ , and can compete with the water nucleophilic attack pathway for the oxygen evolution reaction. In this mechanism, a water molecule is oxidatively activated to an “oxygen atom” which is “stored” at a noncoordinating pyridine. Oxidative activation of a second water molecule, facilitated by coordination expansion of the intermediate N-oxide, generates the second oxygen atom required to produce a dioxygen molecule.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Novel Remediation of Mercury-Contaminated Sediments Using Manganese Oxide and Activated Carbon Amendments - 20394
Mercury contamination in sediments poses a challenging remediation problem because of its ability to biogeochemically cycle and biomagnify in the food chain as methylmercury from low resident sediment and porewater concentrations. One mitigation approach is to lower the overall rate of net methylmercury production by creating conditions unfavorable for sulfate and iron reduction or methanogenesis, the primary pathways for methylation of inorganic mercury. Manganese oxides and other redox-active amendments are a promising and novel in situ amendment technology aimed at reducing net methylation of mercury though control of redox conditions in mercury-contaminated sediment-water systems. This paper reviews the thermodynamic and kinetic framework for this remediation technology, presents experimental and spectroscopic data illustrating the approach using solid manganese oxides, and discusses potential advantages, disadvantages, and applications. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Structure and Reactivity of Pristine and Reduced Spinel CoFe 2 O 4 (001)/(100) Surfaces
Cobalt ferrite, CoFe 2 O 4 (CFO), nanocrystals are efficient and competitive anode materials in the field of electrochemical water splitting. Using density functional theory with on-site Hubbard U corrections (DFT+U), we have investigated the structural, electronic and magnetic properties of CFO (001)/(100) surfaces, as well as their reactivities towards water adsorption. Special attention has been focused on the formation of oxygen vacancies (V O ), due to their key role in the oxidation activity of metal oxides, often based on the Mars-van-Krevelen mechanism. Our results show that vacancy formation is easiest at oxygen sites that are not bound to tetrahedrally-coordinated Fe. Water adsorbs mainly in molecular form on the Co/Fe metal cations, whereas it dissociates at defects. In comparison to other spinels, CFO is similar to NiFe 2 O 4 , exhibiting relatively low energy cost of V O formation and a strong affinity of the vacancies towards water. Furthermore, these findings suggest that CFO may be a more promising oxidation catalyst than NiCo 2 O 4 and Co 3 O 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cu and Ni Co-sputtered heteroatomic thin film for enhanced nonenzymatic glucose detection
Abstract In this work, we report a wafer-scale and chemical-free fabrication of nickel (Ni) and copper (Cu) heteroatomic Cu–Ni thin films using RF magnetron sputtering technique for non-enzymatic glucose sensing application. The as-prepared wafer-scale Cu–Ni thin films exhibits excellent electrocatalytic activity toward glucose oxidation with a 1.86 μM detection limit in the range of 0.01 mM to 20 mM range. The Cu–Ni film shows 1.3- and 5.4-times higher glucose oxidation activity in comparison to the Cu and Ni electrodes, respectively. The improved electrocatalytic activity is attributed to the synergistic effect of the bimetallic catalyst and high density of grain boundaries. The Cu–Ni electrodes also possessed excellent anti-interference characteristics. These results indicate that Cu–Ni heteroatomic thin film can be a potential candidate for the development of non-enzymatic glucose biosensor because of its chemical free synthesis, excellent reproducibility, reusability, and long-term stability.
59 BASIC BIOLOGICAL SCIENCES↗