Role of Redox-Inactive Transition-Metals in the Behavior of Cation-Disordered Rocksalt Cathodes.

Owing to the capacity boost from oxygen redox activities, Li-rich cation-disordered rocksalts (LRCDRS) represent a new class of promising high-energy Li-ion battery cathode materials. Redox-inactive transition-metal (TM) cations, typically d0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d0 TM (Nb5+ and Ti4+ ) is systematically compared on the redox chemistry of Mn-based model LRCDRS cathodes, namely Li1.3 Nb0.3 Mn0.4 O2 (LNMO), Li1.25 Nb0.15 Ti0.2 Mn0.4 O2 (LNTMO), and Li1.2 Ti0.4 Mn0.4 O2 (LTMO). Although electrochemically inactive, d0 TM serves as a modulator for oxygen redox, with Nb5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X-ray scattering reveal that Ti4+ is better in stabilizing the oxidized oxygen anions (On - , 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d0 TM on degradation mechanism further suggests that proper design of redox-inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.

Alleviating oxygen evolution from Li-excess oxide materials through theory-guided surface protection.

Li-excess cathodes comprise one of the most promising avenues for increasing the energy density of current Li-ion technology. However, the first-cycle surface oxygen release in these materials causes cation densification and structural reconstruction of the surface region, leading to encumbered ionic transport and increased impedance. In this work, we use the first principles Density Functional Theory to systematically screen for optimal cation dopants to improve oxygen-retention at the surface. The initial dopant set includes all transition metal, post-transition metal, and metalloid elements. Our screening identifies Os, Sb, Ru, Ir, or Ta as high-ranking dopants considering the combined criteria, and rationalization based on the electronic structure of the top candidates are presented. To validate the theoretical screening, a Ta-doped Li1.3Nb0.3Mn0.4O2 cathode was synthesized and shown to present initial improved electrochemical performance as well as significantly reduced oxygen evolution, as compared with the pristine, un-doped, system.

PREVALENCE AND RISK FACTORS OF TRICHOMONAS GALLINAE AND TRICHOMONOSIS IN GOLDEN EAGLE ( AQUILA CHRYSAETOS) NESTLINGS IN WESTERN NORTH AMERICA.

Avian trichomonosis, caused by the protozoan Trichomonas gallinae, affects bird-eating raptors worldwide. Raptors can develop trichomonosis by feeding on infected prey, particularly Rock Pigeons (C olumba livia), which are a reservoir for T. gallinae. Raptors may be particularly vulnerable to T. gallinae infection in degraded habitats, where changes in resources may cause raptors to switch from foraging on native prey to synanthropic avian species such as Rock Pigeons. Golden Eagles ( Aquila chrysaetos) typically forage on mammals; however, habitat across much of their range is experiencing degradation through changes in land use, climate, and human encroachment. In 2015, we examined the prevalence of T. gallinae infection in Golden Eagle nestlings across western North America and conducted an intensive study on factors associated with T. gallinae infection and trichomonosis in southwestern Idaho. We found T. gallinae infection in 13% (12/96) of eagle nestlings across 10 western states and in 41% (13/32) of nestlings in southwestern Idaho. At the Idaho site, the probability of T. gallinae infection increased as the proportion of Rock Pigeons in nestling diet increased. Nestlings with diets that consisted of ≥10% Rock Pigeons had a very high probability of T. gallinae infection. We compared historical (1971-81) and recent (2014-15) diet data and incidence of trichomonosis lesions of nestling eagles in Idaho and found that the proportion of Rock Pigeons in eagle diets was higher in recent versus historical periods, as was the proportion of eagle nestlings with trichomonosis lesions. Our results suggested that localized shifts in eagle diet that result from habitat degradation and loss of historical prey resources have the potential to affect Golden Eagle nestling survival and supported the hypothesis that land use change can alter biologic communities in a way that might have consequences for disease infection and host susceptibility.

Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials.

There is an urgent need for low-cost, resource-friendly, high-energy-density cathode materials for lithium-ion batteries to satisfy the rapidly increasing need for electrical energy storage. To replace the nickel and cobalt, which are limited resources and are associated with safety problems, in current lithium-ion batteries, high-capacity cathodes based on manganese would be particularly desirable owing to the low cost and high abundance of the metal, and the intrinsic stability of the Mn4+ oxidation state. Here we present a strategy of combining high-valent cations and the partial substitution of fluorine for oxygen in a disordered-rocksalt structure to incorporate the reversible Mn2+/Mn4+ double redox couple into lithium-excess cathode materials. The lithium-rich cathodes thus produced have high capacity and energy density. The use of the Mn2+/Mn4+ redox reduces oxygen redox activity, thereby stabilizing the materials, and opens up new opportunities for the design of high-performance manganese-rich cathodes for advanced lithium-ion batteries.

Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials.

Recent progress in the understanding of percolation theory points to cation-disordered lithium-excess transition metal oxides as high-capacity lithium-ion cathode materials. Nevertheless, the oxygen redox processes required for these materials to deliver high capacity can trigger oxygen loss, which leads to the formation of resistive surface layers on the cathode particles. We demonstrate here that, somewhat surprisingly, fluorine can be incorporated into the bulk of disordered lithium nickel titanium molybdenum oxides using a standard solid-state method to increase the nickel content, and that this compositional modification is very effective in reducing oxygen loss, improving energy density, average voltage, and rate performance. We argue that the valence reduction on the anion site, offered by fluorine incorporation, opens up significant opportunities for the design of high-capacity cation-disordered cathode materials.The performance of lithium-excess cation-disordered oxides as cathode materials relies on the extent to which the oxygen loss during cycling is mitigated. Here, the authors show that incorporating fluorine is an effective strategy which substantially improves the cycling stability of such a material.

Poly(vinylidene fluoride) (PVDF) Binder Degradation in Li-O2 Batteries: A Consideration for the Characterization of Lithium Superoxide.

We show that a common Li-O2 battery cathode binder, poly(vinylidene fluoride) (PVDF), degrades in the presence of reduced oxygen species during Li-O2 discharge when adventitious impurities are present. This degradation process forms products that exhibit Raman shifts (∼1133 and 1525 cm-1) nearly identical to those reported to belong to lithium superoxide (LiO2), complicating the identification of LiO2 in Li-O2 batteries. We show that these peaks are not observed when characterizing extracted discharged cathodes that employ poly(tetrafluoroethylene) (PTFE) as a binder, even when used to bind iridium-decorated reduced graphene oxide (Ir-rGO)-based cathodes similar to those that reportedly stabilize bulk LiO2 formation. We confirm that for all extracted discharged cathodes on which the 1133 and 1525 cm-1 Raman shifts are observed, only a 2.0 e-/O2 process is identified during the discharge, and lithium peroxide (Li2O2) is predominantly formed (along with typical parasitic side product formation). Our results strongly suggest that bulk, stable LiO2 formation via the 1 e-/O2 process is not an active discharge reaction in Li-O2 batteries.

Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration.

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (FexOy nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by FexOy functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. FexOy functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by FexOy functionalized membrane for removal of NA.

Engineered Iron/Iron Oxide Functionalized Membranes for Selenium and Other Toxic Metal Removal from Power Plant Scrubber Water.

The remediation of toxic metals from water with high concentrations of salt has been an emerging area for membrane separation. Cost-effective nanomaterials such as iron and iron oxide nanoparticles have been widely used in reductive and oxidative degradation of toxic organics. Similar procedures can be used for redox transformations of metal species (e.g. metal oxyanions to elemental metal), and/or adsorption of species on iron oxide surface. In this study, iron-functionalized membranes were developed for reduction and adsorption of selenium from coal-fired power plant scrubber water. Iron-functionalized membranes have advantages over iron suspension as the membrane prevents particle aggregation and dissolution. Both lab-scale and full-scale membranes were prepared first by coating polyvinylidene fluoride (PVDF) membranes with polyacrylic acid (PAA), followed by ion exchange of ferrous ions and subsequent reduction to zero-valent iron nanoparticles. Water permeability of membrane decreased as the percent PAA functionalization increased, and the highest ion exchange capacity (IEC) was obtained at 20% PAA with highly pH responsive pores. Although high concentrations of sulfate and chloride in scrubber water decreased the reaction rate of selenium reduction, this was shown to be overcome by integration of nanofiltration (NF) and iron-functionalized membranes, and selenium concentration below 10 µg/L was achieved.

Iron-Based Redox Polymerization of Acrylic Acid for Direct Synthesis of Hydrogel/Membranes, and Metal Nanoparticles for Water Treatment.

Functionalized polymer materials with ion exchange groups and integration of nano-structured materials is an emerging area for catalytic and water pollution control applications. The polymerization of materials such as acrylic acid often requires persulfate initiator and a high temperature start. However, is generally known that metal ions accelerate such polymerizations starting from room temperature. If the metal is properly selected, it can be used in environmental applications adding two advantages simultaneously. This paper deals with this by polymerizing acrylic acid using iron as accelerant and its subsequent use for nanoparticle synthesis in hydrogel and PVDF membranes. Characterizations of hydrogel, membranes and nanoparticles were carried out with different techniques. Nanoparticles sizes of 30-60 nm were synthesized. Permeability and swelling measurements demonstrate an inverse relationship between hydrogel mesh size (6.30 to 8.34 nm) and membrane pores (222 to 110 nm). Quantitative reduction of trichloroethylene/chloride generation by Fe/Pd nanoparticles in hydrogel/membrane platforms was also performed.

Physically constrained maximum likelihood mode filtering.

Mode filtering is most commonly implemented using the sampled mode shapes or pseudoinverse algorithms. Buck et al. [J. Acoust. Soc. Am. 103, 1813-1824 (1998)] placed these techniques in the context of a broader maximum a posteriori (MAP) framework. However, the MAP algorithm requires that the signal and noise statistics be known a priori. Adaptive array processing algorithms are candidates for improving performance without the need for a priori signal and noise statistics. A variant of the physically constrained, maximum likelihood (PCML) algorithm [A. L. Kraay and A. B. Baggeroer, IEEE Trans. Signal Process. 55, 4048-4063 (2007)] is developed for mode filtering that achieves the same performance as the MAP mode filter yet does not need a priori knowledge of the signal and noise statistics. The central innovation of this adaptive mode filter is that the received signal's sample covariance matrix, as estimated by the algorithm, is constrained to be that which can be physically realized given a modal propagation model and an appropriate noise model. Shallow water simulation results are presented showing the benefit of using the PCML method in adaptive mode filtering.

Modal processing for acoustic communications in shallow water experiment.

Acoustical array data from the Shallow Water Acoustics experiment was processed to show the feasibility of broadband mode decomposition as a preprocessing method to reduce the effective channel delay spread and concentrate received signal energy in a small number of independent channels. The data were collected by a vertical array designed at the Woods Hole Oceanographic Institution. Phase-shift Keying (PSK) m-sequence modulated signals with different carrier frequencies were transmitted at a distance 19.2 km from the array. Even during a strong internal waves activity a low bit error rate was achieved.

microRNA modulation of circadian-clock period and entrainment.

microRNAs (miRNAs) are a class of small, noncoding RNAs that regulate the stability or translation of mRNA transcripts. Although recent work has implicated miRNAs in development and in disease, the expression and function of miRNAs in the adult mammalian nervous system have not been extensively characterized. Here, we examine the role of two brain-specific miRNAs, miR-219 and miR-132, in modulating the circadian clock located in the suprachiasmatic nucleus. miR-219 is a target of the CLOCK and BMAL1 complex, exhibits robust circadian rhythms of expression, and the in vivo knockdown of miR-219 lengthens the circadian period. miR-132 is induced by photic entrainment cues via a MAPK/CREB-dependent mechanism, modulates clock-gene expression, and attenuates the entraining effects of light. Collectively, these data reveal miRNAs as clock- and light-regulated genes and provide a mechanistic examination of their roles as effectors of pacemaker activity and entrainment.

The molecular gatekeeper Dexras1 sculpts the photic responsiveness of the mammalian circadian clock.

The mammalian master clock, located in the suprachiasmatic nucleus (SCN), is exquisitely sensitive to photic timing cues, but the key molecular events that sculpt both the phasing and magnitude of responsiveness are not understood. Here, we show that the Ras-like G-protein Dexras1 is a critical factor in these processes. Dexras1-deficient mice (dexras1-/-) exhibit a restructured nighttime phase response curve and a loss of gating to photic resetting during the day. Dexras1 affects the photic sensitivity by repressing or activating time-of-day-specific signaling pathways that regulate extracellular signal-regulated kinase (ERK)/mitogen-activated protein kinase (MAPK). During the late night, Dexras1 limits the capacity of pituitary adenylate cyclase (PAC) activating peptide (PACAP)/PAC1 to affect ERK/MAPK, and in the early night, light-induced phase delays, which are mediated predominantly by NMDA receptors, are reduced as reported previously. Daytime photic phase advances are mediated by a novel signaling pathway that does not affect the SCN core but rather stimulates ERK/MAPK in the SCN shell and triggers downregulation of clock protein expression.

Serologic evidence of West Nile virus infection in three wild raptor populations.

We assayed for West Nile virus (WNV) antibodies to determine the presence and prevalence of WNV infection in three raptor populations in southeast Wisconsin during 2003-04. This study was conducted in the framework of ongoing population studies that started before WNV was introduced to the study area. For 354 samples, 88% of 42 adult Cooper's hawks (Accipiter cooperii), 2.1% of 96 nestling Cooper's hawks, 9.2% of 141 nestling red-tailed hawks (Buteo jamaicensis), and 12% of 73 nestling great horned owls (Bubo virginianus) tested positive for WNV antibodies by the constant virus-serum dilution neutralization test. Samples that tested positive for WNV antibodies were collected across a wide variety of habitat types, including urban habitats (both high and low density), roads, parking areas, recreational areas, croplands, pastures, grasslands, woodlands, and wetlands. Based on the increased prevalence and significantly higher WNV antibody titers in adults compared with nestlings, we suggest that nestlings with detectable antibody levels acquired these antibodies through passive transmission from the mother during egg production. Low levels of WNV antibodies in nestlings could serve as a surrogate marker of exposure in adult raptor populations. Based on breeding population densities and reproductive success over the past 15 yr, we found no apparent adverse effects of WNV infections on these wild raptor populations.