New insights into water splitting at mesoporous α-Fe₂O₃ films: a study by modulated transmittance and impedance spectroscopies

Closed access. This article was published in the Journal of the American Chemical Society [© American Chemical Society] and the definitive version is available at: http://dx.doi.org/10.1021/ja209530sThin mesoporous films of α-Fe2O3 have been prepared on conducting glass substrates using layer-by-layer self-assembly of ca. 4 nm hydrous oxide nanoparticles followed by calcining. The electrodes were used to study the oxygen evolution reaction (OER) in the dark and under illumination using in situ potential-modulated absorption spectroscopy (PMAS) and light-modulated absorption spectroscopy (LMAS) combined with impedance spectroscopy. Formation of surface-bound higher-valent iron species (or “surface trapped holes”) was deduced from the PMAS spectra measured in the OER onset region. Similar LMAS spectra were obtained at more negative potentials in the onset region of photoelectrochemical OER, indicating involvement of the same intermediates. The impedance response of the mesoporous α-Fe2O3 electrodes exhibits characteristic transmission line behavior that is attributed to slow hopping of holes, probably between surface iron species. Frequency-resolved PMAS and LMAS measurements revealed slow relaxation behavior that can be related to the impedance response and that indicates that the lifetime of the intermediates (or trapped holes) involved in the OER is remarkably long

Underpotential surface reduction of mesoporous CeO2 nanoparticle films

The formation of variable-thickness CeO2 nanoparticle mesoporous films from a colloidal nanoparticle solution (approximately 1–3-nm-diameter CeO2) is demonstrated using a layer-by-layer deposition process with small organic binder molecules such as cyclohexanehexacarboxylate and phytate. Film growth is characterised by scanning and transmission electron microscopies, X-ray scattering and quartz crystal microbalance techniques. The surface electrochemistry of CeO2 films before and after calcination at 500 °C in air is investigated. A well-defined Ce(IV/III) redox process confined to the oxide surface is observed. Beyond a threshold potential, a new phosphate phase, presumably CePO4, is formed during electrochemical reduction of CeO2 in aqueous phosphate buffer solution. The voltammetric signal is sensitive to (1) thermal pre-treatment, (2) film thickness, (3) phosphate concentration and (4) pH. The reversible ‘underpotential reduction’ of CeO2 is demonstrated at potentials positive of the threshold. A transition occurs from the reversible ‘underpotential region’ in which no phosphate phase is formed to the irreversible ‘overpotential region’ in which the formation of the cerium(III) phosphate phase is observed. The experimental results are rationalised based on surface reactivity and nucleation effects

Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 10[superscript 8] to 2.2 × 10[superscript 10] molec cm[superscript −3] over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 10[superscript 6] to 2 × 10[superscript 7] molec cm[superscript −3] over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 10[superscript 11] and 2 × 10[superscript 11] molec cm[superscript −3] s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.National Science Foundation (U.S.). Atmospheric Chemistry Program (Grant AGS-1056225)National Science Foundation (U.S.). Atmospheric Chemistry Program (Grant AGS-1245011

Underpotential surface reduction of mesoporous CeO 2 nanoparticle films

This article was published in the Journal of Solid State Electrochemistry, [© Springer] and the original publication is available at www.springerlink.comThe formation of variable-thickness CeO2 nanoparticle mesoporous films from a colloidal nanoparticle solution (approximately 1–3-nm-diameter CeO2) is demonstrated using a layer-by-layer deposition process with small organic binder molecules such as cyclohexanehexacarboxylate and phytate. Film growth is characterised by scanning and transmission electron microscopies, X-ray scattering and quartz crystal microbalance techniques. The surface electrochemistry of CeO2 films before and after calcination at 500 °C in air is investigated. A well-defined Ce(IV/III) redox process confined to the oxide surface is observed. Beyond a threshold potential, a new phosphate phase, presumably CePO4, is formed during electrochemical reduction of CeO2 in aqueous phosphate buffer solution. The voltammetric signal is sensitive to (1) thermal pre-treatment, (2) film thickness, (3) phosphate concentration and (4) pH. The reversible ‘underpotential reduction’ of CeO2 is demonstrated at potentials positive of the threshold. A transition occurs from the reversible ‘underpotential region’ in which no phosphate phase is formed to the irreversible ‘overpotential region’ in which the formation of the cerium(III) phosphate phase is observed. The experimental results are rationalised based on surface reactivity and nucleation effects

Toward reconstructing the evolution of advanced moths and butterflies (Lepidoptera: Ditrysia): an initial molecular study

<p>Abstract</p> <p>Background</p> <p>In the mega-diverse insect order Lepidoptera (butterflies and moths; 165,000 described species), deeper relationships are little understood within the clade Ditrysia, to which 98% of the species belong. To begin addressing this problem, we tested the ability of five protein-coding nuclear genes (6.7 kb total), and character subsets therein, to resolve relationships among 123 species representing 27 (of 33) superfamilies and 55 (of 100) families of Ditrysia under maximum likelihood analysis.</p> <p>Results</p> <p>Our trees show broad concordance with previous morphological hypotheses of ditrysian phylogeny, although most relationships among superfamilies are weakly supported. There are also notable surprises, such as a consistently closer relationship of Pyraloidea than of butterflies to most Macrolepidoptera. Monophyly is significantly rejected by one or more character sets for the putative clades Macrolepidoptera as currently defined (<it>P </it>< 0.05) and Macrolepidoptera excluding Noctuoidea and Bombycoidea sensu lato (<it>P </it>≤ 0.005), and nearly so for the superfamily Drepanoidea as currently defined (<it>P </it>< 0.08). Superfamilies are typically recovered or nearly so, but usually without strong support. Relationships within superfamilies and families, however, are often robustly resolved. We provide some of the first strong molecular evidence on deeper splits within Pyraloidea, Tortricoidea, Geometroidea, Noctuoidea and others.</p> <p>Separate analyses of mostly synonymous versus non-synonymous character sets revealed notable differences (though not strong conflict), including a marked influence of compositional heterogeneity on apparent signal in the third codon position (nt3). As available model partitioning methods cannot correct for this variation, we assessed overall phylogeny resolution through separate examination of trees from each character set. Exploration of "tree space" with GARLI, using grid computing, showed that hundreds of searches are typically needed to find the best-feasible phylogeny estimate for these data.</p> <p>Conclusion</p> <p>Our results (a) corroborate the broad outlines of the current working phylogenetic hypothesis for Ditrysia, (b) demonstrate that some prominent features of that hypothesis, including the position of the butterflies, need revision, and (c) resolve the majority of family and subfamily relationships within superfamilies as thus far sampled. Much further gene and taxon sampling will be needed, however, to strongly resolve individual deeper nodes.</p

A search for W bb and W Higgs production in ppbar collisions at sqrt(s)=1.96 TeV

We present a search for W b \bar{b} production in p \bar{p} collisions at sqrt{s}=1.96 TeV in events containing one electron, an imbalance in transverse momentum, and two b-tagged jets. Using 174 pb-1 of integrated luminosity accumulated by the D0 experiment at the Fermilab Tevatron collider, and the standard-model description of such events, we set a 95% C.L. upper limit on W b \bar{b}$production of 6.6 pb for b quarks with transverse momenta p_T^b > 20 GeV and b \bar{b} separation in pseudorapidity-azimuth space Delta R_bb > 0.75. Restricting the search to optimized b \bar{b} mass intervals provides upper limits on$WH$production of 9.0$-$12.2 pb, for Higgs-boson masses of 105$-$135 GeV.Comment: 7 pages, 4 figures, 1 table, submitted to Physical Review Letter

Can Deliberately Incomplete Gene Sample Augmentation Improve a Phylogeny Estimate for the Advanced Moths and Butterflies (Hexapoda: Lepidoptera)?

This paper addresses the question of whether one can economically improve the robustness of a molecular phylogeny estimate by increasing gene sampling in only a subset of taxa, without having the analysis invalidated by artifacts arising from large blocks of missing data. Our case study stems from an ongoing effort to resolve poorly understood deeper relationships in the large clade Ditrysia ( > 150,000 species) of the insect order Lepidoptera (butterflies and moths). Seeking to remedy the overall weak support for deeper divergences in an initial study based on five nuclear genes (6.6 kb) in 123 exemplars, we nearly tripled the total gene sample (to 26 genes, 18.4 kb) but only in a third (41) of the taxa. The resulting partially augmented data matrix (45% intentionally missing data) consistently increased bootstrap support for groupings previously identified in the five-gene (nearly) complete matrix, while introducing no contradictory groupings of the kind that missing data have been predicted to produce. Our results add to growing evidence that data sets differing substantially in gene and taxon sampling can often be safely and profitably combined. The strongest overall support for nodes above the family level came from including all nucleotide changes, while partitioning sites into sets undergoing mostly nonsynonymous versus mostly synonymous change. In contrast, support for the deepest node for which any persuasive molecular evidence has yet emerged (78–85% bootstrap) was weak or nonexistent unless synonymous change was entirely excluded, a result plausibly attributed to compositional heterogeneity. This node (Gelechioidea + Apoditrysia), tentatively proposed by previous authors on the basis of four morphological synapomorphies, is the first major subset of ditrysian superfamilies to receive strong statistical support in any phylogenetic study. A “more-genes-only” data set (41 taxa×26 genes) also gave strong signal for a second deep grouping (Macrolepidoptera) that was obscured, but not strongly contradicted, in more taxon-rich analyses

A Search for the Flavor-Changing Neutral Current Decay B0_s -> mu^+mu^- in pp(bar) Collisions at \sqrt{s} = 1.96 TeV with the D0 Detector

We present the results of a search for the flavor-changing neutral current decay B0_s -> mu+ mu- using a data set with integrated luminosity of 240 pb^{-1} of pp(bar) collisions at sqrt{s}=1.96 TeV collected with the D0 detector in Run II of the Fermilab Tevatron collider. We find the upper limit on the branching fraction to be Br(B0_s -> mu+ mu-) \leq 5.0 x 10^{-7} at the 95% C.L. assuming no contributions from the decay B0_d -> mu+ mu- in the signal region. This limit is the most stringent upper bound on the branching fraction B0_s -> mu+ mu- to date.Comment: 7 pages, 3 figures, LaTeX, to be submitted to Physical Review Letters, minor changes to text, reference adde