Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis.

The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 resulted in the most active catalyst for the OER.

Redox properties of birnessite from a defect perspective.

Birnessite, a layered-structure MnO, is an earth-abundant functional material with potential for various energy and environmental applications, such as water oxidation. An important feature of birnessite is the existence of Mn(III) within the MnO layers, accompanied by interlayer charge-neutralizing cations. Using first-principles calculations, we reveal the nature of Mn(III) in birnessite with the concept of the small polaron, a special kind of point defect.

Covalent Metal-Metal-Bonded Mn Tetrahedron Inscribed within a Four-Coordinate Manganese Cubane Cluster, As Evidenced by Unexpected Temperature-Independent Diamagnetism.

The electronic structures of the manganese(IV) cubane cluster Mn(μ-NBu)(NBu) (1) and its one-electron-oxidized analogue, the 3:1 Mn/Mn cluster [Mn(μ-NBu)(NBu)][PF] (1[PF]), are described. The S = 0 spin quantum number of 1 is explained by a diamagnetic electronic structure where all metal-based d electrons are paired in Mn-Mn bonding orbitals. Temperature- and power-dependent studies of the S = / electron paramagnetic resonance signal of 1 are consistent with an electronic structure described as a delocalized one-electron radical.

Enhanced Davydov Splitting in Crystals of a Perylene Diimide Derivative.

We report the polarized absorption spectra of high-quality, thin crystals of a perylene diimide (PDI) species with branched side chains (B2). The absorption spectrum shows exemplary polarization-dependent H-like and J-like aggregate behavior upon orthogonal excitation, with a sizable Davydov splitting (DS) of 1230 cm and peak to peak splitting of 3040 cm. The experimental results are compared to theoretical calculations with remarkable agreement.

Effect of Interlayer Spacing on the Activity of Layered Manganese Oxide Bilayer Catalysts for the Oxygen Evolution Reaction.

We investigated the dependence of the electrocatalytic activity for the oxygen evolution reaction (OER) on the interlayer distance of five compositionally distinct layered manganese oxide nanostructures. Each individual electrocatalyst was assembled with a different alkali metal intercalated between two nanosheets (NS) of manganese oxide to form a bilayer structure. Manganese oxide NS were synthesized via the exfoliation of a layered material, birnessite.

Electronic Structure of Manganese Complexes of the Redox-Non-innocent Tetrazene Ligand and Evidence for the Metal-Azide/Imido Cycloaddition Intermediate.

The first synthetic manganese tetrazene complexes are described as a redox pair comprising anionic [Mn(N4 Ad2 )2 ](-) (1) and neutral Mn(N4 Ad2 )2 (2) complexes (N4 Ad2 =[Ad-N-N=N-N-Ad](2-) ). Compound 1 is obtained in two forms as lithium salts, one as a cationic Li2 Mn cluster, and one as a Mn-Li 1D ionic polymer. Compound 1 is electronically described as a Mn(III) center with two [N4 Ad2 ](2-) ligands.

Nickel Confined in the Interlayer Region of Birnessite: an Active Electrocatalyst for Water Oxidation.

We report a synthetic method to enhance the electrocatalytic activity of birnessite for the oxygen evolution reaction (OER) by intercalating Ni(2+) ions into the interlayer region. Electrocatalytic studies showed that nickel (7.7 atomic %)-intercalated birnessite exhibits an overpotential (η) of 400 mV for OER at an anodic current of 10 mA cm(-2) .

Data Verification Tools for Minimizing Management Costs of Dense Air-Quality Monitoring Networks.

Aiming at minimizing the costs, both of capital expenditure and maintenance, of an extensive air-quality measurement network, we present simple statistical methods that do not require extensive training data sets for automated real-time verification of the reliability of data delivered by a spatially dense hybrid network of both low-cost and reference ozone measurement instruments. Ozone is a pollutant that has a relatively smooth spatial spread over a large scale although there can be significant small-scale variations. We take advantage of these characteristics and demonstrate detection of instrument calibration drift within a few days using a rolling 72 h comparison of hourly averaged data from the test instrument with that from suitably defined proxies.

Frustrated Solvation Structures Can Enhance Electron Transfer Rates.

Polar surfaces can interact strongly with nearby water molecules, leading to the formation of highly ordered interfacial hydration structures. This ordering can lead to frustration in the hydrogen bond network, and, in the presence of solutes, frustrated hydration structures. We study frustration in the hydration of cations when confined between sheets of the water oxidation catalyst manganese dioxide.

Copper-Intercalated Birnessite as a Water Oxidation Catalyst.

We report a synthetic method to increase the catalytic activity of birnessite toward water oxidation by intercalating copper in the interlayer region of the layered manganese oxide. Intercalation of copper, verified by XRD, XPS, ICP, and Raman spectroscopy, was accomplished by exposing a suspension of birnessite to a Cu(+)-bearing precursor molecule that underwent disproportionation in solution to yield Cu(0) and Cu(2+). Electrocatalytic studies showed that the Cu-modified birnessite exhibited an overpotential for water oxidation of ∼490 mV (at 10 mA/cm(2)) and a Tafel slope of 126 mV/decade compared to ∼700 mV (at 10 mA/cm(2)) and 240 mV/decade, respectively, for birnessite without copper.

Decoration of the layered manganese oxide birnessite with Mn(II/III) gives a new water oxidation catalyst with fifty-fold turnover number enhancement.

The role of the manganese average oxidation state (AOS) in water oxidation catalysis by birnessite was investigated. Low AOS samples were most active, generating O2 immediately. Samples with a relatively high AOS showed an initial induction period and decreased turnover.

A land use regression model for ultrafine particles in Vancouver, Canada.

Methods to characterize chronic exposure to ultrafine particles (UFP) can help to clarify potential health effects. Since UFP are not routinely monitored in North America, spatiotemporal models are one potential exposure assessment methodology. Portable condensation particle counters were used to measure particle number concentrations (PNC) to develop a land use regression (LUR) model.

Particulate matter exposure along designated bicycle routes in Vancouver, British Columbia.

An instrumented bicycle was used to elucidate particulate matter exposures along bicycle routes passing through a variety of land uses over 14 days during summer and fall in a mid-latitude traffic dominated urban setting. Overall, exposures were low or comparable to those found in studies elsewhere (mean PM(2.5) and PM(10) concentrations over each daily bicycle traverse varied between 7-34 microg m(-3) and 26-77 microg m(-3) respectively).

Evaluation of artificial neural networks for fine particulate pollution (PM10 and PM2.5) forecasting.

Multi-layer perceptron (MLP) artificial neural network (ANN) models are compared with traditional multiple regression (MLR) models for daily maximum and average O3 and particulate matter (PM10 and PM2.5) forecasting. MLP particulate forecasting models show little if any improvement over MLR models and exhibit less skill than do O3 forecasting models.