Redox properties of birnessite from a defect perspective.

Birnessite, a layered-structure MnO2, 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 MnO2 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. Further taking into account the effect of the spatial distribution of Mn(III), we propose a theoretical model to explain the structure-performance dependence of birnessite as an oxygen evolution catalyst. We find an internal potential step which leads to the easy switching of the oxidation state between Mn(III) and Mn(IV) that is critical for enhancing the catalytic activity of birnessite. Finally, we conduct a series of comparative experiments which support our model.

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. In particular, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Furthermore, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O2/mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.

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. Atomic force microscopy was used to determine the heights of the bilayer catalysts. The interlayer spacing of the supported bilayers positively correlates with the size of the alkali cation: NS/Cs+/NS > NS/Rb+/NS > NS/K+/NS > NS/Na+/NS > NS/Li+/NS. The thermodynamic origins of these bilayer heights were investigated using molecular dynamics simulations. The overpotential (η) for the OER correlates with the interlayer spacing; NS/Cs+/NS has the lowest η (0.45 V), while NS/Li+/NS exhibits the highest η (0.68 V) for OER at a current density of 1 mA/cm2. Kinetic parameters (η and Tafel slope) associated with NS/Cs+/NS for the OER were superior to that of the bulk birnessite phase, highlighting the structural uniqueness of these nanoscale assemblies.

Covalent Metal-Metal-Bonded Mn4 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(µ3-NtBu)4(NtBu)4 (1) and its one-electron-oxidized analogue, the 3:1 MnIV/MnV cluster [Mn(µ3-NtBu)4(NtBu)4]+[PF6]- (1+[PF6]), 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 = 1/2 electron paramagnetic resonance signal of 1+ are consistent with an electronic structure described as a delocalized one-electron radical.

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. The one-electron oxidized 2 is crystalized in two morphologies, one as pure 2 and one as an acetonitrile adduct. Despite similar composition, the behavior of 2 differs in the two morphologies. Compound 2-MeCN is relatively air and temperature stable. Crystalline 2, on the other hand, exhibits a compositional, dynamic disorder wherein the tetrazene metallacycle ring-opens into a metal imide/azide complex detectable by X-ray crystallography and FTIR spectroscopy. Electronic structure of 2 was examined by EPR and XPS spectroscopies and DFT calculations, which indicate 2 is best described as a Mn(III) ion with an anion radical delocalized across the two ligands through spin-polarization effects.

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. We define the required characteristics of the proxy measurements by working from a definition of the network purpose and specification, in this case reliable determination of the proportion of hourly averaged ozone measurements that are above a threshold in any given day, and detection of calibration drift of greater than ±30% in slope or ±5 parts-per-billion in offset. By analyzing results of a study of an extensive deployment of low-cost instruments in the Lower Fraser Valley, we demonstrate that proxies can be established using land-use criteria and that simple statistical comparisons can identify low-cost instruments that are not stable and therefore need replacing. We propose that a minimal set of compliant reference instruments can be used to verify the reliability of data from a much more extensive network of low-cost devices.

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) . This η is significantly lower than the η values for birnessite (η≈700 mV) and the active OER catalyst ß-Ni(OH)2 (η≈550 mV). Molecular dynamics simulations suggest that a competition among the interactions between the nickel cation, water, and birnessite promote redox chemistry in the spatially confined interlayer region.

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. Impedance spectroscopy results suggested that the charge transfer resistivity of the Cu-modified sample was significantly lower than Cu-free birnessite, suggesting that Cu in the interlayer increased the conductivity of birnessite leading to an enhancement of water oxidation kinetics. Density functional theory calculations show that the intercalation of Cu(0) into a layered MnO2 model structure led to a change of the electronic properties of the material from a semiconductor to a metallic-like structure. This conclusion from computation is in general agreement with the aforementioned impedance spectroscopy results. X-ray photoelectron spectroscopy (XPS) showed that Cu(0) coexisted with Cu(2+) in the prepared Cu-modified birnessite. Control experiments using birnessite that was decorated with only Cu(2+) showed a reduction in water oxidation kinetics, further emphasizing the importance of Cu(0) for the increased activity of birnessite. The introduction of Cu(0) into the birnessite structure also increased the stability of the electrocatalyst. At a working current of 2 mA, the Cu-modified birnessite took ∼3 times longer for the overpotential for water oxdiation to increase by 100 mV compared to when Cu was not present in the birnessite.

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. PNC, wind speed and direction were measured for sixty minutes at eighty locations during a two-week sampling campaign. We conducted continuous monitoring at four additional locations to assess temporal variation. LUR modeling utilized 135 potential geographic predictors including: road length, vehicle density, restaurant density, population density, land use and others. A novel approach incorporated meteorological data through wind roses as alternates to traditional circular buffers. The range of measured (sixty-minute median) PNC across locations varied seventy-fold (1500-105000 particles/cm(3), mean [SD] = 18200 [15900] particles/cm(3)). Correlations between PNC and concurrently measured two-week average NOX concentrations were 0.6-0.7. A PNC LUR model (R(2) = 0.48, leave-one-out cross validation R(2) = 0.32) including truck route length within 50 m, restaurant density within 200 m, and ln-distance to the port represents the first UFP LUR model in North America. Models incorporating wind roses did not explain more variability in measured PNC.

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-1 and peak to peak splitting of 3040 cm-1. The experimental results are compared to theoretical calculations with remarkable agreement. The theoretical analysis of the polarized absorption spectra shows evidence of a high degree of intermolecular charge transfer, which, along with Coulombic coupling, conspires to create the unprecedented DS for this family of dye molecules. The large polarization dependence of the electronic spectra is attributed to the unique twisted crystal structure, in which a substantial rotational displacement exists between neighboring chromophores within a π-stack. These results highlight the strong sensitivity of the Davydov splitting to intermolecular geometry in PDI systems.

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. Frustrated hydration structures are shown to have profound effects on ion-surface electron transfer through the enhancement of energy gap fluctuations beyond those expected from Marcus theory. These fluctuations are accompanied by a concomitant increase in the electron transfer rate in Marcus's normal regime. We demonstrate the generality of this phenomenon-enhancement of energy gap fluctuations due to frustration-by introducing a charge frustrated XY model, likening the hydration structure of confined cations to topological defects. Our findings shed light on recent experiments suggesting that water oxidation rates depend on the cation charge and Mn-oxidation state in these layered transition metal oxide materials.

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. Mn(ii- and iii)-enriched samples gave a 10-50 fold enhancement in turnover number.

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. Meteorological variables (precipitation, wind, and temperature), persistence, and co-pollutant data are shown to be useful PM predictors. If MLP approaches are adopted for PM forecasting, training methods that improve extreme value prediction are recommended.