A Pseudo-Two-Dimensional (P2D) Model for FeS2 Conversion Cathode Batteries

Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS2 - a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle-Fuller-Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. We provide the code as an open-source Python Battery Mathematical Modelling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials

Landscape, soil, lithology, climate and permafrost control on dissolved carbon, major and trace elements in the Ob River, Western Siberia

In order to foresee possible changes in the elementary composition of Arctic river waters, complex studies with extensive spatial coverage, including gradients in climate and landscape parameters, are needed. Here, we used the unique position of the Ob River, draining through the vast partially frozen peatlands of the western Siberia Lowland and encompassing a sizable gradient of climate, permafrost, vegetation, soils and Quaternary deposits, to assess a snap-shot (8–23 July 2016) concentration of all major and trace elements in the main stem (~3000 km transect from the Tom River confluence in the south to Salekhard in the north) and its 11 tributaries. During the studied period, corresponding to the end of the spring flood-summer baseflow, there was a systematic decrease, from the south to the north, of Dissolved Inorganic Carbon (DIC), Specific Conductivity, Ca and some labile trace elements (Mo, W and U). In contrast, Dissolved Organic Carbon (DOC), Fe, P, divalent metals (Mn, Ni, Cu, Co and Pb) and low mobile trace elements (Y, Nb, REEs, Ti, Zr, Hf and Th) sizably increased their concentration northward. The observed latitudinal pattern in element concentrations can be explained by progressive disconnection of groundwaters from the main river and its tributaries due to a northward increase in the permafrost coverage. A northward increase in bog versus forest coverage and an increase in DOC and Fe export enhanced the mobilization of insoluble, low mobile elements which were present in organo-ferric colloids (1 kDa—0.45 µm), as confirmed by an in-situ dialysis size fractionation procedure. The chemical composition of the sampled mainstream and tributaries demonstrated significant (p < 0.01) control of latitude of the sampling point; permafrost coverage; proportion of bogs, lakes and floodplain coverage and lacustrine and fluvio-glacial Quaternary deposits of the watershed. This impact was mostly pronounced on DOC, Fe, P, divalent metals (Mn, Co, Ni, Cu and Pb), Rb and low mobile lithogenic trace elements (Al, Ti, Cr, Y, Zr, Nb, REEs, Hf and Th). The pH and concentrations of soluble, highly mobile elements (DIC, SO4, Ca, Sr, Ba, Mo, Sb, W and U) positively correlated with the proportion of forest, loesses, eluvial, eolian, and fluvial Quaternary deposits on the watershed. Consistent with these correlations, a Principal Component Analysis demonstrated two main factors explaining the variability of major and trace element concentration in the Ob River main stem and tributaries. The DOC, Fe, divalent metals and trivalent and tetravalent trace elements were presumably controlled by a northward increase in permafrost, floodplain, bogs, lakes and lacustrine deposits on the watersheds. The DIC and labile alkaline-earth metals, oxyanions (Mo, Sb and W) and U were impacted by southward-dominating forest coverage, loesses and eluvial and fertile soils. Assuming that climate warming in the WSL will lead to a northward shift of the forest and permafrost boundaries, a “substituting space for time” approach predicts a future increase in the concentration of DIC and labile major and trace elements and a decrease of the transport of DOC and low soluble trace metals in the form of colloids in the main stem of the Ob River. Overall, seasonally-resolved transect studies of large riverine systems of western Siberia are needed to assess the hydrochemical response of this environmentally-important territory to on-going climate change

Pilot studies of the unique highland palsa mire in Western Sayan (Tuva Republic, Russian Federation)

In contrast to the well-studied West Siberian sector of frozen bogs in the Russian Arctic, the frozen mound bogs (so-called “palsas”) on the highlands of Southern Siberia have not yet been studied, but they are suspected to be even more sensitive to ongoing climate change. This article provides the pilot study on palsa mire Kara-Sug in the highland areas of Western Sayan mountain system, Tuva Republic. The study focuses on the current state of palsa mire and surrounding landscapes, providing wide range of ecological characteristics while describing ongoing transformations of natural landscapes under a changing climate. The study used a variety of field and laboratory methods: the integrated landscape-ecological approach, the study of peat deposits, geobotanical analysis, and modern analysis of the chemical composition of water, peat, and soils. The study shows that highland palsa mires are distinguished by their compactness and high variety of cryogenic landforms leading to high floristic and ecosystem diversity compared with lowland palsa mires. This information brings new insights and contributes to a better understanding of extrazonal highland palsa mires, which remain a “white spot” in the global environmental sciences

Mechanistic studies of a “Declick” reaction

A kinetic analysis of a “declick” reaction is described. Compound 1, previously reported to couple an amine and a thiol (i.e. “click”) under mild aqueous conditions to create 2, undergoes release of the unaltered coupling partners upon triggering with dithiothreitol (DTT). In the study reported herein various aniline derivatives possessing para-electron donating and withdrawing groups were used as the amines. UV/vis spectroscopy of the declick reaction shows time-dependent spectra lacking isosbestic points, implying a multi-step mechanism. Global data fitting using numerical integration of rate equations and singular value decomposition afforded the spectra and time-dependence of each species, as well as rate constants for each step. The kinetic analysis reveals a multi-step process with an intermediate where both thiols of DTT have added prior to expulsion of the aniline leaving group, followed by rearrangement to the final product. Hammett plots show a negative rho value on two of the steps, indicating positive charge building (i.e. reduction of a negative charge) in the step leading to the intermediate and its rate- determining breakdown. Overall, the kinetic study reported herein gives a complete mechanistic picture of the declick reaction.We gratefully acknowledge the support of the Welch Regents Chair (F-0046) to EVA, NSF CHE-1665037, The Center for Dynamics and Control of Materials supported by the NSF (DMR-1720595), and by The Welch Foundation grant F-1604 to KAJ.Center for Dynamics and Control of Material

Rare and endangered plants of specially protected areas of West Siberian boreal coniferous forests (inside Tomsk oblast)

The article deals with various types of specially protected territories participating in preservation of biological diversity of boreal coniferous forests of the West Siberian Plain. Data are presented on species diversity of certain territories of Tomsk oblast established in various landscape and geographical conditions and under various conditions including areas within the Great Vasyugan Mire and the outskirts of Tomsk. The article reviews species of dominant plant families of rivers and lakes of the Polto system in the basin of the Tym river; and the condition of certain species of Orchidaceae, Empetraceae, Cupressaceae, Tiliaceae and Lamiaceae in other parts of the Tomsk region. There is also some analysis of species along with description of sites where 6 plant species were discovered (Orchis militaris, Orchis fuchsii, Juniperus communis, Empetrum nigrum, Tilia cordata, Stachys silvatica) that are protected in the area of study

Rare and endangered plants of specially protected areas of West Siberian boreal coniferous forests (inside Tomsk oblast)

The article deals with various types of specially protected territories participating in preservation of biological diversity of boreal coniferous forests of the West Siberian Plain. Data are presented on species diversity of certain territories of Tomsk oblast established in various landscape and geographical conditions and under various conditions including areas within the Great Vasyugan Mire and the outskirts of Tomsk. The article reviews species of dominant plant families of rivers and lakes of the Polto system in the basin of the Tym river; and the condition of certain species of Orchidaceae, Empetraceae, Cupressaceae, Tiliaceae and Lamiaceae in other parts of the Tomsk region. There is also some analysis of species along with description of sites where 6 plant species were discovered (Orchis militaris, Orchis fuchsii, Juniperus communis, Empetrum nigrum, Tilia cordata, Stachys silvatica) that are protected in the area of study

Landscape, Soil, Lithology, Climate and Permafrost Control on Dissolved Carbon, Major and Trace Elements in the Ob River, Western Siberia

In order to foresee possible changes in the elementary composition of Arctic river waters, complex studies with extensive spatial coverage, including gradients in climate and landscape parameters, are needed. Here, we used the unique position of the Ob River, draining through the vast partially frozen peatlands of the western Siberia Lowland and encompassing a sizable gradient of climate, permafrost, vegetation, soils and Quaternary deposits, to assess a snap-shot (8–23 July 2016) concentration of all major and trace elements in the main stem (~3000 km transect from the Tom River confluence in the south to Salekhard in the north) and its 11 tributaries. During the studied period, corresponding to the end of the spring flood-summer baseflow, there was a systematic decrease, from the south to the north, of Dissolved Inorganic Carbon (DIC), Specific Conductivity, Ca and some labile trace elements (Mo, W and U). In contrast, Dissolved Organic Carbon (DOC), Fe, P, divalent metals (Mn, Ni, Cu, Co and Pb) and low mobile trace elements (Y, Nb, REEs, Ti, Zr, Hf and Th) sizably increased their concentration northward. The observed latitudinal pattern in element concentrations can be explained by progressive disconnection of groundwaters from the main river and its tributaries due to a northward increase in the permafrost coverage. A northward increase in bog versus forest coverage and an increase in DOC and Fe export enhanced the mobilization of insoluble, low mobile elements which were present in organo-ferric colloids (1 kDa—0.45 µm), as confirmed by an in-situ dialysis size fractionation procedure. The chemical composition of the sampled mainstream and tributaries demonstrated significant (p 4, Ca, Sr, Ba, Mo, Sb, W and U) positively correlated with the proportion of forest, loesses, eluvial, eolian, and fluvial Quaternary deposits on the watershed. Consistent with these correlations, a Principal Component Analysis demonstrated two main factors explaining the variability of major and trace element concentration in the Ob River main stem and tributaries. The DOC, Fe, divalent metals and trivalent and tetravalent trace elements were presumably controlled by a northward increase in permafrost, floodplain, bogs, lakes and lacustrine deposits on the watersheds. The DIC and labile alkaline-earth metals, oxyanions (Mo, Sb and W) and U were impacted by southward-dominating forest coverage, loesses and eluvial and fertile soils. Assuming that climate warming in the WSL will lead to a northward shift of the forest and permafrost boundaries, a “substituting space for time” approach predicts a future increase in the concentration of DIC and labile major and trace elements and a decrease of the transport of DOC and low soluble trace metals in the form of colloids in the main stem of the Ob River. Overall, seasonally-resolved transect studies of large riverine systems of western Siberia are needed to assess the hydrochemical response of this environmentally-important territory to on-going climate change

Recognition of Viologen Derivatives in Water by <i>N</i>‑Alkyl Ammonium Resorcinarene Chlorides

Three water-soluble <i>N</i>-alkyl ammonium resorcinarene chlorides decorated with terminal hydroxyl groups at the lower rims were synthesized and characterized. The receptors were decorated at the upper rim with either terminal hydroxyl, rigid cyclohexyl, or flexible benzyl groups. The binding affinities of these receptors toward three viologen derivatives, two of which possess an acetylmethyl group attached to one of the pyridine nitrogens, in water were investigated via ¹H NMR spectroscopy, fluorescence spectroscopy, and isothermal titration calorimetry (ITC). ITC quantification of the binding process gave association constants of up to 10³ M^–1. Analyses reveal a spontaneous binding process which are all exothermic and are both enthalpy and entropy driven