Visualizing atomic-scale redox dynamics in vanadium oxide-based catalysts

Surface redox processes involving oxygen atom exchange are fundamental in catalytic reactions mediated by metal oxides. These processes are often difficult to uncover due to changes in the surface stoichiometry and atomic arrangement. Here we employ high-resolution transmission electron microscopy to study vanadium oxide supported on titanium dioxide, which is of relevance as a catalyst in, e.g., nitrogen oxide emission abatement for environmental protection. The observations reveal a reversible transformation of the vanadium oxide surface between an ordered and disordered state, concomitant with a reversible change in the vanadium oxidation state, when alternating between oxidizing and reducing conditions. The transformation depends on the anatase titanium dioxide surface termination and the vanadium oxide layer thickness, suggesting that the properties of vanadium oxide are sensitive to the supporting oxide. These atomic-resolution observations offer a basis for rationalizing previous reports on shape-sensitive catalytic properties

Enskog Theory for Polydisperse Granular Mixtures II. Sonine Polynomial Approximation

The linear integral equations defining the Navier-Stokes (NS) transport coefficients for polydisperse granular mixtures of smooth inelastic hard disks or spheres are solved by using the leading terms in a Sonine polynomial expansion. Explicit expressions for all the NS transport coefficients are given in terms of the sizes, masses, compositions, density and restitution coefficients. In addition, the cooling rate is also evaluated to first order in the gradients. The results hold for arbitrary degree of inelasticity and are not limited to specific values of the parameters of the mixture. Finally, a detailed comparison between the derivation of the current theory and previous theories for mixtures is made, with attention paid to the implication of the various treatments employed to date.Comment: 26 pages, to be published in Phys. Rev.

Rate of Iceland Sea acidification from time series measurements

The Iceland Sea is one part of the Nordic Seas. Cold Arctic Water prevails there and the deep-water is an important source of North Atlantic Deep Water. We have evaluated time series observations of measured <i>p</i>CO<sub>2</sub> and total CO<sub>2</sub> concentration from discrete seawater samples during 1985–2008 for the surface and 1994–2008 for deep-water, and following changes in response to increasing atmospheric carbon dioxide. The surface pH in winter decreases at a rate of 0.0024 yr<sup>−1</sup>, which is 50% faster than average yearly rates at two subtropical time series stations, BATS and ESTOC. In the deep-water regime (>1500 m), the rate of pH decline is a quarter of that observed in surface waters. The surface seawater carbonate saturation states (Ω) are about 1.5 for aragonite and 2.5 for calcite, about half of levels found in subtropical surface waters. During 1985–2008, the degree of saturation (Ω) decreased at an average rate of 0.0072 yr<sup>−1</sup> for aragonite and 0.012 yr<sup>−1</sup> for calcite. The aragonite saturation horizon is currently at 1710 m and shoaling at 4 m yr<sup>−1</sup>. Based on this rate of shoaling and on the local hypsography, each year another 800 km<sup>2</sup> of seafloor becomes exposed to waters that have become undersaturated with respect to aragonite

Tracer diffusion in granular shear flows

Tracer diffusion in a granular gas in simple shear flow is analyzed. The analysis is made from a perturbation solution of the Boltzmann kinetic equation through first order in the gradient of the mole fraction of tracer particles. The reference state (zeroth-order approximation) corresponds to a Sonine solution of the Boltzmann equation, which holds for arbitrary values of the restitution coefficients. Due to the anisotropy induced in the system by the shear flow, the mass flux defines a diffusion tensor $D_{ij}$ instead of a scalar diffusion coefficient. The elements of this tensor are given in terms of the restitution coefficients and mass and size ratios. The dependence of the diffusion tensor on the parameters of the problem is illustrated in the three-dimensional case. The results show that the influence of dissipation on the elements $D_{ij}$ is in general quite important, even for moderate values of the restitution coefficients. In the case of self-diffusion (mechanically equivalent particles), the trends observed in recent molecular dynamics simulations are similar to those obtained here from the Boltzmann kinetic theory.Comment: 5 figure

Navier-Stokes transport coefficients of dd-dimensional granular binary mixtures at low density

The Navier-Stokes transport coefficients for binary mixtures of smooth inelastic hard disks or spheres under gravity are determined from the Boltzmann kinetic theory by application of the Chapman-Enskog method for states near the local homogeneous cooling state. It is shown that the Navier-Stokes transport coefficients are not affected by the presence of gravity. As in the elastic case, the transport coefficients of the mixture verify a set of coupled linear integral equations that are approximately solved by using the leading terms in a Sonine polynomial expansion. The results reported here extend previous calculations [V. Garz\'o and J. W. Dufty, Phys. Fluids {\bf 14}, 1476 (2002)] to an arbitrary number of dimensions. To check the accuracy of the Chapman-Enskog results, the inelastic Boltzmann equation is also numerically solved by means of the direct simulation Monte Carlo method to evaluate the diffusion and shear viscosity coefficients for hard disks. The comparison shows a good agreement over a wide range of values of the coefficients of restitution and the parameters of the mixture (masses and sizes).Comment: 6 figures, to be published in J. Stat. Phy

Diffusion of impurities in a granular gas

Diffusion of impurities in a granular gas undergoing homogeneous cooling state is studied. The results are obtained by solving the Boltzmann--Lorentz equation by means of the Chapman--Enskog method. In the first order in the density gradient of impurities, the diffusion coefficient $D$ is determined as the solution of a linear integral equation which is approximately solved by making an expansion in Sonine polynomials. In this paper, we evaluate $D$ up to the second order in the Sonine expansion and get explicit expressions for $D$ in terms of the restitution coefficients for the impurity--gas and gas--gas collisions as well as the ratios of mass and particle sizes. To check the reliability of the Sonine polynomial solution, analytical results are compared with those obtained from numerical solutions of the Boltzmann equation by means of the direct simulation Monte Carlo (DSMC) method. In the simulations, the diffusion coefficient is measured via the mean square displacement of impurities. The comparison between theory and simulation shows in general an excellent agreement, except for the cases in which the gas particles are much heavier and/or much larger than impurities. In theses cases, the second Sonine approximation to $D$ improves significantly the qualitative predictions made from the first Sonine approximation. A discussion on the convergence of the Sonine polynomial expansion is also carried out.Comment: 9 figures. to appear in Phys. Rev.

Influence of hydrodynamic processes on the fate of sedimentary organic matter on continental margins

Understanding the effects of hydrodynamic forcing on organic matter (OM) composition is important for assessment of organic carbon (OC) burial in marginal seas on regional and global scales. Here we examine the relationships between regional oceanographic conditions (bottom shear stress), and the physical characteristics (mineral surface area and grain size) and geochemical properties (OC content [OC%] and carbon isotope compositions [13C, 14C]) of a large suite of surface sediments from the Chinese marginal seas to assess the influence of hydrodynamic processes on the fate of OM on shallow continental shelves. Our results suggest that 14C content is primarily controlled by organo‐mineral interactions and hydrodynamically driven resuspension processes, highlighted by (i) positive correlations between 14C content and OC% (and surface area) and (ii) negative correlations between 14C content and grain size (and bottom shear stress). Hydrodynamic processes influence 14C content due to both OC aging during lateral transport and accompanying selective degradation of OM associated with sediment (re) mobilization, these effects being superimposed on the original 14C characteristics of carbon source. Our observations support the hypotheses of Blair and Aller (2012, https://doi.org/10.1146/annurev‐marine‐120709‐142717) and Leithold et al. (2016, https://doi.org/10.1016/j.earscirev.2015.10.011) that hydrodynamically driven sediment translocation results in greater OC 14C depletion in broad, shallow marginal seas common to passive margin settings than on active margins. On a global scale, this may influence the extent to which continental margins act as net carbon sources and sinks. Our findings thus suggest that hydrodynamic processes are important in shaping the nature, dynamics, and magnitude of OC export and burial in passive marginal seas

The chemistry and potential reactivity of the CO2-H2S charged injected waters at the basaltic CarbFix2 site, Iceland

Publisher's version (útgefin grein)The CarbFix2 project aims to capture and store the CO2 and H2S emissions from the Hellisheiði geothermal power plant in Iceland by underground mineral storage. The gas mixture is captured directly by its dissolution into water at elevated pressure. This fluid is then injected, along with effluent geothermal water, into subsurface basalts to mineralize the dissolved acid gases as carbonates and sulfides. Sampled effluent and gas-charged injection waters were analyzed and their mixing geochemically modeled using PHREEQC. Results suggest that carbonates, sulfides, and other secondary minerals would only precipitate after it has substantially reacted with the host basalt. Moreover, the fluid is undersaturated with respect to the most common primary and secondary minerals at the injection well outlet, suggesting that the risk of clogging fluid flow paths near the injection well is limited.This publication has been produced with support from Reykjavik Energy and the European Commission through the projects CarbFix (EC coordinated action 283148) and CO2-REACT (EC Project 317235).Peer Reviewe