Surface Segregation in CuNi Nanoparticle Catalysts During CO₂ Hydrogenation: The Role of CO in the Reactant Mixture

Surface segregation and restructuring in size-selected CuNi nanoparticles were investigated via near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at various temperatures in different gas environments. Particularly in focus were structural and morphological changes occurring under CO2 hydrogenation conditions in the presence of carbon monoxide (CO) in the reactant gas mixture. Nickel surface segregation was observed when only CO was present as adsorbate. The segregation trend is inverted in a reaction gas mixture consisting of CO2, H2, and CO, resulting in an increase of copper concentration on the surface. Density functional theory calculations attributed the inversion of the segregation trend to the formation of a stable intermediate on the nanocatalyst surface (CH3O) in the CO-containing reactant mixture, which modifies the nickel segregation energy, thus driving copper to the surface. The promoting role of CO for the synthesis of methanol was demonstrated by catalytic characterization measurements of silica-supported CuNi NPs in a fixed-bed reactor, revealing high methanol selectivity (over 85%) at moderate pressures (20 bar). The results underline the important role of intermediate reaction species in determining the surface composition of bimetallic nanocatalysts and help understand the effect of CO cofeed on the properties of CO2 hydrogenation catalysts

Structure of the mantle beneath the Alboran basin from magnetotelluric soundings

We present results of marine MT acquisition in the Alboran sea that also incorporates previously acquired land MT from southern Spain into our analysis. The marine data show complex MT response functions with strong distortion due to seafloor topography and the coastline, but inclusion of high resolution topography and bathymetry and a seismically defined sediment unit into a 3D inversion model has allowed us to image the structure in the underlying mantle. The resulting resistivity model is broadly consistent with a geodynamic scenario that includes subduction of an eastward trending plate beneath Gibraltar, which plunges nearly vertically beneath the Alboran. Our model contains three primary features of interest: a resistive body beneath the central Alboran, which extends to a depth of ~150 km. At this depth, the mantle resistivity decreases to values of ~100 Ohm-m, slightly higher than those seen in typical asthenosphere at the same depth. This transition suggests a change in slab properties with depth, perhaps reflecting a change in the nature of the seafloor subducted in the past. Two conductive features in our model suggest the presence of fluids released by the subducting slab or a small amount of partial melt in the upper mantle (or both). Of these, the one in the center of the Alboran basin, in the uppermost-mantle (20-30km depth) beneath Neogene volcanics and west of the termination of the Nekkor Fault, is consistent with geochemical models, which infer highly thinned lithosphere and shallow melting in order to explain the petrology of seafloor volcanics

Global dynamic topography observations reveal limited influence of large-scale mantle flow

Convective circulation of the Earth’s mantle maintains some fraction of surface topography that varies with space and time. Most predictive models show that this dynamic topography has peak amplitudes of about ±2 km, dominated by wavelengths of 104 km. Here, we test these models against our comprehensive observational database of 2,120 spot measurements of dynamic topography that were determined by analysing oceanic seismic surveys. These accurate measurements have typical peak amplitudes of ±1 km and wavelengths of approximately 103 km, and are combined with limited continental constraints to generate a global spherical harmonic model, the robustness of which has been carefully tested and benchmarked. Our power spectral analysis reveals significant discrepancies between observed and predicted dynamic topography. At longer wavelengths (such as 104 km), observed dynamic topography has peak amplitudes of about ±500 m. At shorter wavelengths (such as 103 km), significant dynamic topography is still observed. We show that these discrepancies can be explained if short-wavelength dynamic topography is generated by temperature-driven density anomalies within a sub-plate asthenospheric channel. Stratigraphic observations from adjacent continental margins show that these dynamic topographic signals evolve quickly with time. More rapid temporal and spatial changes in vertical displacement of the Earth’s surface have direct consequences for fields as diverse as mantle flow, oceanic circulation and long-term climate change.This research was supported by a BP-Cambridge collaboration. We are grateful to ION for permission to publish partial seismic reflection profiles shown in Fig. 2 from their IndiaSPAN and Greater BrasilSPAN data sets

How well would modern‐day oceanic property distributions be known with paleoceanographic‐like observations?

Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 31 (2016): 472–490, doi:10.1002/2015PA002917.Compilations of paleoceanographic observations for the deep sea now contain a few hundred points along the oceanic margins, mid-ocean ridges, and bathymetric highs, where seawater conditions are indirectly recorded in the chemistry of buried benthic foraminiferal shells. Here we design an idealized experiment to test our predictive ability to reconstruct modern-day seawater properties by considering paleoceanographic-like data. We attempt to reconstruct the known, modern-day global distributions by using a state estimation method that combines a kinematic tracer transport model with observations that have paleoceanographic characteristics. When a modern-like suite of observations (Θ, practical salinity, seawater δ18O, inline image, PO4, NO3, and O2) is used from the sparse paleolocations, the state estimate is consistent with the withheld data at all depths below 1500 m, suggesting that the observational sparsity can be overcome. Physical features, such as the interbasin gradients in deep inline image and the vertical structure of Atlantic inline image, are accurately reconstructed. The state estimation method extracts useful information from the pointwise observations to infer distributions at the largest oceanic scales (at least 10,000 km horizontally and 1500 m vertically) and outperforms a standard optimal interpolation technique even though neither dynamical constraints nor constraints from surface boundary fluxes are used. When the sparse observations are more realistically restricted to the paleoceanographic proxy observations of δ13C, δ18O, and Cd/Ca, however, the large-scale property distributions are no longer recovered coherently. At least three more water mass tracers are likely needed at the core sites in order to accurately reconstruct the large-scale property distributions of the Last Glacial Maximum.NSF Grant Numbers: 1124880, 11254222016-10-0