Reversible Reaction of CO2 with Superbasic Ionic Liquid [P66614][benzim] Studied with in Situ Photoelectron Spectroscopy

Ionic liquids (ILs) are of significant interest as CO2 capture agents, and one subgroup of ILs that has shown particular promise is that of superbasic ILs. They can absorb large quantities of CO2 in the dry state, but some will have a diminished CO2 capacity when prewetted. In the work presented here, the superbasic IL trihexyl-tetradecylphosphonium benzimidazolide, or [P66614][benzim], was exposed to 3 mbar of CO2, 2 mbar of H2O vapor, and a CO2 + H2O gas mixture and was investigated using near-ambient pressure X-ray photoelectron spectroscopy. The results show that the IL reacts with CO2 to form carbamate and that the reaction is reversible through reduction of the surrounding gas pressure. Regardless of whether the IL was exposed to CO2 or H2O vapor first, the presence of H2O under these experimental conditions does not significantly hinder the IL’s ability to absorb and react with CO2. Furthermore, the IL appears to preferentially react with CO2 over H2O vapor

Structure and Reactivity of a Model Oxide Supported Silver Nanocluster Catalyst Studied by Near Ambient Pressure X-ray Photoelectron Spectroscopy

The photocatalytic activity of anatase TiO2 decorated with metal clusters has been widely documented, but the nature of the metal-metal oxide interface and reaction intermediates in catalytic processes are still not well understood. This in part is due to the fact that use of photoelectron spectroscopy to deduce the surface chemistry of catalytic systems has long been hampered by the huge pressure difference between real-world operation and the requirement of high vacuum for electron detection. Here, the in situ growth of silver nanoparticles on a model metal-oxide catalyst support and their reactivity with a CO/H2O gas mixture has been investigated in detail. Using synchrotron X-ray photoelectron spectroscopy, near-ambient pressure X-ray photoelectron spectroscopy and scanning tunneling microscopy, the interaction of Ag with the anatase TiO2 surface leads to metal-surface charge transfer and low mobility of Ag on the surface. Upon exposure to a 1.5 mbar CO/1.5 mbar H2O gas mixture, partial oxidation of the Ag clusters is observed. There is also evidence suggesting that a Ag-carbonyl species is formed during exposure of the Ag/TiO2 surface to a CO/H2O gas mixture

An Experimental Investigation of the Adsorption of a Phosphonic Acid on the Anatase TiO2(101) Surface

A combination of synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy has been used to study the adsorption of phenylphosphonic acid (PPA) on anatase TiO2(101) single crystal at coverages of 0.15 monolayer (ML) and 0.85 ML. The photoelectron spectroscopy data suggest that at 0.15 ML coverage PPA adsorbs in a bidentate geometry following deprotonation of both phosphonate hydroxyl groups, leaving the P═O group unbound. At 0.85 ML there is a shift to a mixed bidentate/monodentate binding mode. The carbon K-edge NEXAFS spectra were recorded at two azimuths. Our calculations show that for PPA on anatase TiO2(101) the phenyl ring is oriented 65 ± 4° away from the surface plane with an azimuthal twist of 57 ± 11° away from the [101] azimuth

Function Follows Form: From Semiconducting to Metallic toward Superconducting PbS Nanowires by Faceting the Crystal

In the realm of colloidal nanostructures, with its immense capacity for shape and dimensionality control, the form is undoubtedly a driving factor for the tunability of optical and electrical properties in semiconducting or metallic materials. However, influencing the fundamental properties is still challenging and requires sophisticated surface or dimensionality manipulation. In this work, we present such a modification for the example of colloidal lead sulphide nanowires. We show that the electrical properties of lead sulphide nanostructures can be altered from semiconducting to metallic with indications of superconductivity, by exploiting the flexibility of the colloidal synthesis to sculpt the crystal and to form different surface facets. A particular morphology of lead sulphide nanowires has been synthesized through the formation of {111} surface facets, which shows metallic and superconducting properties in contrast to other forms of this semiconducting crystal, which contain other surface facets ({100} and {110}). This effect, which has been investigated with several experimental and theoretical approaches, is attributed to the presence of lead rich {111} facets. The insights promote new strategies for tuning the properties of crystals as well as new applications for lead sulphide nanostructures.Comment: 23 pages, 6 figure

Elucidating the Defect-Induced Changes in the Photocatalytic Activity of TiO2TiO_{2}

The adsorption and subsequent photo-oxidation ofcarbon monoxide on the anatase TiO2(101) and rutile TiO2(110)single crystal surfaces was investigated using low temperature X-rayphotoelectron spectroscopy. Anatase was shown to significantlyoutperform rutile in terms of the rate of carbon dioxide yield onthe stoichiometric surface, and further to this, the presence ofdefects was shown to heavily influence the photocatalyticefficiency. The oxidation rate was reduced on anatase but increasedon rutile. This change is attributed to the location of defects withinthe crystal structure and is further discussed in this work. Thesefindings are of significant importance and demonstrate the possibilities of defect engineering in photocatalysis

Atomic scale step structure and orientation of a curved surface ZnO single crystal

We have investigated the surface structure of a curved ZnO-crystal, going from the (0001)-facet at 0° miscut to the (101¯4)-facet at a miscut of 24.8° using scanning tunneling microscopy and low energy electron diffraction. We find that the surface separates locally into (0001)-terraces and (101¯4)-facets, where the ratio between the facets depends on the miscut angle. In X-ray photoemission spectroscopy (XPS) the intensity of an O 1s component scaling with the step density of the surface is observed. No other facets were observed and the surface maintains a high degree of order over all angles. Such a curved ZnO crystal can be used for systematic studies relating the step density to the chemical reactivity using XPS to probe the curved surface at different positions

Effect of Cr on the hydrogen storage and electronic properties of BCC alloys: Experimental and first-principles study

Inventing an effective method to store large amounts of hydrogen at room temperature is one of the key challenges in developing a hydrogen-based economy. Metal hydrides have attracted attention owing to their promising hydrogen storage capabilities. We have systematically studied the structural and electronic properties of mechanically synthesized Ti$_{0.5}$V$_{1.5-x}$Cr$_x$ (0 ≤ x ≤ 0.3) alloys and investigated the influence of the addition of Cr atoms on the hydrogen storage properties of vanadium-rich body-centered-cubic (V-BCC) alloys. X-ray diffraction (XRD) results indicate that all alloys are composed of BCC main phase, with the lattice parameters exhibiting no change following chemical modification. The kinetic measurements have revealed that Cr-containing alloys exhibit improved hydrogen uptake. X-ray photoelectron spectroscopy (XPS) measurements have shown that the addition of Cr has a significant effect on the anti-oxidation properties of V-BCC alloys, increasing their chemical activity and thus enhancing the hydrogen storage properties. Moreover, XPS results elucidate the role of activation of the studied materials. Additionally, the electrochemical properties of the negative electrodes (as part of Ni-MH$_x$ secondary batteries) made of Ti$_{0.5}$V$_{1.4-x}$Ni$_{0.1}$Cr$_x$ (0 ≤ x ≤ 0.3) system have been studied by cyclic charge-discharge and demonstrate that doping of the V-BCC alloys with Cr can significantly improve the cycle-life stability of anode that exhibits similar discharge performance up to 50 cycles. First principles simulations are used to analyse the changes in the electronic density of states close to the Fermi level, as a function of Cr concentration, as well as binding energies and structural changes upon hydrogen absorption. Furthermore, ab initio studies confirmed that H absorption is favoured with increasing Cr-content. Our study highlights the importance of the addition of Cr to V-BCC alloys on both solid-gas and electrochemical hydrogenation reactions