DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

Do pigs form preferential associations?

This investigation examined whether pigs form long-term preferential associations or ‘friendships’ and factors that may influence the formation of these relationships. Thirty-three pigs from 16 litters were housed together from 4 weeks of age. At 10 weeks they were split into two groups of 16 and 17 pigs and each introduced into 3.05 m × 3.66 m observation pens (1st pen). At 17 weeks the two groups swapped pens (2nd pen). The lying patterns of each group were recorded over 3 weeks in both the 1st and 2nd pens. To identify dyads with preferential associations, association indices were calculated for each pair based on their lying patterns and analysed using SOCPROG1.3 and the permutation method [Whitehead, H., 1999. Programs for analysing social structure. SOCPROG 1.2, http://is.dal.cal/~whitelab/index.htm]. Dyads with high association indices for at least 2 out of 3 weeks in either pen, i.e. =0.10 (twice the mean), were classed as having preferential associations. Mantel tests were used to examine the relationship between the relative sex, weight, familiarity and relatedness of a dyad and their level of association and to examine consistency of associations between pens. The existence of preferential associations was identified in both groups, since the standard deviations for the observed half-weight association index means were significantly higher than for the randomly permuted half-weight association index means (P < 0.001). Of the 33 pigs observed, 32 formed preferential associations with one or more pigs in their group, resulting in 50 dyads. Only six dyads (12 pigs) formed preferential associations in both pens, suggesting that the remaining dyads either formed short-term associations only or were simply displaying a shared preference for the same lying location. Levels of association between pens showed no significant correlation. The relative sex, weight, familiarity and relatedness of dyad members also showed no significant correlation with their level of association. These findings suggest that unrelated pigs are capable of forming preferential associations. However, it is unclear whether such associations are widespread or important to pigs, since most dyads’ preferential associations were not consistent between pens.

The basis for the formation of stable metal clusters on an electrode surface

Metal nanoclusters can be produced cheaply and precisely in an electrochemical environment. Experimentally this method works in some systems, but not in others, and the unusual stability of the clusters has remained a mystery. We have simulated the deposition of the clusters using classical molecular dynamics and studied their stability by grand-canonical Monte Carlo simulations. We find that electrochemically stable clusters occur only in those cases where the two metals involved form stable alloys.

Transport in nanoscale systems: the microcanonical versus grand-canonical picture

We analyse a picture of transport in which two large but finite charged electrodes discharge across a nanoscale junction. We identify a functional whose minimization, within the space of all bound many-body wavefunctions, defines an instantaneous steady state. We also discuss factors that favour the onset of steady-state conduction in such systems, make a connection with the notion of entropy, and suggest a novel source of steady-state noise. Finally, we prove that the true many-body total current in this closed system is given exactly by the one-electron total current, obtained from time-dependent density-functional theory.