Quantitative depth profiling of Ce 3+ in Pt/CeO 2 by in situ high-energy XPS in a hydrogen atmosphere

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Labour Market Prospects of Swiss Career Entrants after Completion of Vocational Education and Training

This study seeks to find the reasons for the rising risk of unemployment for people who have completed basic vocational education and training (VET) in Switzerland. We focus on the long-term structural shift on the demand side of the labour market and its consequences for new entrants? chances of employment in the labour force. A detailed analysis of the development of vacancies for such ?career entrants? in the time period 2001 to 2011 suggests that neither a growing occupational mismatch nor a general shift in the level of education to the disadvantage of workers with vocational education can be made responsible for the rising unemployment of labour market entrants. Instead, the available evidence indicates that a diminishing part of the vacancies suited for VET graduates remains open to entrants because of the increasing job requirements with regard to work experience and further education. Basic vocational education and training alone is increasingly less a guarantee for a smooth entry into the working world.

Atomistic Modeling of Effect of Mg on Oxygen Vacancy Diffusion in α-Alumina

Oxygen diffusion plays an important role in grain growth and densification during the sintering of alumina ceramics and governs high-temperature processes such as creep. The atomistic mechanism for oxygen diffusion in alumina is, however, still debated; atomistic calculations not being able to match experimentally determined activation energies for oxygen vacancy diffusion. These calculations are, however, usually performed for perfectly pure crystals, whereas virtually every experimental alumina sample contains a significant fraction of impurity/dopants ions. In this study, we use atomistic defect cluster and nudged elastic band (NEB) calculations to model the effect of Mg impurities/dopants on defect binding energies and migration barriers. We find that oxygen vacancies can form energetically favorable clusters with Mg, which reduces the number of mobile species and leads to an additional 1.5 eV energy barrier for the detachment of a single vacancy from Mg. The migration barriers of diffusive jumps change such that an enhanced concentration of oxygen vacancies is expected around Mg ions. Mg impurities were also found to cause destabilization of certain vacancy configurations as well as enhanced vacancy–vacancy interaction.

Occupational mobility chains and the role of job opportunities for upward, lateral and downward mobility in Switzerland

This paper addresses the rarely studied relationship between job vacancies and inter-firm upward, lateral, and downward status mobility in an occupationally segmented labor market, taking Switzerland as the example. To conceptualize mobility mechanisms in this type of labor market, we introduce the concept of “occupational mobility chains” and test its validity. This concept provides the backdrop for developing time-dependent measures of individual job opportunities based on Swiss Job Monitor data. We link these measures with career data taken from the Swiss Life History Study and employ event history analysis to test different propositions of the ways in which status mobility is contingent on the number and the status of vacant positions. Results support our assumption that in occupationally segmented labor markets vacant positions affect status mobility only to the degree that they are located within workers’ occupational mobility chains.

Qualifikationsnachfrage und Arbeitsmarkteintritt in der Schweiz: Arbeit im erlernten Beruf, Berufswechsel oder Arbeitslosigkeit

Berufsorientierte Bildungssysteme sind auf die Vermittlung von spezialisierten beruflichen Qualifikationen ausgelegt. Werden diese nach Abschluss einer beruflichen Grundbildung auf dem Arbeitsmarkt wenig nachgefragt, riskieren die Absolventen, die erworbenen berufsspezifischen Qualifikationen nicht verwerten zu können. Dies trifft nicht nur zu, wenn Arbeitsmarkteinsteiger arbeitslos werden, sondern auch, wenn sie den Beruf wechseln müssen. Für die drei verschiedenen Optionen des Arbeitsmarkteinstiegs – Arbeit im erlernten Beruf, Berufswechsel und Arbeitslosigkeit – wird erstens untersucht, welche Bedeutung das individuell passende und das fachfremde Stellenangebot hat. Zweitens wird analysiert, wie eine unterschiedlich ausgeprägte Nachfrage nach fachspezifischen Qualifikationen die Bedeutung ausbildungsbezogener und individueller Merkmale für den Berufseinstieg verändert. Die Schweiz mit ihrem berufsorientierten Bildungssystem und berufsfachlich segmentieren Arbeitsmarkt dient als empirische Referenz. Die multinominalen logistischen Regressionsmodelle basieren auf den Daten des Schweizer Jugendpanels PISA2000/TREE. Die Individualdaten von Lehrabgänger werden auf Berufsebene, zeitpunkt- und regionsspezifisch mit dem individuell passenden und fachfremden Stellenangebot verknüpft, das auf den Stelleninseratendaten des Stellenmarktmonitors Schweiz (SMM) beruht. Dank dieser Verknüpfung von Angebot und Nachfrage nach beruflichen Qualifikationen auf der Mikroebene kann zum ersten Mal die grundlegende Bedeutung der Personalnachfrage für den Berufseinstieg nachgewiesen werden.