Alexander Wokaun’s research while affiliated with Paul Scherrer Institute and other places

The gas-phase reaction dynamics and kinetics in a laser induced plasma are very much dependent on the interactions of the evaporated target material and the background gas. For metal (M) and metal–oxygen (MO) species ablated in an Ar and O2 background, the expansion dynamics in O2 are similar to the expansion dynamics in Ar for M+ ions with an MO+ dissociation energy smaller than O2. This is different for metal ions with an MO+ dissociation energy larger than for O2. This study shows that the plume expansion in O2 differentiates itself from the expansion in Ar due to the formation of MO+ species. It also shows that at a high oxygen background pressure, the preferred kinetic energy range to form MO species as a result of chemical reactions in an expanding plasma, is up to 5 eV.

The quantitative analysis of gas mixtures with gas chromatography is based on the calibration with certified standards and the determination of a response relationship for each species by regression analysis. The conventional assumption of a constant amount-of-substance injected onto the column, the sample size, for all standards analyzed represents one of the largest sources of uncertainties in this analysis technique. For systems using time-based micro injectors, the sample size injected onto the column is determined by the opening time of a pneumatically actuated micro valve and therefore depends upon the gas velocity developed in the injector's microchannel. For this reason, the sample size is not necessarily constant for a given opening time, but strongly correlates - according to fluid mechanic theory - with the gas mixture's dynamic viscosity. Neglecting these sample size variations leads to errors in the analysis up to 30%, depending on the diversity of the standards' viscosities, especially in processes with strongly changing hydrogen contents. A mathematical correction exploiting the inverse proportionality of the sample size and the sample's dynamic viscosity normalizes the injection amounts and minimizes the influence of the sample variations on the calibration regression. The data analysis based on the corrected normalized calibration is no longer viscosity dependent and can be applied to gas mixtures of any composition.

The growth and crystallinity of oxide thin films using a physical vapour deposition technique like molecular beam epitaxy (MBE) or pulsed laser deposition (PLD) is influenced by the flux of materials, the kinetic energy of species, and the substrate temperature. PLD is generating on a short time scale (µs) a large flux of materials, species with large kinetic energies (few eV up to several 10 eV), and requires often higher growth temperatures as compared to oxide MBE. Here, we show as a proof of principle that epitaxial TiO2 thin films can be grown on LaAlO3 (001) at a much-reduced deposition temperature of 300 °C by applying a bias voltage with respect to a grounded substrate. The controlled manipulation of ion energies with an applied electric field can allow to bridge the gap in growth conditions between PLD and oxide MBE.

The solar water splitting process assisted by semiconductor photocatalysts attracts growing research interests worldwide for the production of hydrogen as a clean and sustainable energy carrier. Due to their optical and electrical properties several oxynitride materials show great promise for the fabrication of efficient photocatalysts for solar water splitting. This study reports a comparative investigation of particle- and thin films-based photocatalysts using three different oxynitride materials. The absolute comparison of the photoelectrochemical activities favors the particle-based electrodes due to the better absorption properties and larger electrochemical surface area. However, thin films surpass the particle-based photoelectrodes due to their more suitable morphological features that improve the separation and mobility of the photo-generated charge carriers. Our analysis identifies what specific insights into the properties of materials can be achieved with the two complementary approaches.

Photoelectrochemical solar water splitting is a promising approach to convert solar energy into sustainable hydrogen fuel using semiconductor electrodes. Due to their visible light absorption properties, oxynitrides have shown to be attractive photocatalysts for this application. In this study, the influence of the preparation method of CaNbO2N particles on their morphological and optical properties, and thereby their photoelectrochemical performance, is investigated. The best performing CaNbO2N photoanode is produced by ammonolysis of Nb enriched calcium niobium oxide. The enhanced photoactivity arises from an enlarged surface area and superior visible light absorption properties. The photoactivity of this photoanode was further enhanced by photodeposition of Co-Pi co-catalyst and by atomic layer deposition of an Al2O3 overlayer. A photocurrent density of 70 microA.cm-2 at 1.23 V vs RHE was achieved. The observed enhancement of the photoelectrochemical performance after Co-Pi/Al2O3 deposition is the combined effect of the improved kinetics of oxygen evolution due to the Co-Pi co-catalyst and the reduced surface recombination of the photogenerated carriers at the Al2O3 surface layer.

The size of the band gap and the energy position of the band edges make several oxynitride semiconductors promising candidates for efficient hydrogen and oxygen production under solar light illumination. The intense research efforts dedicated to oxynitride materials have unveiled the majority of their most important properties. However, two crucial aspects have received much less attention. One is the critical issue of the compositional/structural surface modifications occurring during operation and how these affect the photoelectrochemical performance. The second concerns the relation between the electrochemical response and the crystallographic surface orientation of the oxynitride semiconductor. These are indeed topics of fundamental importance since it is exactly at the surface where the visible light-driven electrochemical reaction takes place. In contrast to conventional powder samples, thin films represent the best model system for these investigations. This study reviews current state-of-the-art of oxynitride thin film fabrication and characterization before focusing on LaTiO2N selected as representative photocatalyst. We report the investigation of the initial physicochemical evolution of the surface. Then we show that, after stabilization, the absorbed photon-to-current conversion efficiency of epitaxial thin films can differ by about 50% for different crystallographic surface orientations and be up to 5 times larger than for polycrystalline samples.

The nitrogen substitution into the oxygen sites of several oxide materials leads to a reduction of the band gap to the visible light energy range, which makes these oxynitride semiconductors potential photocatalysts for efficient solar water splitting. Oxynitrides typically show a different crystal structure compare to the pristine oxide material. Since the band gap is correlated to both the chemical composition and the crystal structure, it is not trivial to distinguish what modifications of the electronic structure induced by the nitrogen substitution are related to compositional and/or structural effects. Here, X-ray emission and absorption spectroscopy is used to investigate the electronic structures of orthorhombic perovskite LaTiOxNy thin films in comparison with films of the pristine oxide LaTiOx with similar orthorhombic structure and cationic oxidation state. Experiment and theory show the expected upward shift in energy of the valence band maximum that reduces the band gap as a consequence of the nitrogen incorporation. But this study also shows that the conduction band minimum, typically considered almost unaffected by the nitrogen substitution, undergoes a significant downward shift in energy. For a rational design of oxynitride photocatalysts the observed changes of both the unoccupied and occupied electronic states have to be taken into account to justify the total band gap narrowing induced by the nitrogen incorporation.

The currently discussed alternative fuels for spark ignition engines are numerous. 50 different liquid fuel compounds were identified from literature. Using a thermodynamic engine model, which adapts the engine to the fuel and thereby determines the performance potential of a fuel candidate, the different fuel candidates are investigated in terms of efficiency, tank-to-wheel CO2 emissions, and volumetric fuel consumption. Additionally, the Particulate Matter Index (PMI) of each compound is calculated to estimate the soot emissions. Furthermore possible negative impacts on health and the environment are taken into account. Thereby, the only compound leading to a lower volumetric fuel consumption than gasoline is found to be anisole (8.0 l/100 km), at the cost of increased CO2 emissions (225 g/km) and Particulate Matter Index (PMI) levels (2.27 bar−1). Minimum of tank-to-wheel CO2 emissions are achieved by isopropanol (175 g/km), but at the expense of increasing volumetric fuel consumption (10.2 l/100 km). CO2 reduction potential of 2,2,3-trimethylbutane (180 g/km) is not as significant, in return the increase in volumetric fuel consumption (8.5 l/100 km) is less pronounced. tert-butanol and isopropanol results in minimum PMI values (0.04 bar−1), while tert-butanol shows a slightly worse performance than isopropanol, with a full load efficiency of 36.8% vs. 37.1 %, respectively. Although they contain oxygen, the levulinates are predicted to form a high amount of particulate matter.

The solar water splitting process assisted by semiconductor photocatalysts attracts growing research interests worldwide for the production of hydrogen as a clean and sustainable energy carrier. Due to their optical and electrical properties several oxynitride materials show great promise for the fabrication of efficient photocatalysts for solar water splitting. This study reports a comparative investigation of particle- and thin films-based photocatalysts using three different oxynitride materials. The absolute comparison of the photoelectrochemical activities favors the particle-based electrodes due to the better absorption properties and larger electrochemical surface area. However, thin films surpass the particle-based photoelectrodes due to their more suitable morphological features that improve the separation and mobility of the photo-generated charge carriers. Our analysis identifies what specific insights into the properties of materials can be achieved with the two complementary approaches.

Photoelectrochemical solar water splitting is a promising approach to convert solar energy into sustainable hydrogen fuel using semiconductor electrodes. Due to their visible light absorption properties, oxynitrides have shown to be attractive photocatalysts for this application. In this study, the influence of the preparation method of CaNbO2N particles on their morphological and optical properties, and thereby their photoelectrochemical performance, is investigated. The best performing CaNbO2N photoanode is produced by ammonolysis of Nb enriched calcium niobium oxide. The enhanced photoactivity arises from an enlarged surface area and superior visible light absorption properties. The photoactivity of this photoanode was further enhanced by photodeposition of Co-Pi co-catalyst and by atomic layer deposition of an Al2O3 overlayer. A photocurrent density of 70 µA.cm-2 at 1.23 V vs RHE was achieved. The observed enhancement of the photoelectrochemical performance after Co-Pi/Al2O3 deposition is the combined effect of the improved kinetics of oxygen evolution due to the Co-Pi co-catalyst and the reduced surface recombination of the photogenerated carriers at the Al2O3 surface layer.