No abstract

Our contribution demonstrates that rhodium, an element that has barely been reported as an active metal for selective dehydrogenation of alkanes becomes a very active, selective, and robust dehydrogenation catalyst when exposed to propane in the form of single atoms at the interface of a solid-supported, highly dynamic liquid Ga–Rh mixture. We demonstrate that the transition to a fully liquid supported alloy droplet at Ga/Rh ratios above 80, results in a drastic increase in catalyst activity with high propylene selectivity. The combining results from catalytic studies, X-ray photoelectron spectroscopy, IR-spectroscopy under reaction conditions, microscopy, and density-functional theory calculations, we obtained a comprehensive microscopy picture of the working principle of the Ga–Rh supported catalytically active liquid metal solution.

Transpower New Zealand Limited has measured DC currents in transformer neutrals in the New Zealand electrical network at multiple South Island locations. Near‐continuous archived DC current data exist since 2001, starting with 12 different substations and expanding from 2009 to include 17 substations. From 2001 to 2015 up to 58 individual transformers were simultaneously monitored. Primarily, the measurements were intended to monitor the impact of the high‐voltage DC system linking the North and South Islands when it is operating in “Earth return” mode. However, after correcting for Earth return operation, as described here, the New Zealand measurements provide an unusually long and spatially detailed set of geomagnetically induced current (GIC) measurements. We examine the peak GIC magnitudes observed from these observations during two large geomagnetic storms on 6 November 2001 and 2 October 2013. Currents of ~30–50 A are observed, depending on the measurement location. There are large spatial variations in the GIC observations over comparatively small distances, which likely depend upon network layout and ground conductivity. We then go on to examine the GIC in transformers throughout the South Island during more than 151 h of geomagnetic storm conditions. We compare the GIC to the various magnitude and rate of change components of the magnetic field. Our results show that there is a strong correlation between the magnitude of the GIC and the rate of change of the horizontal magnetic field (H′). This correlation is particularly clear for transformers that show large GIC current during magnetic storms.

Highly monodisperse cobalt crystallites, supported on Stöber silica spheres, as model catalysts for the Fischer-Tropsch synthesis were exposed to simulated high conversion environments in the presence and absence of CO utilising an in house developed in situ magnetometer. The catalyst comprising the smallest crystallites in the metallic state (average diameter of 3.2 nm) experienced pronounced oxidation whilst the ratio of HO to H was increased stepwise to simulate CO conversions from 26% up to complete conversion. Direct exposure of this freshly reduced catalyst to a high conversion Fischer-Tropsch environment resulted in almost spontaneous oxidation of 40% of the metallic cobalt. In contrast, a model catalyst with cobalt crystallites of 5.3 nm only oxidised to a small extent even when exposed to a simulated conversion of over 99%. The largest cobalt crystallites were rather stable and only experienced measurable oxidation when subjected to HO in the absence of H. This size dependency of the stability is in qualitative accordance with reported thermodynamic calculations. However, the cobalt crystallites showed an unexpected low susceptibility to oxidation, i.e. only relatively high ratios of HO to H partial pressure caused oxidation. Similar experiments in the presence of CO revealed the significance of the actual Fischer-Tropsch synthesis on the metallic surface as the dissociation of CO, an elementary step in the Fischer-Tropsch mechanism, was shown to be a prerequisite for oxidation. Direct oxidation of cobalt to CoO by HO seems to be kinetically hindered. Thus, HO may only be capable of indirect oxidation, i.e. high concentrations prevent the removal of adsorbed oxygen species on the cobalt surface leading to oxidation. However, a spontaneous direct oxidation of cobalt at the interface between the support and the crystallites by HO forming presumably cobalt silicate type species was observed in the presence and absence of CO. The formation of these metal-support compounds is in accordance with conducted thermodynamic predictions. None of the extreme Fischer-Tropsch conditions initiated hydrothermal sintering. Seemingly, the formation of metal-support compounds stabilised the metallic crystallites and/or higher partial pressures of CO are required to increase the concentration of mobile, cobalt oxide-type species on the metallic surface.

Supported catalytically active liquid metal solutions (SCALMS) of Pt in Ga (2 at.-% Pt) were studied in the temperature range of 500 to 600 °C for propane dehydrogenation. A facile synthesis procedure using ultrasonication was implemented and compared to a previously reported organo-chemical route for gallium deposition. The procedure was applied to synthesize GaPt-SCALMS catalyst on silica (SiO 2 ), alumina (Al 2 O 3 ), and silicon carbide (SiC) to investigate the effect of the support material on the catalytic performance. The SiC-based SCALMS catalyst showed the highest activity, while SiO 2 -based SCALMS showed the highest stability and lowest cracking tendency at higher temperatures. The selectivity toward propene for the SiO 2 -based catalyst remained above 93% at 600 °C. The catalysts were analyzed for coke content after use by temperature-programmed oxidation (TPO) and Raman spectroscopy. While the SiC- and SiO 2 -supported SCALMS systems showed hardly any coke formation, the Al 2 O 3 -supported systems suffered from pronounced coking. SEM-EDX analyses of the catalysts before and after reaction indicated that no perceivable morphological changes occur during reaction. The SCALMS catalysts under investigation are compared with supported Pt and supported GaPt solid-phase catalyst, and possible deactivation pathways are discussed.