Synthesis and Reactivity of Iron(II) Complexes with a New Tripodal Imine Ligand

A new tripodal imine ligand tris(2-(propan-2-ylideneamino)ethyl)amine (imine₃tren) was prepared in order to stabilize high valent iron-oxido complexes. Iron complexes were synthesized in template reactions from iron(II) salts, tris(2-aminoethyl)amine (tren) and acetone. Due to the reversibility of the imine formation, complexes with different ligands were obtained depending on the reaction conditions. Three complexes, [Fe(imine₃tren)(OAc)₂] ( 1 ), [Fe(imine₃tren)(OAc)]OTf ( 2 ) and [(imine₃tren)₂Fe₂(F)₂](SbF₆)₂ ( 3 ), could be synthesized and structurally characterized. However, reactions with hydrogen peroxide, iodosobenzene or ozone did not lead to any kind of “oxygen adduct” complex that could be spectroscopically observed.     

Magnetic field enhancement of electrochemical hydrogen evolution reaction probed by magneto-optics

External magnetic fields affect various electrochemical processes and can be used to enhance the efficiency of the electrochemical water splitting reaction. However, the driving forces behind this effect are poorly understood due to the analytical challenges of the available interface-sensitive techniques. Here, we present a set-up based on magneto- and electro-optical probing, which allows to juxtapose the magnetic properties of the electrode with the electrochemical current densities in situ at various applied potentials and magnetic fields. On the example of an archetypal hydrogen evolution catalyst, Pt (in a form of Co/Pt superlattice), we provide evidence that a magnetic field acts on the electrochemical double layer affecting the local concentration gradient of hydroxide ions, which simultaneously affects the magneto-optical and magnetocurrent response.     

Research Platform: Decentralized Energy System for Sector Coupling

Industrial facilities usually need multiple energy subsystems, e.g., for heat, cold, and electric power supply. Normally, these energy subsystems are controlled locally and independent of each other. Coupling of the different subsystems can open up additional potential. Fraunhofer IISB has developed a demonstration and research platform for investigating the benefits of such sector coupling. A major precondition is to understand the energy flows in the system and establish an overall and flexible system control to realize the required algorithms for setting up an intelligent decentralized energy system. Major components of the overall system are various storages, which extend the degree of freedom for sector coupling and increase the effectiveness of the different subsystems.     

Application limits and sensitisation behaviour of the manganese- and nitrogen-alloyed austenitic stainless steel P2000 (X13CrMnMoN18-14-3)

Nickel-free high-nitrogen-alloyed stainless steels like the P2000 (X13CrMnMoN18-14-3) were developed to enhance the strength and corrosion resistance of austenitic stainless steels like 304 and 316 while keeping the typical high ductility. The mechanical and corrosive properties of P2000 were investigated and compared with 304 and 316 to highlight the application opportunities of this new alloy. The microstructure of the solution-annealed condition was characterised by electron backscatter diffraction and the mechanical properties were studied by uniaxial tensile tests, Charpy impact tests and hardness measurements. The passivation behaviour was analysed using the electrochemical potentiodynamic reactivation, whereas the pitting corrosion resistance was compared by pitting potentials and pitting temperatures. However, secondary thermal influences or suboptimal heat treatment can impair the corrosion resistance due to the precipitation of secondary phases and the resulting sensitisation. Thermodynamic calculations and artificial ageing treatment in the range of 500–900°C for up to 100 h were used to determine critical time–temperature parameters for sensitisation. The microstructure of the various aged states was evaluated by scanning electron microscopy and compared with the degrading corrosion resistance characterised by the KorroPad method.     

Gas Chromatographic Enantioseparation of Fluorinated Anesthetics: Single‐Column Performance and Scale‐up Estimation

Results of a study devoted to provide the pure enantiomers of isoflurane and desflurane from racemic mixtures using gas chromatography are presented. For that purpose, a cyclodextrin‐based selector described in earlier work was immobilized on porous glass beads. The adsorption isotherms were determined and applied to predict operating parameters which provide the highest possible productivity of the separation. The analysis included evaluation of the performance of larger columns applying simplifying scale‐up considerations. Using repetitive batches, the method can provide per day with a laboratory scale column approximately 1 g pure enantiomer. Selected model predictions were validated experimentally.     

Autonomous allocation of wireless body-sensor networks to frequency channels: modeling with repeated “balls-in-bins” experiments

Wireless Networks - In this paper we model a situation where several wireless body sensor networks (WBSN) compete for occupation of a number of frequency channels. Each channel can host at most one...     

Fiscal decentralization and regional disparities: The importance of good governance

In this paper we consider how government quality mediates the relationship between fiscal decentralization and regional disparities. Previous work has argued that fiscal decentralization has the potential to reduce income differences across regions but that this potential may not be realized because of governance problems associated with sub-national authorities. Our empirical evidence based on a sample of 24 OECD countries over the period 1984 to 2006 lends a measure of support to this idea. We find that fiscal decentralization promotes regional convergence in high government quality settings but, worryingly, it leads to wider regional disparities in countries with poor governance.     

Optical study of twin‐tanked ICS solar heaters combined with asymmetrical CPC‐type reflectors

The distribution of solar irradiance on the absorbing surface of a typical integrated collector storage (ICS) system combined with reflector troughs is commonly studied by means of ray tracing techniques. A conceptually different alternative is offered by the method of the average number of reflections (ANR). In the present work, the latter is employed for the systematic optical study of realistic ICS models. In all cases, the solar devices consist of twin cylindrical storage tanks which are mounted on top of stationary asymmetrical CPC‐type reflectors. The emphasis of the current research is mainly placed on the evaluation of the ANR reliability for the calculation of the optical efficiency of the related twin‐tanked devices. Additionally, useful operational parameters, such as the optical performance of the proposed geometries, are also determined. The behavior of the tested ICS systems reveals that the optical efficiency may vary in the range of 0.75 to 0.91, exhibiting a strong dependence on the geometric parameters of the solar devices. The highest efficiency is achieved by the systems which combine large reflecting area and storage tanks in close proximity.