Hartmut Hieronymus

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

Although catalytic reductions, cross‐couplings, metathesis, and oxidation of CC double bonds are well established, the corresponding catalytic hydroxylations of CH bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, “greenest”, and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidations on various substrates, but these have never achieved an industrial‐scale, owing to a low space‐time‐yield and poor stability. This review illustrates recent advances in aerobic oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications. However, O2 also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale.

Ultrasound and microstructures--a promising combination?

Short diffusion paths and high specific interfacial areas in microstructured devices can increase mass transfer rates and thus accelerate multiphase reactions. This effect can be intensified by the application of ultrasound. Herein, we report on the design and testing of a novel versatile setup for a continuous ultrasound-supported multiphase process in microstructured devices on a preparative scale. The ultrasonic energy is introduced indirectly into the microstructured device through pressurized water as transfer medium. First, we monitored the influence of ultrasound on the slug flow of a liquid/liquid two-phase system in a channel with a high-speed camera. To quantify the influence of ultrasound, the hydrolysis of p-nitrophenyl acetate was utilized as a model reaction. Microstructured devices with varying channel diameter, shape, and material were applied with and without ultrasonication at flow rates in the mL min(-1) range. The continuous procedures were then compared and evaluated by performing a simplified life cycle assessment.

Explosion behaviour of the ‘non-flammable’ CFC substitute 1,1,1,2-tetrafluoroethane (R134a)

The explosion ranges of R134a/nitrogen/oxygen mixtures have been investigated at atmospheric pressure. The results of these full flammability tests at 20 °C and at 280 °C are presented in a triangular diagram. In addition, the influence of pressure on the flammability of R134a/air mixtures has also been studied. Under normal conditions, R134a is a non-flammable gas but exhibits an explosion range at higher oxygen percentages than those in air. At increased temperatures or pressures, R134a also has an explosion range in air, i.e. without any higher oxygen percentage. Using a detonation tube, the detonability of R134a/air mixture has been investigated for pressures between 8–20 bar and temperatures from room temperature to 200 °C. Stable detonations with detonation velocities of 1506–1535 m s−1 were initiated by incoming detonation waves. For an oxygen-enriched R134a/nitrogen/oxygen mixture at 10 bar, using a glowing wire as the ignition source a pressure-pilling effect was observed. In this experiment a pressure of more than 1200 bar was attained.