Aiming at a comparison of microstructure and paramagnetic properties of mesoporous TiO(2) nanoparticle networks, we subjected entirely different TiO(2-x) precursor structures to vacuum annealing. The transformation of an amorphous TiO(2-x) gel--obtained by sol-gel processing of an ethylene glycol-modified titanium precursor--into a network of interconnected anatase nanocrystals was explored by means of X-ray diffraction, nitrogen sorption, and electron microscopy. Crystalline junctions between the particles emerge from temperature treatment. This process of particle network formation is different from that related to the vapor phase grown anatase nanocrystals where particle-particle interface formation is induced by contact with water. It was found that, after annealing up to 873 K and controlled sample purification in oxygen atmosphere, both types of samples exhibit high concentrations of particle-particle interfaces and comparable properties in terms of surface area, porosity, and microstructure. With electron paramagnetic resonance (EPR) we observed on nonstoichiometric TiO(2-x) networks an identical type of subsurface defect which is related to the presence of solid-solid interfaces.

The observable reaction rate of heterogeneously catalyzed reactions is known to be limited either by the intrinsic kinetics of the catalytic transformation or by the rate of pore and/or film diffusion. Here, we show that in gas generation reactions from liquid reactants, the nucleation of gas bubbles in the catalyst pore structure represents an additional important rate-limiting step. This is highlighted for the example of catalytic hydrogen release from the liquid organic hydrogen carrier compound perhydro-dibenzyltoluene. A nucleation-inhibited catalytic system produces only dissolved hydrogen with fast saturation of the fluid phase around the active site, while bubble formation enhances mass transfer by more than a factor of 50 in an oscillating reaction regime. Nucleation can be efficiently triggered not only by temperature changes and catalyst surface modification but also by a mechanical stimulus. Our work sheds new light on performance-limiting factors in reactions that are of highest relevance for the future green hydrogen economy.

Electric arc furnace dust (EAFD) is an important secondary resource for the zinc industry. The most common process for its recycling is the pyro-metallurgical treatment in the Waelz process. However, this process focuses on the recycling of the zinc, whereas the recovery of other metals from the EAFD—such as iron and other alloying elements—is neglected. An up-to-date version of reprocessing can involve multi-metal recycling by means of a metal bath containing carbon. The use of a liquid iron alloy requires a higher processing temperature, which enables the reduction and melting of iron oxides as well as other compounds occurring in the dust. Furthermore, the Zn yield is higher and the reduction kinetics are faster than in the Waelz process. This paper is only focused on the zinc reduction in such a metal bath. In order to determine the influence of the carbon content in the molten metal on the reduction rate, experiments were carried out on the reduction behavior of zinc oxide using a synthetic slag. This slag, with a basicity B2 = 1, was applied to an iron bath with varying carbon contents. (0.85%, 2.16%, 2.89%, and 4.15%) The decrease in the zinc oxide concentration was monitored, along with the reaction rates calculated from these data. It was found that the reaction rate increases with rising carbon content in the melt.

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