The Catalytic Effect of Iron and Alkali and Alkaline Earth Metal Sulfates Loading Series on the Conversion of Cellulose-Derived Hydrochars and Chars.

The catalytic effect of minerals on biomass conversion was studied focusing on Fe as well as alkali and alkaline earth metals as the metallic inorganic elements typically present in minerals found in biomass. A mineral-free reference hydrochar and an analogous char material based on cellulose were systematically doped with sulfates of the different metallic inorganic elements in various amounts via impregnation, thereby excluding differences originating from the counterion and the carbon matrix. Thermogravimetric reactivity measurements were performed in diluted O2 and CO2, and the derivative thermogravimetry curves were fitted using the random pore model. This procedure enabled a quantification of the apparent activation energy decrease due to doping as well as the influence of doping on the carbon structural parameter. Fe sulfate was always among the most active minerals, and alkali metal sulfates were typically more active than alkaline earth metal sulfates. The only exception was the high activity of very small Ca sulfate loadings during gasification. A saturation behavior of the kinetic parameter upon increasing the mineral loading was observed. The Langmuir-type modeling of this dependence further revealed that catalytically influenced devolatilization results in a char with higher oxidation reactivity, whereas for gasification, thermal annealing dominates. The systematically derived parameters provide a comprehensive description of catalytic effects, taking into account the type of mineral, the applied loading, the used atmosphere, and the fuel morphology. The derived activation energies can be used to include catalytic effects into combustion models.

Scalable Synthesis of Multi-Metal Electrocatalyst Powders and Electrodes and their Application for Oxygen Evolution and Water Splitting.

Multi-metal electrocatalysts provide nearly unlimited catalytic possibilities arising from synergistic element interactions. We propose a polymer/metal precursor spraying technique that can easily be adapted to produce a large variety of compositional different multi-metal catalyst materials. To demonstrate this, 11 catalysts were synthesized, characterized, and investigated for the oxygen evolution reaction (OER). Further investigation of the most active OER catalyst, namely CoNiFeMoCr, revealed a polycrystalline structure, and operando Raman measurements indicate that multiple active sites are participating in the reaction. Moreover, Ni foam-supported CoNiFeMoCr electrodes were developed and applied for water splitting in flow-through electrolysis cells with electrolyte gaps and in zero-gap membrane electrode assembly (MEA) configurations. The proposed alkaline MEA-type electrolyzers reached up to 3 A cm-2 , and 24 h measurements demonstrated no loss of current density of 1 A cm-2 .