Ionic liquids (ILs) modification, following the concept of “solid catalyst with ionic liquid layer (SCILL)”, has been demonstrated to be an effective approach to improving both activity and stability of Pt-based catalysts for the oxygen reduction reaction. In this work, the SCILL concept has been applied to a trimetallic PtNiMo/C system, which has been documented recently to be significantly advantageous over the benchmark PtNi-based catalysts for oxygen reduction. To achieve this, two hydrophobic ILs ([BMIM][NTF2] and [MTBD][BETI]) were used to modify PtNiMo/C with four IL-loading amounts between 7 and 38 wt %. We found that the Pt mass activity (@0.9 V) could be improved by up to 50% with [BMIM][NTF2] and even 70% when [MTBD][BETI] is used. Exceeding a specific IL loading amount, however, leads to a mass transport related activity drop. Moreover, it is also disclosed that both ILs can effectively suppress the formation of nonreactive oxygenated species, while at the same time imposing little effect on the electrochemical active surface area. For a deeper understanding of the degradation mechanism of pristine and IL modified PtNiMo/C, we applied identical location transmission electron microscopy and in situ scanning flow cell coupled to inductively coupled plasma mass spectrometry techniques. It is disclosed that the presence of ILs has selectively accelerated the dissolution of Mo and eventually results in a more severe degradation of PtNiMo/C. This shows that future research needs to identify ILs that prevent the Mo dissolution to leverage the potential of the IL modification of PtNiMo catalysts.

A method for obtaining hierarchically structured porous carbons, employing 3D printing to control the structure down to the lower µm scale, is presented. To successfully 3D print a polymer precursor and transfer it to a highly stable and structurally conformal carbon material, stereolithography 3D printing and photoinduced copolymerization of pentaerythritol tetraacrylate and divinylbenzene are employed. Mechanically stable structures result and a resolution of ≈15 µm is demonstrated. This approach can be combined with liquid porogen templating to control the amount and size (up to ≈100 nm) of transport pores in the final carbonaceous material. Additional CO2 activation enables high surface area materials (up to 2200 m2 g‐1) that show the 3D printing controlled µm structure and nm sized transport pores. This unique flexibility holds promise for the identification of optimal carbonaceous structures for energy application, catalysis, and adsorption.

A new strategy affords “non‐nano” carbon materials as dehydrogenation catalysts that perform similarly to nanocarbons. Polymer‐based carbon precursors that combine a soft‐template approach with ion adsorption and catalytic graphitization are key to this synthesis strategy, thus offering control over macroscopic shape, texture, and crystallinity and resulting in a hybrid amorphous/graphitic carbon after pyrolysis. From this intermediate the active carbon catalyst is prepared by removing the amorphous parts of the hybrid carbon materials via selective oxidation. The oxidative dehydrogenation of ethanol was chosen as test reaction, which shows that fine‐tuning the synthesis of the new carbon catalysts allows to obtain a catalytic material with an attractive high selectivity (82 %) similar to a carbon nanotube reference, while achieving 10 times higher space–time yields at 330 °C. This new class of carbon materials is accessible via a technically scalable, reproducible synthetic pathway and exhibits spherical particles with diameters around 100 μm, allowing unproblematic handling similar to classic non‐nano catalysts.

A novel strategy for the immobilization of Wilkinson's catalyst on silica nanoparticles is presented, employing pyridyl linkers as anchoring groups. The coordination binding of the catalyst to the pyridyl linker via ligand exchange of the trans‐phosphine group is verified by 1 D and 2 D solid‐state NMR spectroscopy. Catalytic activities are monitored by GC employing the hydrogenation of styrene as model reaction, and the leaching properties as well as the robustness of the catalyst are investigated. The resulting immobilized catalyst shows high catalytic activity, which is within a factor of three comparable to the homogeneous catalyst, and excellent stability in leaching tests. Finally, it is efficient to produce hyperpolarization in solution by employing parahydrogen‐enriched hydrogen gas for hydrogenation.

The synthesis of a novel immobilized Wilkinson’s catalyst [SiO2∼PvPy-Wilk] is presented. The support material of this catalyst consists of silica particles that are modified with polymer brushes carrying pyridyl moieties that enable the coordination of Wilkinson’s catalyst. The synthesis of this catalyst is monitored by 1D and 2D multinuclear solid-state NMR techniques to confirm the success of the immobilization. The [SiO2∼PvPy-Wilk] catalyst is then tested in the hydrogenation of styrene, and its reusability is inspected showing that significant structural changes after several reaction cycles yield an activation of the catalyst. Finally, the catalyst is tested in PHIP experiments giving rise to about 200-fold enhancement of the signals of the hydrogenation product ethylbenzene.