Nanoscale Hybrid Amorphous/Graphitic Carbon as Key Towards Next-Generation Carbon-Based Oxidative Dehydrogenation Catalysts.

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.

Increasing Accessible Active Site Density of Non-Precious Metal Oxygen Reduction Reaction Catalysts through Ionic Liquid Modification.

Non-precious metal catalysts show great promise to replace the state-of-the-art Pt-based catalysts for catalyzing the oxygen reduction reaction (ORR), while their catalytic activity still needs to be greatly improved before their broad-based application. Here, we report a facile approach to improving the performance of zeolitic imidazolate framework-derived carbon (ZDC) toward the ORR by incorporating a small amount of ionic liquid (IL). The IL would preferentially fill the micropores of ZDC and greatly enhance the utilization of the active sites within the micropores, which are initially not accessible due to insufficient surface wetting. It is also disclosed that the ORR activity in terms of kinetic current at 0.85 V depends on the loading amount of the IL, and the maximum activity is obtained at a mass ratio of IL to ZDC at 1.2. The optimum stems from the counterbalance between the enhanced utilization of the active sites within the micropores and the retarded diffusion of the reactants within the IL phase due to its high viscosity.

Porous graphite as stationary phase for the chromatographic separation of polymer additives - determination of adsorption capability by Raman spectroscopy and physisorption.

Additives are added to polymers in small concentration to achieve desired application properties widely used to tailor the properties. The rapid diversification of their molecular structures, with often only minute differences, necessitates the development of adequate chromatographic techniques. While modified silica so far is the workhorse as stationary phase we have probed the potential of porous graphitic carbon (HypercarbTM) for this purpose. The results show that the multitude of physicochemical interactions between analyte molecules and the graphitic surface enables separations of polyolefin stabilizers with unprecedented selectivity. To support the chromatographic results the adsorption capability of HypercarbTM for selected antioxidants and UV absorbers has been determined by Raman spectroscopy and argon physisorption measurements. The shift of the Graphite-band in the Raman spectra of HypercarbTM upon infusion with additives correlates with the changes in the Adsorption Potential Distributions. The results of argon physisorption measurements go hand in hand with the chronology of desorption of the additives in liquid chromatography experiments. The elution sequence can be explained by van der Waals or London forces, π-π-interactions and electron lone pair donor-acceptor interactions between the graphite surface and analyte functional groups.

Activated Carbon in the Third Dimension-3D Printing of a Tuned Porous Carbon.

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.

Effect of Ionic Liquid Modification on the ORR Performance and Degradation Mechanism of Trimetallic PtNiMo/C Catalysts.

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.