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.

Aqueous Phase Reforming over Platinum Catalysts on Doped Carbon Supports: Exploring Platinum-Heteroatom Interactions.

A series of platinum catalysts supported on carbon nanofibers with various heteroatom dopings were synthesized to investigate the effect of the local platinum environment on the catalytic activity and selectivity in aqueous phase reforming (APR) of ethylene glycol (EG). Typical carbon dopants such as oxygen, nitrogen, sulfur, phosphorus, and boron were chosen based on their ability to bring acidic or basic functional groups to the carbon surface. In situ X-ray absorption spectroscopy (XAS) was used to identify the platinum oxidation state and platinum species formed during APR of EG through multivariate curve resolution alternating least-squares analysis, observing differences in activity, selectivity, and platinum local environment among the catalysts. The platinum-based catalyst on the nitrogen-doped carbon support demonstrated the most favorable properties for H2 production due to high Pt dispersion and basicity (H2 site time yield 22.7 h-1). Direct Pt-N-O coordination was identified by XAS in this catalyst. The sulfur-doped catalyst presented Pt-S contributions with the lowest EG conversion rate and minimal production of the gas phase components. Boron and phosphorus-doped catalysts showed moderate activity, which was affected by low platinum dispersion on the carbon support. The phosphorus-doped catalyst showed preferential selectivity to alcohols in the liquid phase, associated with the presence of acid sites and Pt-P contributions observed under APR conditions.

Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites.

Borocarbonitrides (BCNs) have emerged as highly selective catalysts for the oxidative dehydrogenation (ODH) reaction. However, there is a lack of in-depth understanding of the catalytic mechanism over BCN catalysts due to the complexity of the surface oxygen functional groups. Here, BCN nanotubes with multiple active sites are synthesized for oxygen-assisted methanol conversion reaction. The catalyst shows a notable activity improvement for methanol conversion (29%) with excellent selectivity to formaldehyde (54%). Kinetic measurements indicate that carboxylic acid groups on BCN are responsible for the formation of dimethyl ether, while the redox catalysis to formaldehyde occurs on both ketonic carbonyl and boron hydroxyl (B─OH) sites. The ODH reaction pathway on the B─OH site is further revealed by in situ infrared, x-ray absorption spectra, and density functional theory. The present work provides physical-chemical insights into the functional mechanism of BCN catalysts, paving the way for further development of the underexplored nonmetallic catalytic systems.