Metal-Free Activation of Molecular Oxygen by 9-Fluorenone-Based Porous Organic Polymers for Selective Aerobic Oxidation.

Oxygen activation is a critical step in heterogeneous oxidative processes, particularly in catalytic, electrolytic, and pharmaceutical applications. Among the various catalysts available for photocatalytic O2 activation, homogeneous aryl ketones are at the forefront. To avoid the degradation and deactivation of aryl ketones, 9-fluorenone-based porous organic polymers were designed and regulated by doping them with co-monomers. The obtained heterogeneous photocatalyst showed good performance in O2 activation, and its performance was better than that of homogeneous 9-fluorenone. The obtained heterogeneous photocatalyst showed good reusability. We believe that the presented method and findings represent an important step toward designing catalysts tailored for specific tasks.

Hydrogenation of levulinic acid to γ-valerolactone over hydrophobic Ru@HCP catalysts.

This study introduces an efficient strategy for promoting the synthesis of γ-valerolactone (GVL) via levulinic acid (LA) hydrogenation. A series of hyper-crosslinked porous polymer (HCP) supported Ru catalysts with different monomers were prepared. The wettabilities were controlled by the surface functional groups. The hydrophobic catalysts showed much higher activity than the hydrophilic ones in the hydrogenation of LA to GVL, highly possible due to the substrate enrichment. Further insight showed that the reaction proceeded through the 4-HVA route. These results illustrated the importance of surface wettability in bio-based molecule upgrading, which is beneficial for catalyst design.

Switching Amine Oxidation from Imines to Nitriles by Carbon-Hydrogen Bond Activation via Strong Base Modified Strategy.

Precisely controlling the product selectivity from the complex reaction is always an attractive topic in the catalysis field. In this paper, the Ru/strong base junction formed by the redox strategy was demonstrated as an efficient catalyst to switch the selectivity in aerobic oxidation of benzylamines. The zirconia-supported ruthenium (Ru-ZrO2) catalyst could catalyze benzylamine oxidation coupling to imines; however, the potassium oxide strong base modified zirconia-supported ruthenium (Ru-K-ZrO2) catalyst could catalyze benzylamine oxidation dehydrogenation to nitriles. Insight into the mechanism showed that the base modified catalyst had excellent dehydrogenation ability which was assisted by the C-H bond activation and changed the reaction pathway. The strong base modified strategy may provide a new approach for controlling the performance of heterogeneous catalysts and product selectivity.