Support Engineering for the Stabilisation of Heterogeneous Pd3 P-Based Catalysts for Heck Coupling Reactions.

Herein we report the use of a supported Pd3 P catalyst for Heck coupling reactions. For the stabilisation of Pd3 P and Pd, as reference system, the silica support material was modified via phosphorus doping (0.5 and 1 wt % P). Through this so-called support engineering approach, the catalytic activity of Pd3 P was clearly enhanced. Whereas an iodobenzene conversion of 79 % was witnessed for Pd3 P@SiO2 in the coupling of styrene and iodobenzene in 1 h, 90 % conversion could be achieved using Pd3 P@1P-SiO2 . This improved catalytic activity probably stems from an electronic modulation of the support surface via the introduction of phosphorus. Simultaneously, the recyclability was boosted and the Pd3 P@1P-SiO2 catalyst has shown to maintain its catalytic activity over several recovery tests. Hereby, metal leaching could almost be suppressed completely to 3 % by the use of a P-modified silica support.

A Supported Palladium Phosphide Catalyst for the Wacker-Tsuji-Oxidation of Styrene.

The substitution of pure metal particles by metal phosphides in catalysis represents a promising opportunity to lower the required metal quantity in the context of a sustainable use of metal resources. Herein we show the synthesis of palladium phosphide, Pd3 P, supported on silica, which is tested as catalyst for the Wacker-Tsuji-oxidation of styrene to acetophenone. The synthesized catalyst is characterized by PXRD, SEM-EDX, FTIR, ICP-AES and XPS measurements. Four different reaction systems are investigated in this study including different co-catalysts and reaction media. Conversions of styrene up to 95 % with a selectivity of 73 % towards acetophenone are observed using Pd3 P/SiO2 as catalyst, CuCl2 as co-catalyst and O2 as oxidant. An enhanced selectivity up to 100 % towards acetophenone is obtained in other reaction systems. The use of Pd3 P/SiO2 leads to an optimized selectivity and conversion in the oxidation reaction in comparison with the purely Pd-based system Pd/SiO2 . These results give an insight on how the incorporation of phosphorus has a great effect on the performance of heterogeneous catalysts.