Liquid-Phase Partial Hydrogenation of Phenylacetylene at Ambient Conditions Catalyzed by Pd-Fe-O Nanoparticles Supported on Silica.

Catalysts with no hazardous or toxic components are required for the selective hydrogenation of acetylenic bonds in the synthesis of pharmaceuticals, vitamins, nutraceuticals, and fragrances. The present work demonstrates that a high selectivity to alkene can be reached over a Pd-Fe-O/SiO2 system prepared by the co-impregnation of a silica support with a solution of the metal precursors (NH4)3[Fe(C2O4)3] and [Pd(NH3)4]Cl2 followed by thermal treatment in hydrogen or in air at 400 °C. A DRIFT spectroscopic study of CO adsorption revealed large shifts in the position of the Pdn+-CO bands for this system, indicating the strong effect of Fen+ on the Pd electronic state, resulting in a decreased rate of double C=C bond hydrogenation and an increased selectivity of alkyne hydrogenation to alkene. The prepared catalysts consisted of mono- and bimetallic nanoparticles on an SiO2 carrier and exhibited a selectivity as high as that of the commonly used Lindlar catalyst (which contains such hazardous components as lead and barium), while the activity of the Fe-Pd-O/SiO2 catalyst was an order of magnitude higher. The hydrogenation of a triple bond over the proposed Pd-Fe catalyst opens the way to selective hydrogenation over nontoxic catalysts with a high yield and productivity. Taking into account a simple procedure of catalyst preparation, this direction provides a rationale for the large-scale implementation of these catalysts.

Pd-Fe nanoparticles stabilized by chitosan derivatives for perchloroethene dechlorination.

A series of chitosan-stabilized Pd-NZVI (nano-zero-valent-iron) catalysts for dechlorination with variation in their composition and in the nature of the polymer has been prepared. The synthesis procedures and palladium and chitosan contents were optimized. It was demonstrated by the XPS method that Fe and Pd in Fe-Pd/chitosan samples exist in the metallic state. The positive shift of the binding energy as compared with the bulk metal shows that the iron metal in the surface layers exists as very small nanoparticles. The prepared materials were characterized also by the XAS method. The presence of O and N atoms in the first coordination shell of the central Fe atom in the Fe-Pd/chitosan samples certifies the binding of the Fe metal particles with the chitosan surface via OH and NH(2) groups. The samples are characterized by the high stability of the nanoparticles as compared to unstabilized Pd-NZVI. The materials were tested to evaluate their catalytic activity in the perchloroethene (PCE) dechlorination reaction. Some samples of chitosan-stabilized Pd-NZVI revealed a good performance in PCE degradation as compared to unstabilized Pd-NZVI.