Preparation and Catalytic Performance of Metal-Rich Pd Phosphides for the Solvent-Free Selective Hydrogenation of Chloronitrobenzene

Abstract

A facile synthesis method of palladium phosphide supported on the activated carbon was developed. The effects of Pd precursors for phosphatization, phosphatization temperature, and the ratio of hypophosphite/Pd on the generation of palladium phosphide were investigated, and a generation mechanism of the Pd3P crystal structure is proposed. The results demonstrate that only PdO, rather than Pd or PdCl2, can transform into Pd phosphide without damage to the activated carbon. The penetration of P into the Pd particle can dramatically improve the dispersion of Pd species particles on the activated carbon. The generation of Pd phosphide greatly depends on the phosphatization temperature and the ratio of hypophosphite/Pd. An intact Pd3P crystal structure was obtained when the ratio of hypophosphite/Pd reached 32 and the phosphatization temperature was above 400 °C. The Pd3P supported on the activated carbon exhibited superior catalytic performance in terms of the hydrogenation of halonitrobenzenes to haloanilines because it had few L acids and B acids sites and could not generate deficient-electron active hydrogen atoms as electrophiles.