Chitosan modified Ti-PILC supported PdOx catalysts for coupling reactions of aryl halides with terminal alkynes

Biopolymer of chitosan (CS) and titanium pillared clays (Ti-PILCs) have been combined in a hybrid as advanced supports for immobilization of PdOx=0,1 species to prepare novel PdOx=0,1@Ti-PILC/CS nano-composite catalysts. The Ti-PILC materials showed high specific surface areas and abundant meso-porous structure with many irregular pore channels caused by collapses of layered structure of clay during Ti pillaring process. Both CS chains and sub-nano sized PdOx particles were successfully incorporated into the pore channels of Ti-PILC, resulting in a decrease in both the specific surface areas and uniform distribution of pore size. Besides conventional methods characterizations, the strong interactions between PdOx species and Ti-PILC/CS support were further evidenced with positron annihilation lifetime spectroscopy studies. The resultant PdOx@Ti-PILC/CS catalyst was highly active for the coupling reactions of aryl halides with phenyl acetylenes. It was recyclable and gave excellent yield up to 13 runs with low leaching of Pd species. •CS modified Ti-PILC is proven as an ideal support for PdOx nanoparticle catalysts.•CS chains and PdOx nanoparticle are well incorporated in pore channels of Ti-PILC.•The porous structure of the catalyst is studied by combined N2 adsorption and PALS.•The catalyst shows superior activity and stability in organic liquid phase reactions.