In this study, a combination of the porous carbon (PCN), montmorillonite (MMT), and TiO2 was synthesized into a composite immobilized Pd metal catalyst (TiO2-MMT/PCN@Pd) with effective synergism improvements in catalytic performance. The successful TiO2-pillaring modification for MMT, derivation of carbon from the biopolymer of chitosan, and immobilization of Pd species for the prepared TiO2-MMT/PCN@Pd0 nanocomposites were confirmed using a combined characterization with X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption isotherms, high-resolution transition electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It was shown that the combination of PCN, MMT, and TiO2 as a composite support for the stabilization of the Pd catalysts could synergistically improve the adsorption and catalytic properties. The resultant TiO2-MMT80/PCN20@Pd0 showed a high surface area of 108.9 m2/g. Furthermore, it exhibited moderate to excellent activity (59-99% yield) and high stability (recyclable 19 times) in the liquid-solid catalytic reactions, such as the Sonogashira reactions of aryl halides (I, Br) with terminal alkynes in organic solutions. The positron annihilation lifetime spectroscopy (PALS) characterization sensitively detected the development of sub-nanoscale microdefects in the catalyst after long-term recycling service. This study provided direct evidence for the formation of some larger-sized microdefects during sequential recycling, which would act as leaching channels for loaded molecules, including active Pd species.
Keywords: Sonogashira reactions; heterogeneous catalysis; positron annihilation; structure–performance relations.