Positron annihilation characteristics and catalytic performances of poly (vinyl alcohol) intercalated montmorillonite supported Pd0 nanoparticles composites

The microstructure of poly (vinyl alcohol)/ montmorillonite (PVA/MMT) matrices and Pd@PVA/MMT catalytic composite was characterized by positron annihilation spectroscopy (PAS) and other techniques, such as high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), and X-ray photo electron spectroscopy (XPS). XRD and HR-TEM results showed that 20% was the saturation loading percentage of PVA intercalation into MMT. Ortho-positronium (o-Ps) annihilations were mainly distributed in the interlayer spacing of MMT and/or open spaces (free volume) of PVA. Below the saturation loading percentage of PVA (≤ 20%), it was found that the o-Ps annihilation lifetime became shorter after the intercalation of PVA chains into MMT layers. With further addition of PVA, the o-Ps annihilation lifetime became longer after the formation of exfoliated structure. The 20%-PVA/MMT matrix has been selected as the platform to further immobilize Pd specie for preparing novel 0.2%-Pd@20%-PVA/MMT catalytic composite. The effects of Pd immobilization on the microstructure of PVA/MMT matrices were also sensitively detected by PAS. The mean size of the micro-defects (from Tao-Eldrup model) increased from 0.28 nm (20%-PVA/MMT) to 0.29 nm (0.2%-Pd2+@20%-PVA/MMT or 0.2%-Pd0@20%-PVA/MMT), respectively. This increase in the size of the micro-defects of 20%-PVA/MMT matrix after Pd immobilization was mainly due to the replacement of the inter-molecular hydrogen bodings of PVA chains by the interactions formed between the PVA chains and Pd species. The prepared 0.2%-Pd0@20%-PVA/MMT catalytic composite showed excellent catalytic efficiency and recyclability in both Heck-type and Sonogashira-type coupling reactions. The correlations between the microstructure and performance of the 0.2%-Pd0@20%-PVA/MMT composite were thoroughly discussed.