Insightful understanding of the correlations of the microstructure and catalytic performances of Pd@chitosan membrane catalysts studied by positron annihilation spectroscopy

Abstract

In this study, the catalytic performances of palladium supported on chitosan (Pd@CS) membrane heterogeneous catalysts have been studied from the aspects of free volume by positron annihilation lifetime spectroscopy (PALS). The results showed that the variation in free volume hole size of the Pd@CS membrane catalyst was closely associated with microstructure evolutions, such as increase of Pd content, valence transition of Pd by reduction treatment, solvent swelling, physical aging during catalyst recycling, and so on. The PALS results showed that both the mean free volume hole size of the Pd⁰@CS membrane in the dry or swollen state (analyzed by the LT program) and its distribution (analyzed by the MELT program) are smaller than the molecule size of the reactants and products in the catalysis reaction. However, the results showed that the Pd⁰@CS membrane catalyst has excellent catalytic activity for the Heck coupling reaction of all the reactants with different molecule size. It was revealed that the molecule transport channels of the Pd⁰@CS membrane catalyst in the reaction at high temperature was through a number of instantaneously connected free volume holes rather than a single free volume hole. This hypothesis was powerfully supported by the catalytic activity assessment results of the CS layer sealed Pd⁰@CS membrane catalyst. Meanwhile, it was confirmed that the leaching of Pd⁰ nanoparticles of the reused Pd⁰@CS membrane catalyst during the recycling process was also through such instantaneously connected free volume holes.