Size-controllable ultrafine palladium nanoparticles immobilized on calcined chitin microspheres as efficient and recyclable catalysts for hydrogenation

Abstract

In the present work, chitin microspheres were impregnated at different concentrations of palladium salt solution to generate the precursor-Pd²⁺/chitin, and then a series of size-controllable palladium nanocatalysts (Pd@chitin) were successfully constructed by calcining the composite microspheres. Transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) provided reliable evidence for well-dispersed and ultrafine palladium nanoparticles (Pd NPs) with mean diameters from about 1 to 3 nm. Chitin microspheres, as the supporting framework of these catalysts, played a significant role for stabilizing the highly dispersed Pd NPs based on their abundant functional groups and large surface areas. Moreover, the chitin matrix acted as a reductant for the precursor-Pd²⁺ during calcination, and the calcination process made Pd@chitin more stable. These Pd@chitin catalysts were further tested for the hydrogenations of styrene and benzaldehyde, and they displayed superior catalytic activities compared to commercial Pd/C and unsupported homogeneous Pd(OAc)₂ catalysts. Notably, the most active catalyst of 1.2 wt% Pd@chitin had a highly competitive turnover frequency (TOF) of 50 000 h⁻¹ in the hydrogenation of styrene, and the catalyst could be repeatedly used for more than 10 cycles with no decay of the catalytic activity, suggesting potential industrial applications.