Research Update: Distribution and stabilization of Pd catalysts in porous carbon-based supports by aggregation of pre-doped colloidal particles

Abstract

In this work, the synthesis of a stable supported Pd catalyst by aggregation of colloidal particles (CPs) of polyacrylonitrile (PAN) containing the noble metal is discussed. The metal is initially incorporated during the polymerization reaction (0.5 wt. %) and results to be well embedded inside the polymeric structure and anchored to the nitrogen atom of acrylonitrile. Moreover, aiming to provide free access towards the catalyst active sites, a KOH-activated heat treatment was performed on the PAN CP aggregates, thus creating pore sizes between 0.7 and 5 nm with surface area SBET = 1150 m2/g. After the harsh heat treatment, the amount of Pd remaining in the pyrolyzed polymer is 2.8 wt. %, as measured by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), which then corresponds to a total weight loss of 83% (assuming no loss of Pd). This result indicates a remarkable stability of Pd inside the polymer structure and that minimal Pd leaching can be expected during the catalyst use. X-ray absorption spectroscopic studies of pyrolyzed Pd-containing PAN and following extended X-ray absorption fine structure fitting showed no sign of bulk Pd(0), while a dominant proportion of Pd is present as dispersed Pd carbides. These results are consistent with the data obtained using X-ray absorption near edge structure. Finally, the catalyst was tested on a Suzuki coupling in the liquid phase and showed good activity, hence proving the accessibility of the active sites to reactants.