Influence of Surface Chemistry of Carbon Nanofibers on the Hydrodechlorination of Chloroform to Olefins

Functionalized carbon nanofibers (CNF) are fascinating materials to be used as supports in Pd-based catalysts for the treatment of waste chloroform (TCM) to produce light olefins through the catalytic hydrodechlorination (HDC). The CNF were functionalized by HNO3, HCl, and urea. Compared to the Pd supported on un-treated CNF, all the catalysts using functionalized CNF as support showed lower turnover frequency values with higher stability, owing to their smaller Pd nanoparticles (NPs). These smaller Pd NPs are formed due to the stronger metal–support interactions promoted by the higher concentration of surface groups on the functionalized catalysts. Since the smaller Pd NPs could hinder the hydrogenation of olefins to paraffins, the selectivity to olefins increased on the functionalized catalysts. Moreover, the N-doped CNF was successfully formed on the catalyst functionalized by urea. Since the nitrogen functional groups (pyridinic N and pyrrolic N) could provide much stronger metal–support interactions compared to the oxygen functional groups on the other catalysts, the catalyst functionalized by urea showed the smallest Pd NPs among the four catalysts, leading to the highest selectivity to light olefins.