Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles

Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO2 containing 1 MPa of H2 at 40–50 °C. Kinetic studies based on in situ UV/Vis spectra of the CO2 phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.