Turnover Numbers and Soluble Metal Nanoparticles

Abstract The catalytic activity expressed by turnover number (TON) and turnover frequency (TOF) in different fields of catalysis (enzymatic, homogeneous (single‐site), heterogeneous (multi‐site), and nanocatalysis (oligo‐site)) are usually estimated in slightly different ways and with slightly different, yet important meanings. For soluble metal nanoparticles, the ideal is to determine the TON by using the titrated number of active catalytic sites before the catalyst is inactivated. However, in the absence of reliable titration methods it is suggested that TON figures should always be reported as the number of moles of reactants consumed per mol of soluble metal catalyst, and that they should also be corrected by the number of exposed surface atoms by using the metal atom’s magic number approach. Moreover, it is strongly recommended that the TOF should be determined from the slope of plots of turnover numbers versus time, because in various cases the size and shape of the soluble nanoparticles might change dramatically during the reaction. As in organometallic catalysis, in the absence of TON vs. time data, the TOF should be estimated for low substrate conversions.