Cluster size dependent kinetics: analysis of different reaction mechanisms

Quantitative description for turnover frequency dependence on the metal cluster size is discussed for competitive Langmuir–Hinshelwood mechanism showing that the apparent reaction orders depend on the cluster size. Position of the maximum rate of the turnover frequency for a two-step sequence is a function on temperature and only in a special case, maximum of the turnover frequency is temperature independent on reaction temperature. For the same reaction mechanism the impact of internal diffusion limitations on structure sensitivity is discussed.