Understanding and\nPredicting the Reactivity and Selectivity\nfor Formic Acid Decomposition on Au Nanoparticles

Formic acid decomposition (FAD) plays a significant role\nin the\nhydrogen economy, particularly in fuel cell technology, where Au nanoparticles\n(NPs) are among the best heterogeneous catalysts. These Au NPs not\nonly offer high activity for H<sub>2</sub> production but also tightly\ncontrol the yield of CO, a byproduct from the side reaction. Theoretical\nstudies of activity and selectivity at the nanoscale presents great\nchallenges, especially when the selectivity of the side reaction is\nthe primary concern. In this work, we utilize the enhanced extended\nphenomenological kinetics (XPK) method to investigate the impact of\nparticle size on FAD over Au NPs. The simulation results provide a\ndetailed examination of how particle size influences the reaction\nkinetics. Based on the enhanced XPK simulation results, simple kinetic\nmodels using the “generalized coordination number (GCN)”\nas descriptors are proposed. These models allow for the fast prediction\nof activity and selectivity of FAD on Au NPs of varying sizes. The\nenhanced XPK method and the kinetic models for fast prediction offer\nvaluable insights into the size effects of metal NPs on catalytic\nactivity and, in particular, selectivity, which can be useful for\ndesigning high-performance NP catalysts.