Adsorption-Induced Liquid-to-Solid Phase Transition of Cu Clusters in Catalytic Dissociation of CO2.

Abstract

Sub-nanometer metal clusters widely existing in catalysts have a large ensemble of metastable isomers that can interconvert during catalytic reactions, exhibiting complex dynamical catalytic effects. In this work, we systematically investigate the temperature dependent structural dynamics of the Cu13 cluster in CO2 dissociation using ab initio molecular dynamics and the free energy calculation method. We find an abnormal entropic effect due to adsorption-induced liquid-to-solid phase transition of the cluster during the course of the elementary dissociation step at transition temperatures. In the dissociation product, the formation of a rigid Cu3O unit decreases the dynamical fluidity of the cluster and increases the melting temperature, causing a decrease in the entropy of the dissociation product. Our work demonstrates the nontrivial effects of surface adsorption on phase transition behaviors of dynamic clusters and offers a new perspective to dynamic catalysis.