A Computational Study of HCOO Spillover on Cu@UiO-66

Spillover phenomena play a pivotal role in heterogeneous catalysis; however, the migration of the formate (HCOO) species remains scarcely investigated. Herein, we present a systematic density functional theory (DFT) study elucidating the distinct spillover patterns of HCOO on Cu surfaces and at the interface between Cu nanoclusters and the UiO-66 metal-organic framework. Our findings indicate that HCOO migration is generally facile at ambient conditions on the Cu surface, at the interfacial site, or between them, but it becomes kinetically difficult when steric hindrance and electronic repulsion of coadsorbed reactants are involved. The present work also includes exploration of H spillover patterns, all of which are found to be kinetically favorable on the Cu surface.