Band alignment of CoO(100)-water and CoO(111)-water interfaces accelerated by machine learning potentials

Cobalt monoxide (CoO) nanomaterials have drawn attention for their remarkable photocatalytic water splitting without an externally applied potential or co-catalyst. The success of overall water splitting is due to the appropriate band edge positions of the catalyst, which span the redox potentials of water splitting. Typically, CoO nanomaterials possess complex morphologies, which consist of multiple active surfaces. As a result, the precise roles of the surfaces in the overall water-splitting process remain to be elucidated. In this work, we have undertaken a thorough investigation into the band alignments at the CoO(100)-water and CoO(111)-water interfaces using ab initio molecular dynamics and machine learning accelerated molecular dynamics simulations. The results of band alignment reveal that CoO(100) supports both the Hydrogen Evolution Reaction (HER) and the oxygen evolution reaction, whereas CoO(111) only facilitates the HER. Moreover, the variance in band positions between CoO(100) and CoO(111) results in an intrinsic potential difference, facilitating the migration of electrons toward CoO(100), while holes accumulate on CoO(111). The separation of photoexcited carriers effectively promotes water splitting in CoO.