Local Ordering of Molten Salts at NiO Crystal Interfaces Promotes High‐Index Faceting

Given the strong influence of surface structure on the reactivity of heterogeneous catalysts, understanding the mechanisms that control crystal morphology is an important component of designing catalytic materials with targeted shape and functionality. Herein, we employ density functional theory to examine the impact of growth media on NiO crystal faceting in line with experimental findings, showing that molten‐salt synthesis in alkali chlorides (KCl, LiCl, and NaCl) imposes shape selectivity on NiO particles. We find that the production of NiO octahedra is attributed to the dissociative adsorption of H(2)O, whereas the formation of trapezohedral particles is associated with the control of the growth kinetics exerted by ordered salt structures on high‐index facets. To our knowledge, this is the first observation that growth inhibition of metal‐oxide facets occurs by a localized ordering of molten salts at the crystal–solvent interface. These findings provide new molecular‐level insight on kinetics and thermodynamics of molten‐salt synthesis as a predictive route to shape‐engineer metal‐oxide crystals.