Metal oxides exposing high-index facets are potentially impactful in catalysis and adsorption processes owing to under-coordinated ions and polarities that alter their interfacial properties compared to low-index facets. Here, we report molten-salt syntheses of NiO particles exposing a variety of crystal facets. We show that for a given anion (nitrate or chloride), the alkali cation has a notable impact on the formation of crystals exposing {311}, {611}, {100}, and {111} faces. Based on a parametric analysis of synthesis conditions, we postulate that the crystallization mechanism is governed by the formation of growth units consisting of NiII complexes whose coordination numbers are determined by temperature and the selection of anion (associated to the coordination sphere) and alkali cation (associated with the outer coordination sphere). Notably, our findings reveal that high-index facets are particularly favored in chloride media and are stable under prolonged periods of catalysis and steaming.
Keywords: crystal growth; crystal habit; flux-mediated method; molten-salt route; nickel oxide.
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