High‐Index NiO Particle Synthesis in Alkali Chloride Salts: Nonclassical Crystallization Pathways and Thermally‐Induced Surface Restructuring

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-06, Vol.20 (26), p.e2308166-n/a
• Main Authors: Susman, Mariano D., Pham, Hien N., West, David, Chinta, Sivadinarayana, Datye, Abhaya K., Rimer, Jeffrey D.
• Format: Article
• Language: English
• Subjects: Chlorides; Colloiding; Crystal growth; Crystal surfaces; Crystallization; Grain boundaries; high‐index facets; Material properties; melt synthesis; metal oxide; Metal oxides; molten salt route; Molten salts; Nickel oxides; Nucleation; polar surfaces; Synthesis; Thermal decomposition
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202308166

The formation mechanism(s) of high‐index facets in metal oxides is not widely understood but remains a topic of interest owing to the challenges of stabilizing high‐energy surfaces. These metal oxide crystal surfaces are expected to provide unique physicochemical characteristics; therefore, understanding crystallization pathways may enable the rational design of materials with controlled properties. Here the crystallization of NiO via thermal decomposition of a nickel source in excess of alkali chlorides is examined, focusing on KCl, which produces trapezohedral NiO (311) particles that are difficult to achieve through alternative methods. Trapezohedral NiO crystals are confirmed to grow via a molten eutectic where NiO nucleation is followed by nonclassical crystallization through processes resembling colloidal assembly. Aggregates comprised of NiO nanocrystals form mesostructures that ripen with heating time and exhibit fewer grain boundaries as they transition into single‐crystalline particles. At temperatures higher than those of NiO crystallization, there is a restructuring of (311) facets into microfacets exposing (111) and (100) surfaces. These findings illustrate the complex crystallization processes taking place during molten salt synthesis. The ability to generate metal oxide particles with high‐index facets has the potential to be a more generalized approach to unlock the physicochemical properties of materials for diverse applications. The synthesis of NiO in alkali halide molten salts occurs by a nonclassical mechanism involving colloidal assembly and ripening/densification from the exterior to the interior of the crystal. The (311) facets generated in KCl growth media undergo restructuring at temperatures much higher than those used to synthesize the metal oxide.