Nanocrystal Geometry Governs Phase Transformation Pathways in Palladium Hydride

Abstract

Pathways and structural dynamics of phase transformations impact performance of materials in energy and information storage technologies. Palladium hydride ($\mathrm{PdH}_x$) nanocrystals are an ideal model system for studying solute-induced phase transformations, where elastic energy from lattice mismatch between $\alpha$-$\mathrm{PdH}_x$ and $\beta$-$\mathrm{PdH}_x$ phases is often considered a key to determining the transformation pathways. $\alpha/\beta$-$\mathrm{PdH}_x$ interfacial elastic energy is affected by the confined geometry of a nanocrystal. However, how nanocrystal geometry influences phase transformation pathways is largely unknown. Using in situ liquid phase transmission electron microscopy, we directly visualize hydrogenation in Pd nanocrystals with two geometries -- a nanocube and a hexagonal nanoplate. Both follow similar sequences of an initially curved nucleus, interface flattening, and reverse-stage nucleation; however, their evolving $\alpha/\beta$-$\mathrm{PdH}_x$ interfaces exhibit geometry-dependent crystallographic alignments. In nanocubes, $\{100\}$-aligned configurations conform to static elastic energy ordering, representing a pathway that maintains a local mechanical equilibrium, whereas nanoplates display both $\{110\}$- and $\{211\}$-aligned interfaces. Theoretical simulations show that geometry determines the accessibility of alternative phase transformation pathways as the system is driven far from equilibrium during hydrogenation. These findings identify geometry as a fundamental parameter for directing phase transformation pathways, offering design principles for accessing atypical configurations and improving properties of intercalation-based devices.