Facet-Controlled Synthesis of Unconventional-Phase Metal Alloys for Highly Efficient Hydrogen Oxidation

Facet control and phase engineering of metal nanomaterials are both important strategies to regulate their physicochemical properties and improve their applications. However, it is still a challenge to tune the exposed facets of metal nanomaterials with unconventional crystal phases, hindering the exploration of the facet effects on their properties and functions. In this work, by using Pd nanoparticles with unconventional hexagonal close-packed (<i>hcp</i>, 2H type) phase, referred to as 2H-Pd, as seeds, a selective epitaxial growth method is developed to tune the predominant growth directions of secondary materials on 2H-Pd, forming Pd@NiRh nanoplates (NPLs) and nanorods (NRs) with 2H phase, referred to as 2H-Pd@2H-NiRh NPLs and NRs, respectively. The 2H-Pd@2H-NiRh NRs expose more (100)_h and (101)_h facets on the 2H-NiRh shells compared to the 2H-Pd@2H-NiRh NPLs. Impressively, when used as electrocatalysts toward hydrogen oxidation reaction (HOR), the 2H-Pd@2H-NiRh NRs show superior activity compared to the NiRh alloy with conventional face-centered cubic (<i>fcc</i>) phase (<i>fcc</i>-NiRh) and the 2H-Pd@2H-NiRh NPLs, revealing the crucial role of facet control in enhancing the catalytic performance of unconventional-phase metal nanomaterials. Density functional theory (DFT) calculations further unravel that the excellent HOR activity of 2H-Pd@2H-NiRh NRs can be attributed to the more exposed (100)_h and (101)_h facets on the 2H-NiRh shells, which possess high electron transfer efficiency, optimized H* binding energy, enhanced OH* binding energy, and a low energy barrier for the rate-determining step during the HOR process.