Engineering the crystal structure of Pt–M (M = transition metal) nanoalloys to chemically ordered ones has drawn increasing attention in oxygen reduction reaction (ORR) electrocatalysis due to their high resistance against M etching in acid. Although Pt–Ni alloy nanoparticles (NPs) have demonstrated respectable initial ORR activity in acid, their stability remains a big challenge due to the fast etching of Ni. In this work, sub‐6 nm monodisperse chemically ordered
In the context of metal particle catalysts, composition, shape, exposed facets, crystal structure, and atom distribution dictate activity. While techniques have been developed to control each of these parameters, there is no general method that allows one to optimize all parameters in the context of polyelemental systems. Herein, by combining a solid-state, Bi-influenced, high-index facet shape regulation strategy with thermal annealing, we achieve control over crystal structure and atom distribution on the exposed high-index facets, resulting in an unprecedentedly diverse library of chemically disordered and ordered multimetallic (Pt, Co, Ni, Cu, Fe, and Mn) tetrahexahedral (THH) nanoparticles. Density functional theory calculations show that surface Bi modification stabilizes the {210} high-index facets of the nanoparticles, regardless of their internal atomic ordering. Moreover, we find that the ordering transition temperatures for the nanoparticles are dependent on their composition, and, in the case of Pt3Fe1THH nanoparticles, increasing Ni substitution leads to an order-to-disorder transition at 900 °C. Finally, we have discovered that ordered intermetallic THH Pt1Co1nanocatalysts exhibit a catalytic performance superior to disordered THH Pt1Co1nanoparticles and commercial Pt/C catalysts toward methanol electrooxidation, highlighting the importance of crystal structure and atom distribution control on high-index facets in nanoscale catalysts.
more » « less- PAR ID:
- 10252212
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 118
- Issue:
- 26
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- Article No. e2105722118
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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