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.
Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of “ordered” catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. Here, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order–disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing process to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity.
more » « less- NSF-PAR ID:
- 10083744
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 116
- Issue:
- 6
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- p. 1974-1983
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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