4.8 Article

Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk Energy

期刊

NANO LETTERS
卷 22, 期 9, 页码 3591-3597

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.1c05009

关键词

metal nanocrystal; crystal phase; metastable phase; structure-property relationship; polymorphism

资金

  1. NSF [CHE 2105602]
  2. Georgia Institute of Technology
  3. National Science Foundation [ECCS-2025462]
  4. U.S. Department of Energy (DOE), Office of Sciences [ERKCZ55]
  5. Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE, Office of Science User Facility at Oak Ridge National Laboratory

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The crystal phase of the deposited metal depends on the lateral size of the face-centered cubic (fcc)-Pd nanoplate templates, with smaller plates resulting in fcc-Ru and larger plates resulting in hexagonalclosed-packed (hcp)-Ru. The performance of Pd@fcc-Ru nanoplates is better than Pd@hcp-Ru nanoplates in oxidation reactions.
Despite the successful control of crystal phase using template-directed growth, much remains unknown about theunderlying mechanisms. Here, we demonstrate that the crystalphase taken by the deposited metal depends on the lateral size offace-centered cubic (fcc)-Pd nanoplate templates with 12 nmplates givingfcc-Ru while 18-26 nm plates result in hexagonalclosed-packed (hcp)-Ru. Although Ru overlayers with a metastablefcc- (high in bulk energy) or stablehcp-phase (low in bulk energy)can be epitaxially deposited on the basal planes, the latticemismatch will lead to jaggedhcp- (high in surface energy) andsmoothfcc-facets (low in surface energy), respectively, on the sidefaces. As the proportion of basal and side faces on the nanoplatesvaries with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. ThePd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions

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