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Title: Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure

Abstract

Noble-metal nanocages with ultrathin (less than 2 nm) walls and well-defined facets have received great interest owing to their remarkable utilization efficiency of atoms and facet-dependent catalytic activities toward various reactions. Here, we report the synthesis of Ru-based octahedral nanocages covered by {111} facets, together with ultrathin walls in a face-centered cubic (fcc) structure rather than the hexagonal close-packed (hcp) of bulk Ru. The involvement of slow injection for the Ru(III) precursor, the introduction of KBr, and the use of elevated temperature were all instrumental to the formation of Pd@Ru core–shell octahedra with a conformal, uniform shell and a smooth surface. The {111} facets were well preserved during the selective removal of the Pd cores via wet etching, even when the Ru walls were only five atomic layers in thickness. Through in situ XRD, we demonstrated that the fcc structure of the Ru nanocages was stable up to 300 °C. We also used first-principles, self-consistent density functional theory calculations to study the adsorption and dissociation of N2 as a means to predict the catalytic performance toward ammonia synthesis. Our results suggested that the small proportions of Pd atoms left behind in the walls during etching could play a key rolemore » in stabilizing the adsorption of N2 as well as in reducing the activation energy barrier to N2 dissociation.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [4];  [1]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [6]
  1. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
  2. Department of Chemical and Biological Engineering, University of Wisconsin—Madison, Madison, Wisconsin 53706, United States
  3. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States; Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  4. The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta, Georgia 30332, United States
  5. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  6. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States; The Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology and Emory University, Atlanta, Georgia 30332, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1480061
DOE Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 21; Journal ID: ISSN 0897-4756
Country of Publication:
United States
Language:
English

Citation Formats

Zhao, Ming, Elnabawy, Ahmed O., Vara, Madeline, Xu, Lang, Hood, Zachary D., Yang, Xuan, Gilroy, Kyle D., Figueroa-Cosme, Legna, Chi, Miaofang, Mavrikakis, Manos, and Xia, Younan. Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b03092.
Zhao, Ming, Elnabawy, Ahmed O., Vara, Madeline, Xu, Lang, Hood, Zachary D., Yang, Xuan, Gilroy, Kyle D., Figueroa-Cosme, Legna, Chi, Miaofang, Mavrikakis, Manos, & Xia, Younan. Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure. United States. doi:10.1021/acs.chemmater.7b03092.
Zhao, Ming, Elnabawy, Ahmed O., Vara, Madeline, Xu, Lang, Hood, Zachary D., Yang, Xuan, Gilroy, Kyle D., Figueroa-Cosme, Legna, Chi, Miaofang, Mavrikakis, Manos, and Xia, Younan. Mon . "Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure". United States. doi:10.1021/acs.chemmater.7b03092.
@article{osti_1480061,
title = {Facile Synthesis of Ru-Based Octahedral Nanocages with Ultrathin Walls in a Face-Centered Cubic Structure},
author = {Zhao, Ming and Elnabawy, Ahmed O. and Vara, Madeline and Xu, Lang and Hood, Zachary D. and Yang, Xuan and Gilroy, Kyle D. and Figueroa-Cosme, Legna and Chi, Miaofang and Mavrikakis, Manos and Xia, Younan},
abstractNote = {Noble-metal nanocages with ultrathin (less than 2 nm) walls and well-defined facets have received great interest owing to their remarkable utilization efficiency of atoms and facet-dependent catalytic activities toward various reactions. Here, we report the synthesis of Ru-based octahedral nanocages covered by {111} facets, together with ultrathin walls in a face-centered cubic (fcc) structure rather than the hexagonal close-packed (hcp) of bulk Ru. The involvement of slow injection for the Ru(III) precursor, the introduction of KBr, and the use of elevated temperature were all instrumental to the formation of Pd@Ru core–shell octahedra with a conformal, uniform shell and a smooth surface. The {111} facets were well preserved during the selective removal of the Pd cores via wet etching, even when the Ru walls were only five atomic layers in thickness. Through in situ XRD, we demonstrated that the fcc structure of the Ru nanocages was stable up to 300 °C. We also used first-principles, self-consistent density functional theory calculations to study the adsorption and dissociation of N2 as a means to predict the catalytic performance toward ammonia synthesis. Our results suggested that the small proportions of Pd atoms left behind in the walls during etching could play a key role in stabilizing the adsorption of N2 as well as in reducing the activation energy barrier to N2 dissociation.},
doi = {10.1021/acs.chemmater.7b03092},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 21,
volume = 29,
place = {United States},
year = {2017},
month = {10}
}