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Title: Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters

The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Pt n (n=8-15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Pt n (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt 13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt 13 by a temperature increase up to 400 K leading to ethylidyne formation. As a result, control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.
Authors:
 [1] ;  [1] ;  [2] ; ORCiD logo [1] ;  [1] ;  [3] ;  [3]
  1. Technische Univ. Munchen, Garching (Germany)
  2. Air Force Research Lab., Elgin, FL (United States); Technische Univ. Munchen, Garching (Germany)
  3. Georgia Institute of Technology, Atlanta, GA (United States)
Publication Date:
Grant/Contract Number:
FG05-86ER45234
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Georgia Inst. of Technology, Atlanta, GA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical sciences; catalysis; materials science; physical chemistry
OSTI Identifier:
1242980

Crampton, Andrew S., Rötzer, Marian D., Ridge, Claron J., Schweinberger, Florian F., Heiz, Ueli, Yoon, Bokwon, and Landman, Uzi. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters. United States: N. p., Web. doi:10.1038/ncomms10389.
Crampton, Andrew S., Rötzer, Marian D., Ridge, Claron J., Schweinberger, Florian F., Heiz, Ueli, Yoon, Bokwon, & Landman, Uzi. Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters. United States. doi:10.1038/ncomms10389.
Crampton, Andrew S., Rötzer, Marian D., Ridge, Claron J., Schweinberger, Florian F., Heiz, Ueli, Yoon, Bokwon, and Landman, Uzi. 2016. "Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters". United States. doi:10.1038/ncomms10389. https://www.osti.gov/servlets/purl/1242980.
@article{osti_1242980,
title = {Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters},
author = {Crampton, Andrew S. and Rötzer, Marian D. and Ridge, Claron J. and Schweinberger, Florian F. and Heiz, Ueli and Yoon, Bokwon and Landman, Uzi},
abstractNote = {The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Ptn (n=8-15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to structure insensitivity found for larger particles. The onset of catalysed hydrogenation occurs for Ptn (n≥10) clusters at T>150 K, with maximum room temperature reactivity observed for Pt13. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt13 by a temperature increase up to 400 K leading to ethylidyne formation. As a result, control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.},
doi = {10.1038/ncomms10389},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {1}
}