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Title: Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes

Abstract

It is essential to bridge the structure-properties relationship of bimetallic catalysts for the rational design of heterogeneous catalysts. Different from random alloys, intermetallic compounds (IMCs) present atomically-ordered structures, which is advantageous for catalytic mechanism studies. Here, we used Pt-based intermetallic nanoparticles (iNPs), individually encapsulated in mesoporous silica shells, as catalysts for the hydrogenation of nitroarenes to functionalized anilines. With the capping-free nature and ordered atomic structure, PtSn iNPs show >99% selectivity to hydrogenate the nitro group of 3-nitrostyrene albeit with a lower activity, in contrast to Pt3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminating Pt threefold sites hampers the adsorption/dissociation of molecular H2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt3Sn and Pt surfaces are saturated by atomic H. Calculations using density functional theory (DFT) suggest a preferential adsorption of the nitro group on the intermetallic PtSn surface contributing to its high selectivity.

Authors:
 [1];  [1];  [1];  [2];  [1];  [3];  [4];  [3];  [3];  [5];  [6];  [1]
+ Show Author Affiliations
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; Ames Lab., Ames, IA (United States)
  2. Ames Lab., Ames, IA (United States)
  3. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  4. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering, Dept. of Chemistry
  5. ( [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering, Dept. of Chemistry
  6. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1408911
Alternate Identifier(s):
OSTI ID: 1566204
Report Number(s):
IS-J 9489
Journal ID: ISSN 0021-9517; PII: S0021951717303627
Grant/Contract Number:  
AC02-07CH11358; SC0014561
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 356; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; intermetallic compounds; platinum-tin alloy; 3-Nitrostyrene; threefold site; horiuti-polany mehanism; hydrogen dissociation

Citation Formats

Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Wang, Lin-Lin, Maligal-Ganesh, Raghu V., MacMurdo, Heather L., Zhang, Shiran, Xiao, Chaoxian, Li, Xinle, Feng) Tao, Franklin, Johnson, Duane D., and Huang, Wenyu. Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes. United States: N. p., 2017. Web. doi:10.1016/j.jcat.2017.10.011.
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Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Wang, Lin-Lin, Maligal-Ganesh, Raghu V., MacMurdo, Heather L., Zhang, Shiran, Xiao, Chaoxian, Li, Xinle, Feng) Tao, Franklin, Johnson, Duane D., & Huang, Wenyu. Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes. United States. https://doi.org/10.1016/j.jcat.2017.10.011
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Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Wang, Lin-Lin, Maligal-Ganesh, Raghu V., MacMurdo, Heather L., Zhang, Shiran, Xiao, Chaoxian, Li, Xinle, Feng) Tao, Franklin, Johnson, Duane D., and Huang, Wenyu. Tue . "Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes". United States. https://doi.org/10.1016/j.jcat.2017.10.011. https://www.osti.gov/servlets/purl/1408911.
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@article{osti_1408911,
title = {Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes},
author = {Pei, Yuchen and Qi, Zhiyuan and Goh, Tian Wei and Wang, Lin-Lin and Maligal-Ganesh, Raghu V. and MacMurdo, Heather L. and Zhang, Shiran and Xiao, Chaoxian and Li, Xinle and Feng) Tao, Franklin and Johnson, Duane D. and Huang, Wenyu},
abstractNote = {It is essential to bridge the structure-properties relationship of bimetallic catalysts for the rational design of heterogeneous catalysts. Different from random alloys, intermetallic compounds (IMCs) present atomically-ordered structures, which is advantageous for catalytic mechanism studies. Here, we used Pt-based intermetallic nanoparticles (iNPs), individually encapsulated in mesoporous silica shells, as catalysts for the hydrogenation of nitroarenes to functionalized anilines. With the capping-free nature and ordered atomic structure, PtSn iNPs show >99% selectivity to hydrogenate the nitro group of 3-nitrostyrene albeit with a lower activity, in contrast to Pt3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminating Pt threefold sites hampers the adsorption/dissociation of molecular H2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt3Sn and Pt surfaces are saturated by atomic H. Calculations using density functional theory (DFT) suggest a preferential adsorption of the nitro group on the intermetallic PtSn surface contributing to its high selectivity.},
doi = {10.1016/j.jcat.2017.10.011},
journal = {Journal of Catalysis},
number = C,
volume = 356,
place = {United States},
year = {Tue Nov 14 00:00:00 EST 2017},
month = {Tue Nov 14 00:00:00 EST 2017}
}
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    Hydrogen Diffusion Guided Design of Pt‐Based Alloys for Inhibition of Butadiene Over‐Hydrogenation
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    Intermetallic Pd 3 Pb nanocubes with high selectivity for the 4-electron oxygen reduction reaction pathway
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    Hydrogen Diffusion Guided Design of Pt‐Based Alloys for Inhibition of Butadiene Over‐Hydrogenation
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