Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes
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 Pt 3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminating Pt threefold sites hampers the adsorption/dissociation of molecular H 2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt 3Sn 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:
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[1]
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; [3]
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- Iowa State Univ., Ames, IA (United States). Dept. of Chemistry; Ames Lab., Ames, IA (United States)
- Ames Lab., Ames, IA (United States)
- Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
- Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering, Dept. of Chemistry
- ( [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering, Dept. of Chemistry
- Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Report Number(s):
- IS-J 9489
Journal ID: ISSN 0021-9517; PII: S0021951717303627
- Grant/Contract Number:
- AC02-07CH11358; SC0014561
- Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 356; Journal Issue: C; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Research Org:
- Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
- 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
- OSTI Identifier:
- 1408911
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.,
Web. doi:10.1016/j.jcat.2017.10.011.
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. doi:10.1016/j.jcat.2017.10.011.
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. 2017.
"Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes". United States.
doi:10.1016/j.jcat.2017.10.011.
@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 = {2017},
month = {11}
}