Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes

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

doi:10.1016/j.jcat.2017.10.011

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

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2017.10.011· OSTI ID:1408911

Pei, Yuchen ^[1]; Qi, Zhiyuan ^[1]; Goh, Tian Wei ^[1]; Wang, Lin-Lin ^[2]; Maligal-Ganesh, Raghu V. ^[1]; MacMurdo, Heather L. ^[3]; Zhang, Shiran ^[4]; Xiao, Chaoxian ^[3]; Li, Xinle ^[3]; (Feng) Tao, Franklin ^[4]; Johnson, Duane D. ^[5]; Huang, Wenyu ^[1]

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
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering

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.

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Research Organization:: Ames Lab., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-07CH11358; SC0014561

OSTI ID:: 1408911

Alternate ID(s):: OSTI ID: 1566204

Report Number(s):: IS-J 9489; PII: S0021951717303627

Journal Information:: Journal of Catalysis, Vol. 356, Issue C; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 41 works

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

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