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.
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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