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.
Pei, Yuchen, et al. "Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes." Journal of Catalysis, vol. 356, no. C, Nov. 2017. https://doi.org/10.1016/j.jcat.2017.10.011
Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, et al., "Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes," Journal of Catalysis 356, no. C (2017), https://doi.org/10.1016/j.jcat.2017.10.011
@article{osti_1408911,
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 and others},
title = {Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes},
annote = {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},
url = {https://www.osti.gov/biblio/1408911},
journal = {Journal of Catalysis},
issn = {ISSN 0021-9517},
number = {C},
volume = {356},
place = {United States},
publisher = {Elsevier},
year = {2017},
month = {11}}