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Title: Subsurface catalysis-mediated selectivity of dehydrogenation reaction

Abstract

Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C–C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C3H6 selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [1]; ORCiD logo [1]
  1. Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin (China)
  2. Univ. of Kansas, Lawrence, KS (United States)
  3. (Feng) [Univ. of Kansas, Lawrence, KS (United States)
Publication Date:
Research Org.:
Univ. of Kansas, Lawrence, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1499915
Grant/Contract Number:  
SC0014561
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 8; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, and Gong, Jinlong. Subsurface catalysis-mediated selectivity of dehydrogenation reaction. United States: N. p., 2018. Web. doi:10.1126/sciadv.aar5418.
Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, & Gong, Jinlong. Subsurface catalysis-mediated selectivity of dehydrogenation reaction. United States. doi:10.1126/sciadv.aar5418.
Cai, Weiting, Mu, Rentao, Zha, Shenjun, Sun, Guodong, Chen, Sai, Zhao, Zhi-Jian, Li, Hao, Tian, Hao, Tang, Yu, Tao, Franklin, Zeng, Liang, and Gong, Jinlong. Fri . "Subsurface catalysis-mediated selectivity of dehydrogenation reaction". United States. doi:10.1126/sciadv.aar5418. https://www.osti.gov/servlets/purl/1499915.
@article{osti_1499915,
title = {Subsurface catalysis-mediated selectivity of dehydrogenation reaction},
author = {Cai, Weiting and Mu, Rentao and Zha, Shenjun and Sun, Guodong and Chen, Sai and Zhao, Zhi-Jian and Li, Hao and Tian, Hao and Tang, Yu and Tao, Franklin and Zeng, Liang and Gong, Jinlong},
abstractNote = {Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C–C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C3H6 selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.},
doi = {10.1126/sciadv.aar5418},
journal = {Science Advances},
number = 8,
volume = 4,
place = {United States},
year = {2018},
month = {8}
}

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Figures / Tables:

Fig. 1. Fig. 1.: Structural characterization of the Pt and PtFe nanoparticle catalysts. TEM images of leached (A) PtFe@Pt/SiO2 and (B) PtFe@Pt/SBA-15 via same reduction treatment. The insets in (A) and (B) show the size distribution of PtFe@Pt/SiO2 and PtFe@Pt/SBA-15, respectively. (C) Concentration of Fe and Pt in acid solution as amore » function of leaching time. The values from the unreduced sample are included as a reference. (D) EDS line profiles of leached PtFe@Pt/SBA-15 (inset of the nanoparticle). a.u., arbitrary units. (E) XPS Fe2p peaks from unleached PtFe/SBA-15 and leached PtFe@Pt/SBA-15 catalysts after air exposure at room temperature. (F) XANES Fe K-edge structures from PtFe/SBA-15 and PtFe@Pt/SBA-15 catalysts after air exposure at roomtemperature. Standard Fe foil and Fe2O3 samples are included as references. NP, nanoparticle.« less

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