skip to main content

DOE PAGESDOE PAGES

Title: Subsurface catalysis-mediated selectivity of dehydrogenation reaction

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 C 3H 6 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:
Grant/Contract Number:
SC0014561
Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 8; Journal ID: ISSN 2375-2548
Publisher:
AAAS
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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1499915

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., 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. 2018. "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}
}

Works referenced in this record:

Preferential CO Oxidation in Hydrogen: Reactivity of Core?Shell Nanoparticles
journal, June 2010
  • Nilekar, Anand Udaykumar; Alayoglu, Selim; Eichhorn, Bryan
  • Journal of the American Chemical Society, Vol. 132, Issue 21, p. 7418-7428
  • DOI: 10.1021/ja101108w

Special points for Brillouin-zone integrations
journal, June 1976
  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters
journal, January 2007

Ru�Pt core�shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen
journal, March 2008
  • Alayoglu, Selim; Nilekar, Anand U.; Mavrikakis, Manos
  • Nature Materials, Vol. 7, Issue 4, p. 333-338
  • DOI: 10.1038/nmat2156

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
  • Henkelman, Graeme; Uberuaga, Blas P.; J�nsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability
journal, January 2007
  • Stamenkovic, V. R.; Fowler, B.; Mun, B. S.
  • Science, Vol. 315, Issue 5811, p. 493-497
  • DOI: 10.1126/science.1135941