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:
-
[1];
[1];
[1];
[1];
[1];
[2];
[3];
[1]
- Tianjin University (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin (China)
- Univ. of Kansas, Lawrence, KS (United States)
- (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). Chemical Sciences, Geosciences, and 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. https://doi.org/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. https://doi.org/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.: 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 »
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Works referenced in this record:
Dry reforming of methane over Ni/La2O3 nanorod catalysts with stabilized Ni nanoparticles
journal, March 2017
- Li, Xinyu; Li, Di; Tian, Hao
- Applied Catalysis B: Environmental, Vol. 202
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
Bayesian Error Estimation in Density-Functional Theory
journal, November 2005
- Mortensen, J. J.; Kaasbjerg, K.; Frederiksen, S. L.
- Physical Review Letters, Vol. 95, Issue 21
A combined in situ time-resolved UV–Vis, Raman and high-energy resolution X-ray absorption spectroscopy study on the deactivation behavior of Pt and PtSn propane dehydrogenation catalysts under industrial reaction conditions
journal, December 2010
- Iglesias-Juez, Ana; Beale, Andrew M.; Maaijen, Karin
- Journal of Catalysis, Vol. 276, Issue 2
State of tin in Pt-Sn/Al2O3 reforming catalysts investigated by TPR and chemisorption
journal, November 1984
- Lieske, H.
- Journal of Catalysis, Vol. 90, Issue 1
PtNi Nanocrystals Supported on Hollow Carbon Spheres: Enhancing the Electrocatalytic Performance through High-Temperature Annealing and Electrochemical CO Stripping Treatments
journal, August 2017
- Zhang, Chunmei; Zhang, Ruizhong; Li, Xiaokun
- ACS Applied Materials & Interfaces, Vol. 9, Issue 35
A study of the core level electrons in iron and its three oxides by means of X-ray photoelectron spectroscopy
journal, May 1983
- Mills, P.; Sullivan, J. L.
- Journal of Physics D: Applied Physics, Vol. 16, Issue 5
Selectivity in Propene Dehydrogenation on Pt and Pt 3 Sn Surfaces from First Principles
journal, November 2013
- Nykänen, Lauri; Honkala, Karoliina
- ACS Catalysis, Vol. 3, Issue 12
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
The Nature of the Metal-Metal Bond in Bimetallic Surfaces
journal, August 1992
- Rodriguez, J. A.; Goodman, D. W.
- Science, Vol. 257, Issue 5072
How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry
journal, June 2012
- Armbrüster, Marc; Behrens, Malte; Cinquini, Fabrizio
- ChemCatChem, Vol. 4, Issue 8
Effect of Surface Composition on Electronic Structure, Stability, and Electrocatalytic Properties of Pt-Transition Metal Alloys: Pt-Skin versus Pt-Skeleton Surfaces
journal, July 2006
- Stamenkovic, Vojislav R.; Mun, Bongjin Simon; Mayrhofer, Karl J. J.
- Journal of the American Chemical Society, Vol. 128, Issue 27
Oscillation of Surface Structure and Reactivity of PtNi Bimetallic Catalysts with Redox Treatments at Variable Temperatures
journal, October 2011
- Mu, Rentao; Guo, Xiaoguang; Fu, Qiang
- The Journal of Physical Chemistry C, Vol. 115, Issue 42
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters
journal, January 2007
- Zhang, J.; Sasaki, K.; Sutter, E.
- Science, Vol. 315, Issue 5809, p. 220-222
Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials
journal, February 2008
- Yamashita, Toru; Hayes, Peter
- Applied Surface Science, Vol. 254, Issue 8
XAFS Characterization of Pt–Fe/zeolite Catalysts for Preferential Oxidation of CO in Hydrogen Fuel Gases
journal, October 2005
- Kotobuki, Masashi; Shido, Takafumi; Tada, Mizuki
- Catalysis Letters, Vol. 103, Issue 3-4
Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis
journal, June 2017
- Zhu, Wenshuai; Wu, Zili; Foo, Guo Shiou
- Nature Communications, Vol. 8, Issue 1
Dehydrogenation of propane over Pt-SBA-15: Effect of Pt particle size
journal, March 2008
- Santhosh Kumar, M.; Chen, De; Walmsley, John C.
- Catalysis Communications, Vol. 9, Issue 5
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes
journal, July 1997
- Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G.
- Journal of the American Chemical Society, Vol. 119, Issue 27
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
The Roles of Subsurface Carbon and Hydrogen in Palladium-Catalyzed Alkyne Hydrogenation
journal, April 2008
- Teschner, D.; Borsodi, J.; Wootsch, A.
- Science, Vol. 320, Issue 5872
Propane Dehydrogenation over Pt/TiO 2 –Al 2 O 3 Catalysts
journal, November 2014
- Jiang, Feng; Zeng, Liang; Li, Shuirong
- ACS Catalysis, Vol. 5, Issue 1
Mechanistic Study of Pt–Re/γ-Al 2 O 3 Catalyst Deactivation by Chemical Imaging of Carbonaceous Deposits Using Advanced X-ray Detection in Scanning Transmission Electron Microscopy
journal, December 2013
- Sanchez, Sergio I.; Moser, Mark D.; Bradley, Steven A.
- ACS Catalysis, Vol. 4, Issue 1
Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties
journal, May 2008
- Chen, Jingguang G.; Menning, Carl A.; Zellner, Michael B.
- Surface Science Reports, Vol. 63, Issue 5
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 111, Issue 15
Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals
journal, June 2004
- Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.
- The Journal of Chemical Physics, Vol. 120, Issue 21
Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis
journal, August 2017
- Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.
- Nano Letters, Vol. 17, Issue 9
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012
- Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas
- Physical Review B, Vol. 85, Issue 23
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Simultaneous Improvements in Performance and Durability of an Octahedral PtNi x /C Electrocatalyst for Next-Generation Fuel Cells by Continuous, Compressive, and Concave Pt Skin Layers
journal, June 2017
- Zhao, Xiao; Takao, Shinobu; Higashi, Kotaro
- ACS Catalysis, Vol. 7, Issue 7
Highly active Pt–Fe bicomponent catalysts for CO oxidation in the presence and absence of H 2
journal, January 2012
- Xu, Hong; Fu, Qiang; Yao, Yunxi
- Energy Environ. Sci., Vol. 5, Issue 4
On the role of Cs, Cl and subsurface O in promoting selectivity in Ag/-AlO catalysed oxidation of ethene to ethene epoxide
journal, October 2005
- Atkins, M.; Couves, J.; Hague, M.
- Journal of Catalysis, Vol. 235, Issue 1
Propane dehydrogenation over Pt–Cu bimetallic catalysts: the nature of coke deposition and the role of copper
journal, January 2014
- Han, Zhiping; Li, Shuirong; Jiang, Feng
- Nanoscale, Vol. 6, Issue 17
Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction
journal, April 2010
- Hansgen, Danielle A.; Vlachos, Dionisios G.; Chen, Jingguang G.
- Nature Chemistry, Vol. 2, Issue 6
Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation
journal, February 2011
- Mu, Rentao; Fu, Qiang; Xu, Hong
- Journal of the American Chemical Society, Vol. 133, Issue 6
Long time scale kinetic Monte Carlo simulations without lattice approximation and predefined event table
journal, December 2001
- Henkelman, Graeme; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 115, Issue 21
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts
journal, April 2010
- Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli
- Nature Chemistry, Vol. 2, Issue 6
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
Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters.
journal, April 2007
- Zhang, J.; Sasaki, K.; Sutter, E.
- ChemInform, Vol. 38, Issue 15
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
Works referencing / citing this record:
Microenvironment Engineering of Ruthenium Nanoparticles Incorporated into Silica Nanoreactors for Enhanced Hydrogenations
journal, August 2019
- Ren, Xiaomin; Guo, Miao; Li, He
- Angewandte Chemie, Vol. 131, Issue 41
Microenvironment Engineering of Ruthenium Nanoparticles Incorporated into Silica Nanoreactors for Enhanced Hydrogenations
journal, August 2019
- Ren, Xiaomin; Guo, Miao; Li, He
- Angewandte Chemie International Edition, Vol. 58, Issue 41
Perovskite-Derived Pt–Ni/Zn(Ni)TiO3/SiO2 Catalyst for Propane Dehydrogenation to Propene
journal, June 2019
- Liu, Yatian; Li, Yanyong; Ge, Meng
- Catalysis Letters, Vol. 149, Issue 9
Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors
journal, November 2019
- Zhao, Zhi-Jian; Liu, Sihang; Zha, Shenjun
- Nature Reviews Materials, Vol. 4, Issue 12
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