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Title: Subsurface catalysis-mediated selectivity of dehydrogenation reaction

Journal Article · · Science Advances

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.

Research Organization:
Univ. of Kansas, Lawrence, KS (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0014561
OSTI ID:
1499915
Journal Information:
Science Advances, Journal Name: Science Advances Journal Issue: 8 Vol. 4; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English

References (53)

Bayesian Error Estimation in Density-Functional Theory journal November 2005
Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals journal June 2004
Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters journal January 2007
Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis journal August 2017
Special points for Brillouin-zone integrations journal June 1976
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
Bayesian Error Estimation in Density Functional Theory text January 2005
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
Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters. journal April 2007
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
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
Dehydrogenation of propane over Pt-SBA-15: Effect of Pt particle size journal March 2008
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
State of tin in Pt-Sn/Al2O3 reforming catalysts investigated by TPR and chemisorption journal November 1984
PtNi Nanocrystals Supported on Hollow Carbon Spheres: Enhancing the Electrocatalytic Performance through High-Temperature Annealing and Electrochemical CO Stripping Treatments journal August 2017
Dry reforming of methane over Ni/La2O3 nanorod catalysts with stabilized Ni nanoparticles journal March 2017
Preferential CO Oxidation in Hydrogen: Reactivity of Core−Shell Nanoparticles
  • Nilekar, Anand Udaykumar; Alayoglu, Selim; Eichhorn, Bryan
  • Journal of the American Chemical Society, Vol. 132, Issue 21, p. 7418-7428 https://doi.org/10.1021/ja101108w
journal June 2010
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
The Roles of Subsurface Carbon and Hydrogen in Palladium-Catalyzed Alkyne Hydrogenation journal April 2008
Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties journal May 2008
PtNi Nanocrystals Supported on Hollow Carbon Spheres: Enhancing the Electrocatalytic Performance through High-Temperature Annealing and Electrochemical CO Stripping Treatments journal August 2017
How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry journal June 2012
The Nature of the Metal-Metal Bond in Bimetallic Surfaces journal August 1992
Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability journal January 2007
Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis journal August 2017
Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation journal February 2011
A study of the core level electrons in iron and its three oxides by means of X-ray photoelectron spectroscopy journal May 1983
Propane dehydrogenation over Pt–Cu bimetallic catalysts: the nature of coke deposition and the role of copper journal January 2014
Synergetic Effect of Surface and Subsurface Ni Species at Pt−Ni Bimetallic Catalysts for CO Oxidation journal February 2011
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
XAFS Characterization of Pt–Fe/zeolite Catalysts for Preferential Oxidation of CO in Hydrogen Fuel Gases journal October 2005
Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen journal March 2008
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
The Nature of the Metal-Metal Bond in Bimetallic Surfaces journal August 1992
Propane Dehydrogenation over Pt/TiO 2 –Al 2 O 3 Catalysts journal November 2014
Oscillation of Surface Structure and Reactivity of PtNi Bimetallic Catalysts with Redox Treatments at Variable Temperatures journal October 2011
Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials journal February 2008
How to Control the Selectivity of Palladium-based Catalysts in Hydrogenation Reactions: The Role of Subsurface Chemistry journal June 2012
Selectivity in Propene Dehydrogenation on Pt and Pt 3 Sn Surfaces from First Principles journal November 2013
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts journal April 2010
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes journal July 1997
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation journal June 2012
Selectivity in Propene Dehydrogenation on Pt and Pt 3 Sn Surfaces from First Principles journal November 2013
Long time scale kinetic Monte Carlo simulations without lattice approximation and predefined event table journal December 2001
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction journal April 2010
Propane dehydrogenation over Pt–Cu bimetallic catalysts: the nature of coke deposition and the role of copper journal January 2014
Preferential CO Oxidation in Hydrogen: Reactivity of Core−Shell Nanoparticles
  • Nilekar, Anand Udaykumar; Alayoglu, Selim; Eichhorn, Bryan
  • Journal of the American Chemical Society, Vol. 132, Issue 21, p. 7418-7428 https://doi.org/10.1021/ja101108w
journal June 2010
Highly active Pt–Fe bicomponent catalysts for CO oxidation in the presence and absence of H 2 journal January 2012
Using first principles to predict bimetallic catalysts for the ammonia decomposition reaction journal April 2010
Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis journal June 2017

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