Origin of Electronic Modification of Platinum in a Pt3V Alloy and Its Consequences for Propane Dehydrogenation Catalysis

Stephen C. Purdy; Pushkar Ghanekar; Garrett Mitchell; A. Jeremy Kropf; Dmitry Y. Zemlyanov; Yang Ren; Fabio Ribeiro; W. Nicholas Delgass; Jeffrey Greeley; Jeffrey T. Miller

doi:10.1021/acsaem.9b01373

Origin of Electronic Modification of Platinum in a Pt₃V Alloy and Its Consequences for Propane Dehydrogenation Catalysis

Stephen C. Purdy, Pushkar Ghanekar, Garrett Mitchell, A. Jeremy Kropf, Dmitry Y. Zemlyanov, Yang Ren, Fabio Ribeiro, W. Nicholas Delgass, Jeffrey Greeley, Jeffrey T. Miller

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

We demonstrate the synthesis of a Pt₃V alloy and Pt/Pt₃V core/shell catalysts, which are highly selective for propane dehydrogenation. The selectivity is a result of the Pt₃V intermetallic phase, which was characterized by in situ synchrotron XRD and XAS. Formation of a continuous alloy surface layer 2-3 atomic layers thick was sufficient to obtain identical catalytic properties between a core-shell and full alloy catalyst, which demonstrates the length scale over which electronic effects pertinent to dehydrogenation act. Electronic characterization of the alloy phase was investigated by using DFT, XPS, XANES, and RIXS, all of which show a change in the energy of the filled and unfilled Pt 5d states resulting from Pt-V bonding. The electronic modification leads to a change in the most stable binding site of hydrocarbon fragments, which bind to V containing ensembles despite the presence of 3-fold Pt ensembles in Pt₃V. In addition, electronic modification destabilizes deeply dehydrogenated species thought to be responsible for hydrogenolysis and coke formation.

Original language	English
Pages (from-to)	1410-1422
Number of pages	13
Journal	ACS Applied Energy Materials
Volume	3
Issue number	2
DOIs	https://doi.org/10.1021/acsaem.9b01373
State	Published - Feb 24 2020
Externally published	Yes

Funding

This paper is based upon work supported in part by the National Science Foundation under Cooperative Agreement EEC-1647722. Use of the advanced photon source was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. MRCAT operations, beamline 10-BM and 10-ID, are supported by the Department of Energy and the MRCAT member institutions. The authors also acknowledge the use of the 11-ID-C beamline at the advanced photon source. XPS data were collected at the Surface Analysis Facility of the Birck Nanotechnology Center of Purdue University. Use of the Center for Nanoscale Materials (CNM), a U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences User Facility, Information Technology at Purdue (West Lafayette, IN), and computational resources from the National Energy Research Scientific Computing Center is gratefully acknowledged. This material is based upon work supported, in part, by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, & Biosciences (CSBG) division. The authors acknowledge Joseph Kubal, Brandon Bukowski, and Siddharth Deshpande for valuable discussions.

Funders	Funder number
CSBG
Center for Nanoscale Materials
Chemical Sciences, Geosciences, & Biosciences
National Science Foundation	1647722, EEC-1647722
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC02-06CH11357
National Energy Research Scientific Computing Center

Keywords

PtV nanoparticle
dehydrogenation selectivity
electronic effects in alloy catalysts
in situ X-ray absorption spectroscopy
in situ synchrotron X-ray diffraction
intermetallic alloy catalyst
propane dehydrogenation
resonant inelastic X-ray scattering

Access to Document

10.1021/acsaem.9b01373

Cite this

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title = "Origin of Electronic Modification of Platinum in a Pt3V Alloy and Its Consequences for Propane Dehydrogenation Catalysis",

abstract = "We demonstrate the synthesis of a Pt3V alloy and Pt/Pt3V core/shell catalysts, which are highly selective for propane dehydrogenation. The selectivity is a result of the Pt3V intermetallic phase, which was characterized by in situ synchrotron XRD and XAS. Formation of a continuous alloy surface layer 2-3 atomic layers thick was sufficient to obtain identical catalytic properties between a core-shell and full alloy catalyst, which demonstrates the length scale over which electronic effects pertinent to dehydrogenation act. Electronic characterization of the alloy phase was investigated by using DFT, XPS, XANES, and RIXS, all of which show a change in the energy of the filled and unfilled Pt 5d states resulting from Pt-V bonding. The electronic modification leads to a change in the most stable binding site of hydrocarbon fragments, which bind to V containing ensembles despite the presence of 3-fold Pt ensembles in Pt3V. In addition, electronic modification destabilizes deeply dehydrogenated species thought to be responsible for hydrogenolysis and coke formation.",

keywords = "PtV nanoparticle, dehydrogenation selectivity, electronic effects in alloy catalysts, in situ X-ray absorption spectroscopy, in situ synchrotron X-ray diffraction, intermetallic alloy catalyst, propane dehydrogenation, resonant inelastic X-ray scattering",

author = "Purdy, {Stephen C.} and Pushkar Ghanekar and Garrett Mitchell and Kropf, {A. Jeremy} and Zemlyanov, {Dmitry Y.} and Yang Ren and Fabio Ribeiro and Delgass, {W. Nicholas} and Jeffrey Greeley and Miller, {Jeffrey T.}",

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AU - Ghanekar, Pushkar

AU - Mitchell, Garrett

AU - Kropf, A. Jeremy

AU - Zemlyanov, Dmitry Y.

AU - Ren, Yang

AU - Ribeiro, Fabio

AU - Delgass, W. Nicholas

AU - Greeley, Jeffrey

AU - Miller, Jeffrey T.

PY - 2020/2/24

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N2 - We demonstrate the synthesis of a Pt3V alloy and Pt/Pt3V core/shell catalysts, which are highly selective for propane dehydrogenation. The selectivity is a result of the Pt3V intermetallic phase, which was characterized by in situ synchrotron XRD and XAS. Formation of a continuous alloy surface layer 2-3 atomic layers thick was sufficient to obtain identical catalytic properties between a core-shell and full alloy catalyst, which demonstrates the length scale over which electronic effects pertinent to dehydrogenation act. Electronic characterization of the alloy phase was investigated by using DFT, XPS, XANES, and RIXS, all of which show a change in the energy of the filled and unfilled Pt 5d states resulting from Pt-V bonding. The electronic modification leads to a change in the most stable binding site of hydrocarbon fragments, which bind to V containing ensembles despite the presence of 3-fold Pt ensembles in Pt3V. In addition, electronic modification destabilizes deeply dehydrogenated species thought to be responsible for hydrogenolysis and coke formation.

AB - We demonstrate the synthesis of a Pt3V alloy and Pt/Pt3V core/shell catalysts, which are highly selective for propane dehydrogenation. The selectivity is a result of the Pt3V intermetallic phase, which was characterized by in situ synchrotron XRD and XAS. Formation of a continuous alloy surface layer 2-3 atomic layers thick was sufficient to obtain identical catalytic properties between a core-shell and full alloy catalyst, which demonstrates the length scale over which electronic effects pertinent to dehydrogenation act. Electronic characterization of the alloy phase was investigated by using DFT, XPS, XANES, and RIXS, all of which show a change in the energy of the filled and unfilled Pt 5d states resulting from Pt-V bonding. The electronic modification leads to a change in the most stable binding site of hydrocarbon fragments, which bind to V containing ensembles despite the presence of 3-fold Pt ensembles in Pt3V. In addition, electronic modification destabilizes deeply dehydrogenated species thought to be responsible for hydrogenolysis and coke formation.

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