Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species

Abstract

Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (PdnAu100–n), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ~ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified formore » the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. Finally, the implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [2];  [3];  [4];  [5];  [1]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. State Univ. of New York (SUNY), Binghamton, NY (United States)
  2. Army Research Lab., Adelphi, MD (United States)
  3. Central Michigan Univ., Mount Pleasant, MI (United States)
  4. Xiamen Univ. (China)
  5. Japan Advanced Institute of Science and Technology, Nomi, Ishikawa (Japan)
Publication Date:
Research Org.:
Central Michigan Univ., Mount Pleasant, MI (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of Education; National Science Foundation (NSF)
OSTI Identifier:
1610909
Alternate Identifier(s):
OSTI ID: 1482135
Grant/Contract Number:  
SC0006877; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 23; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; thermochemically-tuned nanoalloys; palladium-gold nanoparticles; support effect; in-situ DRIFTS probing; surface catalytic sites; intermediate species; propane oxidation

Citation Formats

Kareem, Haval, Shan, Shiyao, Wu, Zhi-Peng, Velasco, Leslie, Moseman, Kelli, O'Brien, Casey P., Tran, Dat T., Lee, Ivan C., Maswadeh, Yazan, Yang, Lefu, Mott, Derrick, Luo, Jin, Petkov, Valeri, and Zhong, Chuan-Jian. Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species. United States: N. p., 2018. Web. doi:10.1039/c8cy01704b.
Copy to clipboard
Kareem, Haval, Shan, Shiyao, Wu, Zhi-Peng, Velasco, Leslie, Moseman, Kelli, O'Brien, Casey P., Tran, Dat T., Lee, Ivan C., Maswadeh, Yazan, Yang, Lefu, Mott, Derrick, Luo, Jin, Petkov, Valeri, & Zhong, Chuan-Jian. Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species. United States. https://doi.org/10.1039/c8cy01704b
Copy to clipboard
Kareem, Haval, Shan, Shiyao, Wu, Zhi-Peng, Velasco, Leslie, Moseman, Kelli, O'Brien, Casey P., Tran, Dat T., Lee, Ivan C., Maswadeh, Yazan, Yang, Lefu, Mott, Derrick, Luo, Jin, Petkov, Valeri, and Zhong, Chuan-Jian. Wed . "Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species". United States. https://doi.org/10.1039/c8cy01704b. https://www.osti.gov/servlets/purl/1610909.
Copy to clipboard
@article{osti_1610909,
title = {Catalytic Oxidation of Propane over Palladium Alloyed with Gold: An Assessment of the Chemical and Intermediate Species},
author = {Kareem, Haval and Shan, Shiyao and Wu, Zhi-Peng and Velasco, Leslie and Moseman, Kelli and O'Brien, Casey P. and Tran, Dat T. and Lee, Ivan C. and Maswadeh, Yazan and Yang, Lefu and Mott, Derrick and Luo, Jin and Petkov, Valeri and Zhong, Chuan-Jian},
abstractNote = {Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (PdnAu100–n), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ~ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified for the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. Finally, the implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed.},
doi = {10.1039/c8cy01704b},
journal = {Catalysis Science and Technology},
number = 23,
volume = 8,
place = {United States},
year = {Wed Nov 14 00:00:00 EST 2018},
month = {Wed Nov 14 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/c8cy01704b
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

CO Tolerance of Pd-Rich Platinum Palladium Carbon-Supported Electrocatalysts
journal, January 2002

  • Papageorgopoulos, D. C.; Keijzer, M.; Veldhuis, J. B. J.
  • Journal of The Electrochemical Society, Vol. 149, Issue 11
  • DOI: 10.1149/1.1510131

Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane
journal, January 2012

Chemical Potential of Metal Atoms in Supported Nanoparticles: Dependence upon Particle Size and Support
journal, November 2017

Atomic-Structural Synergy for Catalytic CO Oxidation over Palladium–Nickel Nanoalloys
journal, May 2014

  • Shan, Shiyao; Petkov, Valeri; Yang, Lefu
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja5026744

Discerning the Role of Ag–O–Al Entities on Ag/γ-Al 2 O 3 Surface in NOx Selective Reduction by Ethanol
journal, January 2015

  • Deng, Hua; Yu, Yunbo; He, Hong
  • The Journal of Physical Chemistry C, Vol. 119, Issue 6
  • DOI: 10.1021/jp5114416

Catalytic combustion of C3 hydrocarbons and oxygenates over Mn3O4
journal, March 1998

The influence of temperature on the deactivation of commercial Pd/Rh automotive catalysts
journal, September 2009

  • Fernandes, Daniela Meyer; Scofield, Cynthia Fraga; Neto, Arnaldo Alcover
  • Process Safety and Environmental Protection, Vol. 87, Issue 5
  • DOI: 10.1016/j.psep.2009.05.002

Size-dependent adhesion energy of shape-selected Pd and Pt nanoparticles
journal, January 2016

  • Ahmadi, M.; Behafarid, F.; Cuenya, B. Roldan
  • Nanoscale, Vol. 8, Issue 22
  • DOI: 10.1039/C6NR02166B

In situ FT-IR and TPD-MS study of carbon monoxide oxidation over a CeO2/Co3O4 catalyst
journal, March 2013

A common feature of H 2 -assisted HC-SCR over Ag/Al 2 O 3
journal, January 2014

  • Yu, Yunbo; He, Hong; Zhang, Xiuli
  • Catal. Sci. Technol., Vol. 4, Issue 5
  • DOI: 10.1039/C3CY01033C

Oxidation of carbon monoxide, propene, propane and methane over a Pd/Al2O3 catalyst. Effect of the chemical state of Pd
journal, December 1997

EXAFS and XRD characterization of palladium sorbents for high temperature mercury capture from fuel gas
journal, January 2010

  • Poulston, Stephen; Hyde, Timothy I.; Hamilton, Hugh
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 2
  • DOI: 10.1039/B911941H

Catalytic Oxidation of Methane over ZrO2-Supported Pd Catalysts
journal, February 1999

NOx reduction on a transition metal-free γ-Al2O3 catalyst using dimethylether (DME)
journal, July 2008

Trends in Adhesion Energies of Gold on MgO(100), Rutile TiO 2 (110), and CeO 2 (111) Surfaces: A Comparative DFT Study
journal, December 2017

  • Tosoni, Sergio; Pacchioni, Gianfranco
  • The Journal of Physical Chemistry C, Vol. 121, Issue 51
  • DOI: 10.1021/acs.jpcc.7b09429

Restructuring of AuPd Nanoparticles Studied by a Combined XAFS/DRIFTS Approach
journal, May 2015

Effects of support and additive on oxidation state and activity of Pt catalyst in propane combustion
journal, November 2003

IR Investigation of the Oxidation of Propane and Likely C 3 and C 2 Products over Group IVB Metal Oxide Catalysts
journal, December 2002

  • Hasan, M. A.; Zaki, M. I.; Pasupulety, L.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 49
  • DOI: 10.1021/jp0214413

Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts
journal, March 2017

  • Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit
  • The Journal of Physical Chemistry C, Vol. 121, Issue 14
  • DOI: 10.1021/acs.jpcc.7b00139

An FT-IR and flow reactor study of the conversion of propane on γ-Al2O3 in oxygen-containing atmosphere
journal, January 2000

Oxygen storage capacity measurements of three-way catalysts under transient conditions
journal, January 2002

Evolution of surface catalytic sites on thermochemically-tuned gold–palladium nanoalloys
journal, January 2018

  • Kareem, Haval; Shan, Shiyao; Lin, Fang
  • Nanoscale, Vol. 10, Issue 8
  • DOI: 10.1039/C7NR08748A

Bonding and Electron Energy-Level Alignment at Metal/TiO 2 Interfaces: A Density Functional Theory Study
journal, January 2016

  • Chen, Hungru; Li, Peng; Umezawa, Naoto
  • The Journal of Physical Chemistry C, Vol. 120, Issue 10
  • DOI: 10.1021/acs.jpcc.5b12681

An Investigation of the Reaction Mechanism for the Promotion of Propane Oxidation over Pt/Al2O3 by SO2
journal, July 2001

  • Hinz, Andreas; Skoglundh, Magnus; Fridell, Erik
  • Journal of Catalysis, Vol. 201, Issue 2
  • DOI: 10.1006/jcat.2001.3248

Promotion of a Pd/Al2O3 close-coupled catalyst by Ni
journal, July 2015

Yucca-derived synthesis of gold nanomaterial and their catalytic potential
journal, January 2014

  • Krishnamurthy, Sneha; Esterle, Andrea; Sharma, Nilesh C.
  • Nanoscale Research Letters, Vol. 9, Issue 1
  • DOI: 10.1186/1556-276X-9-627

Nanoengineered PtCo and PtNi Catalysts for Oxygen Reduction Reaction: An Assessment of the Structural and Electrocatalytic Properties
journal, December 2010

  • Loukrakpam, Rameshwori; Luo, Jin; He, Ting
  • The Journal of Physical Chemistry C, Vol. 115, Issue 5
  • DOI: 10.1021/jp109630n

Emissions of liquefied petroleum gas (LPG) from motor vehicles
journal, March 2009

Au–Pd/3DOM Co 3 O 4 : Highly active and stable nanocatalysts for toluene oxidation
journal, February 2015

The selective oxidation of ethylene glycol and 1,2-propanediol on Au, Pd, and Au–Pd bimetallic catalysts
journal, November 2013

  • Griffin, Michael B.; Rodriguez, Abraham A.; Montemore, Matthew M.
  • Journal of Catalysis, Vol. 307
  • DOI: 10.1016/j.jcat.2013.07.012

Low temperature propane oxidation over Co3O4 based nano-array catalysts: Ni dopant effect, reaction mechanism and structural stability
journal, January 2016

IR characterization of propane oxidation on Pt/CeO2–ZrO2: The reaction mechanism and the role of Pt
journal, April 2012

Structural characteristics of selected metal oxides used for the catalytic pyrolysis of sunflower oil
journal, July 2015

  • Demrew Yigezu, Zerihun; Muthukumar, Karuppan
  • Journal of Analytical and Applied Pyrolysis, Vol. 114
  • DOI: 10.1016/j.jaap.2015.05.002

Toluene combustion over palladium supported on various metal oxide supports
journal, September 2003

Study of Supported PtCu and PdAu Bimetallic Nanoparticles Using In-Situ X-ray Tools
journal, June 2010

  • Oxford, Sean M.; Lee, Peter L.; Chupas, Peter J.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 40
  • DOI: 10.1021/jp103675n

In situ characterizations of Pd/Al2O3 and Pd/CeO2/Al2O3 catalysts for oxidative steam reforming of propane
journal, October 2009

  • Faria, Wagner L. S.; Perez, Carlos A. C.; César, Deborah V.
  • Applied Catalysis B: Environmental, Vol. 92, Issue 1-2
  • DOI: 10.1016/j.apcatb.2009.07.001

Complete catalytic oxidation of volatile organics
journal, November 1987

  • Spivey, James J.
  • Industrial & Engineering Chemistry Research, Vol. 26, Issue 11
  • DOI: 10.1021/ie00071a001

FTIR studies on the selective oxidation and combustion of light hydrocarbns at metal oxide surfaces. Propane and propene oxidation on MgCr2O4
journal, January 1994

  • Finocchio, Elisabetta; Busca, Guido; Lorenzelli, Vincenzo
  • Journal of the Chemical Society, Faraday Transactions, Vol. 90, Issue 21
  • DOI: 10.1039/ft9949003347

A novel insight into enhanced propane combustion performance on PtUSY catalyst
journal, June 2016

Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology
journal, January 2017

Novel Nanoporous Au−Pd Alloy with High Catalytic Activity and Excellent Electrochemical Stability
journal, January 2010

  • Lang, X. Y.; Guo, H.; Chen, L. Y.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 6
  • DOI: 10.1021/jp907682x

Oxophilicity and Structural Integrity in Maneuvering Surface Oxygenated Species on Nanoalloys for CO Oxidation
journal, November 2013

  • Shan, Shiyao; Petkov, Valeri; Yang, Lefu
  • ACS Catalysis, Vol. 3, Issue 12
  • DOI: 10.1021/cs400700r

Growth of Pd, Pt, Ag and Au nanoparticles on carbon nanotubes
journal, January 2001

  • Xue, Bin; Chen, Ping; Hong, Qi
  • Journal of Materials Chemistry, Vol. 11, Issue 9
  • DOI: 10.1039/b100618p

Properties and performance of Pd based catalysts for catalytic oxidation of volatile organic compounds
journal, November 2009

PtCo/C cathode catalyst for improved durability in PEMFCs
journal, June 2005

Methane combustion on Mg-doped LaMnO3 perovskite catalysts
journal, April 1999

Surface Segregation of Pd from TiO 2 -Supported AuPd Nanoalloys under CO Oxidation Conditions Observed In situ by ETEM and DRIFTS
journal, February 2013

  • Delannoy, Laurent; Giorgio, Suzanne; Mattei, Jean Gabriel
  • ChemCatChem, Vol. 5, Issue 9
  • DOI: 10.1002/cctc.201200618

Reactivity of the free and (5,5)-carbon nanotube-supported AuPt bimetallic clusters towards O 2 activation: a theoretical study
journal, January 2015

  • Shojaei, Fazel; Mousavi, Masoumeh; Nazari, Fariba
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 5
  • DOI: 10.1039/C4CP05109B

The Application of Diffuse Reflectance Infrared Spectroscopy and Temperature-Programmed Desorption To Investigate the Interaction of Methanol on η-Alumina
journal, November 2005

  • McInroy, Alastair R.; Lundie, David T.; Winfield, John M.
  • Langmuir, Vol. 21, Issue 24
  • DOI: 10.1021/la051429c

Interaction of Ester Functional Groups with Aluminum Oxide Surfaces Studied Using Infrared Reflection Absorption Spectroscopy
journal, July 2004

  • van den Brand, J.; Blajiev, O.; Beentjes, P. C. J.
  • Langmuir, Vol. 20, Issue 15
  • DOI: 10.1021/la049456a

The Composition and Structure of Pd−Au Surfaces
journal, October 2005

  • Yi, C. -W.; Luo, K.; Wei, T.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 39
  • DOI: 10.1021/jp053515r

Noble-transition metal nanoparticle breathing in a reactive gas atmosphere
journal, January 2013

  • Petkov, Valeri; Shan, Shiyao; Chupas, Peter
  • Nanoscale, Vol. 5, Issue 16
  • DOI: 10.1039/c3nr02582a

Palladium Nanocrystals on Al 2 O 3 : Structure and Adhesion Energy
journal, November 1999

Effect of acid and base modification on the catalytic activity of Pt/Al2O3 for propene oxidation
journal, March 2014

Activation of Lattice Oxygen of TiO 2 by Pd 2+ Ion: Correlation of Low-Temperature CO and Hydrocarbon Oxidation with Structure of Ti 1– x Pd x O 2– x ( x = 0.01–0.03)
journal, November 2012

  • Mukri, Bhaskar Devu; Dutta, Gargi; Waghmare, Umesh V.
  • Chemistry of Materials, Vol. 24, Issue 23
  • DOI: 10.1021/cm301704u
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: