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Title: Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum

Abstract

Pd- and Pt-based catalysts are highly studied materials due to their widespread use in emissions control catalysis. However, claims continue to vary regarding the active phase and oxidation state of the metals. Different conclusions have likely been reached due to the heterogeneous nature of such materials containing various metal nanoparticle sizes and compositions, which may each possess unique redox features. In this work, using uniform nanocrystal catalysts, we study the effect of particle size and alloying on redox properties of Pd-based catalysts and show their contribution to methane combustion activity using operando quick extended x-ray absorption fine structure measurements. Results demonstrate that for all studied Pd sizes (3 nm–16 nm), Pd oxidation directly precedes CH4 combustion to CO2, suggesting Pd oxidation as a prerequisite step to methane combustion, and an oxidation pretreatment shows equal or better catalysis than a reduction pretreatment. Results are then extended herein to uniform alloyed PtxPd1–x nanoparticles, where oxidative pretreatments are shown to enhance low-temperature combustion. In these uniform alloys, we observe a composition-dependent effect with Pt-rich alloys showing the maximum difference between oxidative and reductive pretreatments. In Pt-rich alloys, we initially observe that the presence of Pt maintains Pd in a lower-activity reduced state. However,more » with time on stream, PdO eventually segregates under oxidizing combustion conditions, leading to a slowly increasing activity. Overall, across particle sizes and alloy compositions, we relate increased catalytic activity to Pd oxidation, thus shedding light on previous contrasting results related to the methane combustion activity of these catalysts.« less

Authors:
 [1];  [1];  [1];  [2];  [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [3];  [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis and Dept. of Chemical Engineering
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry and National Center for Electron Microscopy
  4. Paul Scherrer Institute, Villigen, Switzerland
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1596989
Alternate Identifier(s):
OSTI ID: 1570868
Grant/Contract Number:  
ECCS-1542152; DGE-1656518; AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 15; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Goodman, Emmett D., Ye, Angela A., Aitbekova, Aisulu, Mueller, Oliver, Riscoe, Andrew R., Nguyen Taylor, Temy, Hoffman, Adam S., Boubnov, Alexey, Bustillo, Karen C., Nachtegaal, Maarten, Bare, Simon R., and Cargnello, Matteo. Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum. United States: N. p., 2019. Web. doi:10.1063/1.5126219.
Goodman, Emmett D., Ye, Angela A., Aitbekova, Aisulu, Mueller, Oliver, Riscoe, Andrew R., Nguyen Taylor, Temy, Hoffman, Adam S., Boubnov, Alexey, Bustillo, Karen C., Nachtegaal, Maarten, Bare, Simon R., & Cargnello, Matteo. Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum. United States. https://doi.org/10.1063/1.5126219
Goodman, Emmett D., Ye, Angela A., Aitbekova, Aisulu, Mueller, Oliver, Riscoe, Andrew R., Nguyen Taylor, Temy, Hoffman, Adam S., Boubnov, Alexey, Bustillo, Karen C., Nachtegaal, Maarten, Bare, Simon R., and Cargnello, Matteo. Fri . "Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum". United States. https://doi.org/10.1063/1.5126219. https://www.osti.gov/servlets/purl/1596989.
@article{osti_1596989,
title = {Palladium oxidation leads to methane combustion activity: Effects of particle size and alloying with platinum},
author = {Goodman, Emmett D. and Ye, Angela A. and Aitbekova, Aisulu and Mueller, Oliver and Riscoe, Andrew R. and Nguyen Taylor, Temy and Hoffman, Adam S. and Boubnov, Alexey and Bustillo, Karen C. and Nachtegaal, Maarten and Bare, Simon R. and Cargnello, Matteo},
abstractNote = {Pd- and Pt-based catalysts are highly studied materials due to their widespread use in emissions control catalysis. However, claims continue to vary regarding the active phase and oxidation state of the metals. Different conclusions have likely been reached due to the heterogeneous nature of such materials containing various metal nanoparticle sizes and compositions, which may each possess unique redox features. In this work, using uniform nanocrystal catalysts, we study the effect of particle size and alloying on redox properties of Pd-based catalysts and show their contribution to methane combustion activity using operando quick extended x-ray absorption fine structure measurements. Results demonstrate that for all studied Pd sizes (3 nm–16 nm), Pd oxidation directly precedes CH4 combustion to CO2, suggesting Pd oxidation as a prerequisite step to methane combustion, and an oxidation pretreatment shows equal or better catalysis than a reduction pretreatment. Results are then extended herein to uniform alloyed PtxPd1–x nanoparticles, where oxidative pretreatments are shown to enhance low-temperature combustion. In these uniform alloys, we observe a composition-dependent effect with Pt-rich alloys showing the maximum difference between oxidative and reductive pretreatments. In Pt-rich alloys, we initially observe that the presence of Pt maintains Pd in a lower-activity reduced state. However, with time on stream, PdO eventually segregates under oxidizing combustion conditions, leading to a slowly increasing activity. Overall, across particle sizes and alloy compositions, we relate increased catalytic activity to Pd oxidation, thus shedding light on previous contrasting results related to the methane combustion activity of these catalysts.},
doi = {10.1063/1.5126219},
journal = {Journal of Chemical Physics},
number = 15,
volume = 151,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 23 works
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Figures / Tables:

Fig. 1 Fig. 1: Transmission electron microscopy of monometallic Pd/Al203 materials. Representative TEM images of (a) 2.5 nm Pd/Al203, (b) 7.9 nm Pd/Al203, and (c) 14.7 nm Pd/Al203 catalysts. All catalysts are 1.0 wt.% Pd/Al203. Particle size distributions have been reported in a past work.

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Works referenced in this record:

Inhibition of methane adsorption on PdO(101) by water and molecular oxygen
journal, November 2013


The Metal-Support Interaction Concerning the Particle Size Effect of Pd/Al 2 O 3 on Methane Combustion
journal, November 2017

  • Murata, Kazumasa; Mahara, Yuji; Ohyama, Junya
  • Angewandte Chemie International Edition, Vol. 56, Issue 50
  • DOI: 10.1002/anie.201709124

The Turnover Rate for the Catalytic Combustion of Methane over Palladium Is Not Sensitive to the Structure of the Catalyst
journal, August 2004

  • Zhu, Guanghui; Han, Jinyi; Zemlyanov, Dmitri Y.
  • Journal of the American Chemical Society, Vol. 126, Issue 32
  • DOI: 10.1021/ja049406s

Catalyst deactivation via decomposition into single atoms and the role of metal loading
journal, August 2019

  • Goodman, Emmett D.; Johnston-Peck, Aaron C.; Dietze, Elisabeth M.
  • Nature Catalysis, Vol. 2, Issue 9
  • DOI: 10.1038/s41929-019-0328-1

Deconvoluting Transient Water Effects on the Activity of Pd Methane Combustion Catalysts
journal, July 2018

  • Huang, Weixin; Goodman, Emmett D.; Losch, Pit
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 31
  • DOI: 10.1021/acs.iecr.8b01915

Effect of Pt:Pd ratio on CO and hydrocarbon oxidation
journal, April 2018


Systematic Structure–Property Relationship Studies in Palladium-Catalyzed Methane Complete Combustion
journal, October 2017

  • Willis, Joshua J.; Gallo, Alessandro; Sokaras, Dimosthenis
  • ACS Catalysis, Vol. 7, Issue 11
  • DOI: 10.1021/acscatal.7b02414

Support effect on methane combustion over palladium catalysts
journal, February 2007

  • Yoshida, Hisao; Nakajima, Tomoyuki; Yazawa, Yoshiteru
  • Applied Catalysis B: Environmental, Vol. 71, Issue 1-2
  • DOI: 10.1016/j.apcatb.2006.08.010

The Active Phase of Palladium during Methane Oxidation
journal, February 2012

  • Hellman, A.; Resta, A.; Martin, N. M.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 6
  • DOI: 10.1021/jz300069s

Investigation of Pt/Al2O3 and Pd/Al2O3 catalysts for the combustion of methane at low concentrations
journal, December 1994


Microstructure of Bimetallic PtPd Catalysts under Oxidizing Conditions
journal, July 2013

  • Johns, Tyne R.; Gaudet, Jason R.; Peterson, Eric J.
  • ChemCatChem, Vol. 5, Issue 9
  • DOI: 10.1002/cctc.201300181

Consequences of Metal–Oxide Interconversion for C–H Bond Activation during CH 4 Reactions on Pd Catalysts
journal, October 2013

  • Chin, Ya-Huei (Cathy); Buda, Corneliu; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja405004m

Trapping mobile Pt species by PdO in diesel oxidation catalysts: Smaller is better
journal, September 2016


Quick scanning monochromator for millisecond in situ and in operando X-ray absorption spectroscopy
journal, September 2015

  • Müller, O.; Lützenkirchen-Hecht, D.; Frahm, R.
  • Review of Scientific Instruments, Vol. 86, Issue 9
  • DOI: 10.1063/1.4929866

Combustion of Methane over Palladium-Based Catalysts: Support Interactions
journal, April 2012

  • Schwartz, William R.; Pfefferle, Lisa D.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 15
  • DOI: 10.1021/jp2119668

Exceptional Activity for Methane Combustion over Modular Pd@CeO2 Subunits on Functionalized Al2O3
journal, August 2012


Uniform Pt/Pd Bimetallic Nanocrystals Demonstrate Platinum Effect on Palladium Methane Combustion Activity and Stability
journal, May 2017


The quantitative analysis of thin specimens
journal, March 1975


Methane Catalytic Combustion over Hierarchical Pd@CeO 2 /Si-Al 2 O 3 : Effect of the Presence of Water
journal, October 2014


Metastable Pd ↔ PdO Structures During High Temperature Methane Oxidation
journal, March 2017


Characterization of Surface Structure and Oxidation/Reduction Behavior of Pd–Pt/Al 2 O 3 Model Catalysts
journal, December 2016

  • Martin, Natalia M.; Nilsson, Johan; Skoglundh, Magnus
  • The Journal of Physical Chemistry C, Vol. 120, Issue 49
  • DOI: 10.1021/acs.jpcc.6b09223

Dynamics and Thermodynamics of Pd–PdO Phase Transitions: Effects of Pd Cluster Size and Kinetic Implications for Catalytic Methane Combustion
journal, January 2016

  • Chin, Ya-Huei (Cathy); García-Diéguez, Mónica; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 120, Issue 3
  • DOI: 10.1021/acs.jpcc.5b06677

Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals
journal, August 2017

  • Willis, Joshua J.; Goodman, Emmett D.; Wu, Liheng
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b06260

Catalytic Oxidation of Methane: Pd and Beyond: Catalytic Oxidation of Methane: Pd and Beyond
journal, June 2018

  • Monai, Matteo; Montini, Tiziano; Gorte, Raymond J.
  • European Journal of Inorganic Chemistry, Vol. 2018, Issue 25
  • DOI: 10.1002/ejic.201800326

NIH Image to ImageJ: 25 years of image analysis
journal, June 2012

  • Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W.
  • Nature Methods, Vol. 9, Issue 7
  • DOI: 10.1038/nmeth.2089

Methane removal and atmospheric restoration
journal, May 2019


Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution
journal, January 2016

  • Müller, Oliver; Nachtegaal, Maarten; Just, Justus
  • Journal of Synchrotron Radiation, Vol. 23, Issue 1
  • DOI: 10.1107/s1600577515018007

Efficient Removal of Organic Ligands from Supported Nanocrystals by Fast Thermal Annealing Enables Catalytic Studies on Well-Defined Active Phases
journal, May 2015

  • Cargnello, Matteo; Chen, Chen; Diroll, Benjamin T.
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b03333

Low-Temperature Oxidation of Methane
journal, August 2012


Experimental and modeling study of CO and hydrocarbons light-off on various Pt-Pd/γ-Al 2 O 3 diesel oxidation catalysts
journal, September 2017


Works referencing / citing this record:

Partial oxidation of methane to methanol by isolated Pt catalyst supported on a CeO 2 nanoparticle
journal, February 2020

  • Kye, So-Hwang; Park, Hee Sun; Zhang, Renqin
  • The Journal of Chemical Physics, Vol. 152, Issue 5
  • DOI: 10.1063/1.5135741

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.