Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys
Abstract
Platinum group metals (PGMs) serve as highly active catalysts in a variety of heterogeneous chemical processes. Unfortunately, their high activity is accompanied by a high affinity for CO and thus, PGMs are susceptible to poisoning. Alloying PGMs with metals exhibiting lower affinity to CO could be an effective strategy toward preventing such poisoning. In this work, we use density functional theory to demonstrate this strategy, focusing on highly dilute alloys of PGMs (Pd, Pt, Rh, Ir and Ni) with poison resistant coinage metal hosts (Cu, Ag, Au), such that individual PGM atoms are dispersed at the atomic limit forming single atom alloys (SAAs). We show that compared to the pure metals, CO exhibits lower binding strength on the majority of SAAs studied, and we use kinetic Monte Carlo simulation to obtain relevant temperature programed desorption spectra, which are found to be in good agreement with experiments. Additionally, we consider the effects of CO adsorption on the structure of SAAs. We calculate segregation energies which are indicative of the stability of dopant atoms in the bulk compared to the surface layer, as well as aggregation energies to determine the stability of isolated surface dopant atoms compared to dimer and trimer configurations.more »
- Authors:
-
- Univ. of College London, London (United Kingdom)
- Tufts Univ., Medford, MA (United States)
- Publication Date:
- Research Org.:
- Tufts Univ., Medford, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1502103
- Grant/Contract Number:
- SC0004738
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Topics in Catalysis
- Additional Journal Information:
- Journal Volume: 61; Journal Issue: 5-6; Journal ID: ISSN 1022-5528
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Carbon monoxide; Catalyst stability; Catalyst poisoning; Highly dilute alloy; Platinum group metals; Ensemble effects
Citation Formats
Darby, Matthew T., Sykes, E. Charles H., Michaelides, Angelos, and Stamatakis, Michail. Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys. United States: N. p., 2018.
Web. doi:10.1007/s11244-017-0882-1.
Darby, Matthew T., Sykes, E. Charles H., Michaelides, Angelos, & Stamatakis, Michail. Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys. United States. doi:10.1007/s11244-017-0882-1.
Darby, Matthew T., Sykes, E. Charles H., Michaelides, Angelos, and Stamatakis, Michail. Mon .
"Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys". United States. doi:10.1007/s11244-017-0882-1. https://www.osti.gov/servlets/purl/1502103.
@article{osti_1502103,
title = {Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys},
author = {Darby, Matthew T. and Sykes, E. Charles H. and Michaelides, Angelos and Stamatakis, Michail},
abstractNote = {Platinum group metals (PGMs) serve as highly active catalysts in a variety of heterogeneous chemical processes. Unfortunately, their high activity is accompanied by a high affinity for CO and thus, PGMs are susceptible to poisoning. Alloying PGMs with metals exhibiting lower affinity to CO could be an effective strategy toward preventing such poisoning. In this work, we use density functional theory to demonstrate this strategy, focusing on highly dilute alloys of PGMs (Pd, Pt, Rh, Ir and Ni) with poison resistant coinage metal hosts (Cu, Ag, Au), such that individual PGM atoms are dispersed at the atomic limit forming single atom alloys (SAAs). We show that compared to the pure metals, CO exhibits lower binding strength on the majority of SAAs studied, and we use kinetic Monte Carlo simulation to obtain relevant temperature programed desorption spectra, which are found to be in good agreement with experiments. Additionally, we consider the effects of CO adsorption on the structure of SAAs. We calculate segregation energies which are indicative of the stability of dopant atoms in the bulk compared to the surface layer, as well as aggregation energies to determine the stability of isolated surface dopant atoms compared to dimer and trimer configurations. Our calculations reveal that CO adsorption induces dopant atom segregation into the surface layer for all SAAs considered here, whereas aggregation and island formation may be promoted or inhibited depending on alloy constitution and CO coverage. Furthermore, this observation suggests the possibility of controlling ensemble effects in novel catalyst architectures through CO-induced aggregation and kinetic trapping.},
doi = {10.1007/s11244-017-0882-1},
journal = {Topics in Catalysis},
number = 5-6,
volume = 61,
place = {United States},
year = {2018},
month = {1}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Resistance to sulfur poisoning of Ni-based alloy with coinage (IB) metals
journal, December 2015
- Xu, Xiaopei; Zhang, Yanxing; Yang, Zongxian
- Applied Surface Science, Vol. 357
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
CO induced surface segregation as a means of improving surface composition and enhancing performance of CuPd bimetallic catalysts
journal, September 2015
- McCue, Alan J.; Anderson, James A.
- Journal of Catalysis, Vol. 329
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Tackling CO Poisoning with Single-Atom Alloy Catalysts
journal, May 2016
- Liu, Jilei; Lucci, Felicia R.; Yang, Ming
- Journal of the American Chemical Society, Vol. 138, Issue 20
A graph-theoretical kinetic Monte Carlo framework for on-lattice chemical kinetics
journal, June 2011
- Stamatakis, Michail; Vlachos, Dionisios G.
- The Journal of Chemical Physics, Vol. 134, Issue 21
Extraction of kinetic parameters in temperature programmed desorption: A comparison of methods
journal, December 1987
- Miller, J. B.; Siddiqui, H. R.; Gates, S. M.
- The Journal of Chemical Physics, Vol. 87, Issue 11
Preparation, Structure, and Surface Chemistry of Ni–Au Single Atom Alloys
journal, June 2016
- Wang, Zhi-Tao; Darby, Matthew T.; Therrien, Andrew J.
- The Journal of Physical Chemistry C, Vol. 120, Issue 25
Hydrogen Dissociation and Spillover on Individual Isolated Palladium Atoms
journal, December 2009
- Tierney, Heather L.; Baber, Ashleigh E.; Kitchin, John R.
- Physical Review Letters, Vol. 103, Issue 24
The carbon-tolerance mechanism of Ni-based alloy with coinage metals
journal, November 2013
- Wang, Mingyang; Fu, Zhaoming; Yang, Zongxian
- Physics Letters A, Vol. 377, Issue 34-36
Reaction pathways and poisons—II
journal, January 1975
- Vogel, W.; Lundquist, L.; Ross, P.
- Electrochimica Acta, Vol. 20, Issue 1
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
Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit
journal, October 2015
- Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.
- Nature Communications, Vol. 6, Issue 1
DFT study of the M segregation on MAu alloys (M=Ni, Pd, Pt) in presence of adsorbed oxygen O and O2
journal, January 2012
- Dhouib, Adnene; Guesmi, Hazar
- Chemical Physics Letters, Vol. 521
Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions
journal, December 2013
- Nielsen, Jens; d’Avezac, Mayeul; Hetherington, James
- The Journal of Chemical Physics, Vol. 139, Issue 22
Ag Alloyed Pd Single-Atom Catalysts for Efficient Selective Hydrogenation of Acetylene to Ethylene in Excess Ethylene
journal, May 2015
- Pei, Guang Xian; Liu, Xiao Yan; Wang, Aiqin
- ACS Catalysis, Vol. 5, Issue 6
Surface restructuring of Cu-based single-atom alloy catalysts under reaction conditions: the essential role of adsorbates
journal, January 2017
- Yang, Kunran; Yang, Bo
- Physical Chemistry Chemical Physics, Vol. 19, Issue 27
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen
journal, August 2016
- Shan, Junjun; Lucci, Felicia R.; Liu, Jilei
- Surface Science, Vol. 650
Molecular-Scale Perspective of Water-Catalyzed Methanol Dehydrogenation to Formaldehyde
journal, June 2013
- Boucher, Matthew B.; Marcinkowski, Matthew D.; Liriano, Melissa L.
- ACS Nano, Vol. 7, Issue 7
Reactivity of Bimetallic Systems Studied from First Principles
journal, March 2006
- Groß, Axel
- Topics in Catalysis, Vol. 37, Issue 1
The adsorption of Xe and CO on Ag(111)
journal, March 1976
- McElhiney, G.; Papp, H.; Pritchard, J.
- Surface Science, Vol. 54, Issue 3
Equilibrium Constants and Rate Constants for Adsorbates: Two-Dimensional (2D) Ideal Gas, 2D Ideal Lattice Gas, and Ideal Hindered Translator Models
journal, May 2016
- Campbell, Charles T.; Sprowl, Lynza H.; Árnadóttir, Líney
- The Journal of Physical Chemistry C, Vol. 120, Issue 19
STM studies of ordered CO islands on Ag(111)
journal, April 2005
- Kulawik, M.; Rust, H. -P.; Nilius, N.
- Physical Review B, Vol. 71, Issue 15
Surface segregation and ordering of alloy surfaces in the presence of adsorbates
journal, November 2005
- Han, B. C.; Van der Ven, A.; Ceder, G.
- Physical Review B, Vol. 72, Issue 20
Chemisorbed atomic oxygen inducing Pd segregation in PdAu(111) alloy: Energetic and electronic DFT analysis
journal, February 2011
- Guesmi, Hazar; Louis, Catherine; Delannoy, Laurent
- Chemical Physics Letters, Vol. 503, Issue 1-3
The adsorption of CO, O2, and H2 on Pt
journal, December 1977
- Collins, D. M.; Spicer, W. E.
- Surface Science, Vol. 69, Issue 1
Unraveling the Complexity of Catalytic Reactions via Kinetic Monte Carlo Simulation: Current Status and Frontiers
journal, November 2012
- Stamatakis, Michail; Vlachos, Dionisios G.
- ACS Catalysis, Vol. 2, Issue 12
On the CO tolerance of novel colloidal PdAu/carbon electrocatalysts
journal, March 2001
- Schmidt, T. J.; Jusys, Z.; Gasteiger, H. A.
- Journal of Electroanalytical Chemistry, Vol. 501, Issue 1-2
Density functional theory study of CO-induced segregation in gold-based alloys
journal, August 2014
- Sansa, Myriam; Dhouib, Adnene; Guesmi, Hazar
- The Journal of Chemical Physics, Vol. 141, Issue 6
Adsorption of CO on Surfaces of 4d and 5d Elements in Group VIII
journal, January 2007
- Liu, W.; Zhu, Y. F.; Lian, J. S.
- The Journal of Physical Chemistry C, Vol. 111, Issue 2
Surface electronic structure and reactivity of transition and noble metals1Communication presented at the First Francqui Colloquium, Brussels, 19–20 February 1996.1
journal, February 1997
- Ruban, A.; Hammer, B.; Stoltze, P.
- Journal of Molecular Catalysis A: Chemical, Vol. 115, Issue 3
Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations
journal, March 2012
- Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D.
- Science, Vol. 335, Issue 6073
Pd on carbon nanotubes-supported Ag for formate oxidation: The effect of Ag on anti-poisoning performance
journal, August 2016
- Wang, Jianshe; Liu, Changhai; Lushington, Andrew
- Electrochimica Acta, Vol. 210
The oxidation of carbon monoxide on the Au(110) surface
journal, January 1987
- Outka, Duane A.; Madix, R. J.
- Surface Science, Vol. 179, Issue 2-3
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site
journal, January 2017
- Miura, Hiroki; Endo, Keisuke; Ogawa, Ryoichi
- ACS Catalysis, Vol. 7, Issue 3
CO adsorption studies on pure and Ni-covered Cu(111) surfaces
journal, November 1986
- Kirstein, W.; Krüger, B.; Thieme, F.
- Surface Science, Vol. 176, Issue 3
First-principles study of Au–Cu alloy surface changes induced by gas adsorption of CO, NO, or O 2
journal, July 2016
- Dhifallah, Marwa; Dhouib, Adnene; Aldulaijan, Sarah
- The Journal of Chemical Physics, Vol. 145, Issue 2
A facile route to monodisperse MPd (M = Co or Cu) alloy nanoparticles and their catalysis for electrooxidation of formic acid
journal, January 2014
- Ho, Sally Fae; Mendoza-Garcia, Adriana; Guo, Shaojun
- Nanoscale, Vol. 6, Issue 12
Chemisorption of H on Pd(111): An ab initio approach with ultrasoft pseudopotentials
journal, July 1996
- Dong, W.; Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 3
First-Principles-Based Kinetic Monte Carlo Simulation of the Structure Sensitivity of the Water–Gas Shift Reaction on Platinum Surfaces
journal, November 2011
- Stamatakis, Michail; Chen, Ying; Vlachos, Dionisios G.
- The Journal of Physical Chemistry C, Vol. 115, Issue 50
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999
- Hammer, B.; Hansen, L. B.; Nørskov, J. K.
- Physical Review B, Vol. 59, Issue 11
Evidence of Pd segregation and stabilization at edges of AuPd nano-clusters in the presence of CO: A combined DFT and DRIFTS study
journal, December 2013
- Zhu, Beien; Thrimurthulu, Gode; Delannoy, Laurent
- Journal of Catalysis, Vol. 308
Atomic-Scale Imaging and Electronic Structure Determination of Catalytic Sites on Pd/Cu Near Surface Alloys
journal, March 2009
- Tierney, Heather L.; Baber, Ashleigh E.; Sykes, E. Charles H.
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys
journal, January 2014
- Lucci, Felicia R.; Lawton, Timothy J.; Pronschinske, Alex
- The Journal of Physical Chemistry C, Vol. 118, Issue 6
Surface segregation energies in transition-metal alloys
journal, June 1999
- Ruban, A. V.; Skriver, H. L.; Nørskov, J. K.
- Physical Review B, Vol. 59, Issue 24
Controlling a spillover pathway with the molecular cork effect
journal, April 2013
- Marcinkowski, Matthew D.; Jewell, April D.; Stamatakis, Michail
- Nature Materials, Vol. 12, Issue 6
Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions
journal, January 2013
- Boucher, Matthew B.; Zugic, Branko; Cladaras, George
- Physical Chemistry Chemical Physics, Vol. 15, Issue 29
Carbon monoxide poisoning of proton exchange membrane fuel cells
journal, January 2001
- Baschuk, J. J.; Li, Xianguo
- International Journal of Energy Research, Vol. 25, Issue 8
Surface segregation in bimetallic Pt3M (M=Fe, Co, Ni) alloys with adsorbed oxygen
journal, January 2009
- Ma, Yuguang; Balbuena, Perla B.
- Surface Science, Vol. 603, Issue 2
Surface energies of elemental crystals
journal, September 2016
- Tran, Richard; Xu, Zihan; Radhakrishnan, Balachandran
- Scientific Data, Vol. 3, Issue 1
Dual role of CO in the stability of subnano Pt clusters at the Fe 3 O 4 (001) surface
journal, July 2016
- Bliem, Roland; van der Hoeven, Jessi E. S.; Hulva, Jan
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 32
Poisoning of Pt/C catalysts by CO and its consequences over the kinetics of hydrogen chemisorption
journal, November 2009
- Trens, Philippe; Durand, Robert; Coq, Bernard
- Applied Catalysis B: Environmental, Vol. 92, Issue 3-4
A review of PEM hydrogen fuel cell contamination: Impacts, mechanisms, and mitigation
journal, March 2007
- Cheng, Xuan; Shi, Zheng; Glass, Nancy
- Journal of Power Sources, Vol. 165, Issue 2
Significance of single-electron energies for the description of CO on Pt(111)
journal, August 2003
- Kresse, G.; Gil, A.; Sautet, P.
- Physical Review B, Vol. 68, Issue 7
The CO/Pt(111) Puzzle †
journal, May 2001
- Feibelman, Peter J.; Hammer, B.; Nørskov, J. K.
- The Journal of Physical Chemistry B, Vol. 105, Issue 18
Controlling Hydrogen Activation, Spillover, and Desorption with Pd–Au Single-Atom Alloys
journal, January 2016
- Lucci, Felicia R.; Darby, Matthew T.; Mattera, Michael F. G.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
An Atomic-Scale View of Palladium Alloys and their Ability to Dissociate Molecular Hydrogen
journal, October 2010
- Baber, Ashleigh E.; Tierney, Heather L.; Lawton, Timothy J.
- ChemCatChem, Vol. 3, Issue 3
Dependence of effective desorption kinetic parameters on surface coverage and adsorption temperature: CO on Pd(111)
journal, June 1989
- Guo, Xingcai; Yates, John T.
- The Journal of Chemical Physics, Vol. 90, Issue 11
Works referencing / citing this record:
Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies
journal, January 2020
- Wegener, Evan C.; Bukowski, Brandon C.; Yang, Dali
- ChemCatChem, Vol. 12, Issue 5
The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au 3 Pd(111)
journal, September 2019
- Do, Quan K.; Tran, Hung-Vu; Wang, Shengguang
- Energy Technology, Vol. 8, Issue 8
Single atom alloy catalyst for SO 3 decomposition: enhancement of platinum catalyst's performance by Ag atom embedding
journal, January 2018
- Nigam, Sandeep; Majumder, Chiranjib
- Nanoscale, Vol. 10, Issue 44
Predicting aggregation energy for single atom bimetallic catalysts on clean and O* adsorbed surfaces through machine learning models
journal, January 2020
- Lu, Zhuole; Yadav, Shwetank; Singh, Chandra Veer
- Catalysis Science & Technology, Vol. 10, Issue 1
Elucidating the composition of PtAg surface alloys with atomic-scale imaging and spectroscopy
journal, October 2019
- Patel, Dipna A.; Kress, Paul L.; Cramer, Laura A.
- The Journal of Chemical Physics, Vol. 151, Issue 16
Figures / Tables found in this record: