A versatile approach for quantification of surface site fractions using reaction kinetics: The case of CO oxidation on supported Ir single atoms and nanoparticles
Abstract
Supported metal single-atom catalysts have shown unique activity and selectivity for several reactions. Investigating the reaction mechanism on single-atom catalysts and unambiguous assignment of the activity and selectivity requires catalysts with exclusively single atoms. Yet, it is challenging to prepare pure single-atom catalysts with conventional impregnation methods, which typically result in a mixture of single atoms and nanoparticles. In this work, we show that owing to different reaction mechanisms on single atoms and nanoparticles, reaction kinetics can serve as a surface sensitive characterization technique for quantifying their surface site fractions. As a case study, we use CO oxidation kinetics on Ir/MgAl2O4 to quantify the surface site fractions of single atoms and nanoparticles and the results are consistent with aberration-corrected scanning transmission electron microscopy, X-ray absorption fine structure and infrared spectroscopies. Furthermore, by carefully choosing the reaction conditions, the activity of single atoms (or nanoparticles) can be made dominant, enabling detection of a small fraction, or allowing a study of their reaction mechanism on a catalyst containing a mixture of single atoms and nanoparticles. These results are general and could be applied to other systems where two types of sites have different reaction mechanisms.
- Authors:
-
[1];
[1];
[1]
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1582221
- Alternate Identifier(s):
- OSTI ID: 1560787
- Grant/Contract Number:
- W911NF-16-1-0400; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 378; Journal Issue: C; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Single-atom catalyst; Kinetics; CO oxidation; X-ray absorption spectroscopy; Infrared spectroscopy; Scanning transmission electron microscopy
Citation Formats
Lu, Yubing, Kuo, Chun-Te, Kovarik, Libor, Hoffman, Adam S., Boubnov, Alexey, Driscoll, Darren M., Morris, John R., Bare, Simon R., and Karim, Ayman M. A versatile approach for quantification of surface site fractions using reaction kinetics: The case of CO oxidation on supported Ir single atoms and nanoparticles. United States: N. p., 2019.
Web. doi:10.1016/j.jcat.2019.08.023.
Lu, Yubing, Kuo, Chun-Te, Kovarik, Libor, Hoffman, Adam S., Boubnov, Alexey, Driscoll, Darren M., Morris, John R., Bare, Simon R., & Karim, Ayman M. A versatile approach for quantification of surface site fractions using reaction kinetics: The case of CO oxidation on supported Ir single atoms and nanoparticles. United States. https://doi.org/10.1016/j.jcat.2019.08.023
Lu, Yubing, Kuo, Chun-Te, Kovarik, Libor, Hoffman, Adam S., Boubnov, Alexey, Driscoll, Darren M., Morris, John R., Bare, Simon R., and Karim, Ayman M. Mon .
"A versatile approach for quantification of surface site fractions using reaction kinetics: The case of CO oxidation on supported Ir single atoms and nanoparticles". United States. https://doi.org/10.1016/j.jcat.2019.08.023. https://www.osti.gov/servlets/purl/1582221.
@article{osti_1582221,
title = {A versatile approach for quantification of surface site fractions using reaction kinetics: The case of CO oxidation on supported Ir single atoms and nanoparticles},
author = {Lu, Yubing and Kuo, Chun-Te and Kovarik, Libor and Hoffman, Adam S. and Boubnov, Alexey and Driscoll, Darren M. and Morris, John R. and Bare, Simon R. and Karim, Ayman M.},
abstractNote = {Supported metal single-atom catalysts have shown unique activity and selectivity for several reactions. Investigating the reaction mechanism on single-atom catalysts and unambiguous assignment of the activity and selectivity requires catalysts with exclusively single atoms. Yet, it is challenging to prepare pure single-atom catalysts with conventional impregnation methods, which typically result in a mixture of single atoms and nanoparticles. In this work, we show that owing to different reaction mechanisms on single atoms and nanoparticles, reaction kinetics can serve as a surface sensitive characterization technique for quantifying their surface site fractions. As a case study, we use CO oxidation kinetics on Ir/MgAl2O4 to quantify the surface site fractions of single atoms and nanoparticles and the results are consistent with aberration-corrected scanning transmission electron microscopy, X-ray absorption fine structure and infrared spectroscopies. Furthermore, by carefully choosing the reaction conditions, the activity of single atoms (or nanoparticles) can be made dominant, enabling detection of a small fraction, or allowing a study of their reaction mechanism on a catalyst containing a mixture of single atoms and nanoparticles. These results are general and could be applied to other systems where two types of sites have different reaction mechanisms.},
doi = {10.1016/j.jcat.2019.08.023},
journal = {Journal of Catalysis},
number = C,
volume = 378,
place = {United States},
year = {Mon Sep 09 00:00:00 EDT 2019},
month = {Mon Sep 09 00:00:00 EDT 2019}
}
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Works referenced in this record:
Atomically Dispersed Supported Metal Catalysts
journal, July 2012
- Flytzani-Stephanopoulos, Maria; Gates, Bruce C.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 3, Issue 1
Alkali-Metal-Promoted Pt/TiO2 Opens a More Efficient Pathway to Formaldehyde Oxidation at Ambient Temperatures
journal, August 2012
- Zhang, Changbin; Liu, Fudong; Zhai, Yanping
- Angewandte Chemie International Edition, Vol. 51, Issue 38
Activation of surface lattice oxygen in single-atom Pt/CeO 2 for low-temperature CO oxidation
journal, December 2017
- Nie, Lei; Mei, Donghai; Xiong, Haifeng
- Science, Vol. 358, Issue 6369
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013
- Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
- Accounts of Chemical Research, Vol. 46, Issue 8
Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011
- Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
- Nature Chemistry, Vol. 3, Issue 8
Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts
journal, November 2017
- Shan, Junjun; Li, Mengwei; Allard, Lawrence F.
- Nature, Vol. 551, Issue 7682
Remarkable Performance of Ir 1 /FeO x Single-Atom Catalyst in Water Gas Shift Reaction
journal, October 2013
- Lin, Jian; Wang, Aiqin; Qiao, Botao
- Journal of the American Chemical Society, Vol. 135, Issue 41
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping
journal, July 2016
- Jones, J.; Xiong, H.; DeLaRiva, A. T.
- Science, Vol. 353, Issue 6295
Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation
journal, March 2018
- Li, Hongliang; Wang, Liangbing; Dai, Yizhou
- Nature Nanotechnology, Vol. 13, Issue 5
Tuning selectivity of electrochemical reactions by atomically dispersed platinum catalyst
journal, March 2016
- Choi, Chang Hyuck; Kim, Minho; Kwon, Han Chang
- Nature Communications, Vol. 7, Issue 1
Single-Atom Pt Catalyst for Effective C–F Bond Activation via Hydrodefluorination
journal, September 2018
- Huang, Dahong; de Vera, Glen Andrew; Chu, Chiheng
- ACS Catalysis, Vol. 8, Issue 10
Photochemical route for synthesizing atomically dispersed palladium catalysts
journal, May 2016
- Liu, P.; Zhao, Y.; Qin, R.
- Science, Vol. 352, Issue 6287
Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation
journal, July 2017
- Zhang, Zailei; Zhu, Yihan; Asakura, Hiroyuki
- Nature Communications, Vol. 8, Issue 1
Hexairidium Clusters Supported on γ-Al 2 O 3 : Synthesis, Structure, and Catalytic Activity for Toluene Hydrogenation
journal, January 1996
- Zhao, A.; Gates, B. C.
- Journal of the American Chemical Society, Vol. 118, Issue 10
Tetrairidium clusters supported on .gamma.-alumina: formation from [Ir4(CO)12] and carbon monoxide-induced morphology changes
journal, May 1993
- Kawi, S.; Chang, J. R.; Gates, B. C.
- The Journal of Physical Chemistry, Vol. 97, Issue 20
CO Oxidation on Supported Single Pt Atoms: Experimental and ab Initio Density Functional Studies of CO Interaction with Pt Atom on θ-Al 2 O 3 (010) Surface
journal, August 2013
- Moses-DeBusk, Melanie; Yoon, Mina; Allard, Lawrence F.
- Journal of the American Chemical Society, Vol. 135, Issue 34
Probe Microscope Observation of Platinum Atoms Deposited on the TiO 2 (110)-(1 × 1) Surface
journal, July 2006
- Sasahara, Akira; Pang, Chi Lun; Onishi, Hiroshi
- The Journal of Physical Chemistry B, Vol. 110, Issue 27
Oxidation-Induced Structural Changes in Sub-Nanometer Platinum Supported on Alumina
journal, June 2015
- Moses-DeBusk, Melanie; Allard, Lawrence F.; Blom, Douglas A.
- ChemCatChem, Vol. 7, Issue 15
Advantages of MgAlO x over γ-Al 2 O 3 as a Support Material for Potassium-Based High-Temperature Lean NO x Traps
journal, July 2015
- Luo, Jinyong; Gao, Feng; Karim, Ayman M.
- ACS Catalysis, Vol. 5, Issue 8
Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy
journal, March 2010
- Krivanek, Ondrej L.; Chisholm, Matthew F.; Nicolosi, Valeria
- Nature, Vol. 464, Issue 7288
Imaging single atoms using secondary electrons with an aberration-corrected electron microscope
journal, September 2009
- Zhu, Y.; Inada, H.; Nakamura, K.
- Nature Materials, Vol. 8, Issue 10
Direct Imaging of Pt Single Atoms Adsorbed on TiO 2 (110) Surfaces
journal, December 2013
- Chang, Teng-Yuan; Tanaka, Yusuke; Ishikawa, Ryo
- Nano Letters, Vol. 14, Issue 1
Migration of Single Iridium Atoms and Tri-iridium Clusters on MgO Surfaces: Aberration-Corrected STEM Imaging and Ab Initio Calculations
journal, November 2015
- Han, Chang Wan; Iddir, Hakim; Uzun, Alper
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
Highly Efficient Catalysis of Preferential Oxidation of CO in H 2 -Rich Stream by Gold Single-Atom Catalysts
journal, September 2015
- Qiao, Botao; Liu, Jiaxin; Wang, Yang-Gang
- ACS Catalysis, Vol. 5, Issue 11
High-resolution detection of Au catalyst atoms in Si nanowires
journal, February 2008
- Allen, Jonathan E.; Hemesath, Eric R.; Perea, Daniel E.
- Nature Nanotechnology, Vol. 3, Issue 3
Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016
- Yin, Peiqun; Yao, Tao; Wu, Yuen
- Angewandte Chemie International Edition, Vol. 55, Issue 36
Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
journal, November 2014
- Yang, Ming; Li, Sha; Wang, Yuan
- Science, Vol. 346, Issue 6216
Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO 2
journal, September 2017
- DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly
- Journal of the American Chemical Society, Vol. 139, Issue 40
Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015
- Ding, K.; Gulec, A.; Johnson, A. M.
- Science, Vol. 350, Issue 6257
Water-Mediated Mars–Van Krevelen Mechanism for CO Oxidation on Ceria-Supported Single-Atom Pt 1 Catalyst
journal, December 2016
- Wang, Chunlei; Gu, Xiang-Kui; Yan, Huan
- ACS Catalysis, Vol. 7, Issue 1
Towards ALD thin film stabilized single-atom Pd 1 catalysts
journal, January 2016
- Piernavieja-Hermida, Mar; Lu, Zheng; White, Anderson
- Nanoscale, Vol. 8, Issue 33
Zeolite- and MgO-Supported Molecular Iridium Complexes: Support and Ligand Effects in Catalysis of Ethene Hydrogenation and H–D Exchange in the Conversion of H 2 + D 2
journal, October 2011
- Lu, Jing; Serna, Pedro; Gates, Bruce C.
- ACS Catalysis, Vol. 1, Issue 11
A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms
journal, July 2014
- Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong
- Angewandte Chemie International Edition, Vol. 53, Issue 34
Direct Observation of a Long-Lived Single-Atom Catalyst Chiseling Atomic Structures in Graphene
journal, January 2014
- Wang, Wei Li; Santos, Elton J. G.; Jiang, Bin
- Nano Letters, Vol. 14, Issue 2
Design of a Highly Active Ir/Fe(OH) x Catalyst: Versatile Application of Pt-Group Metals for the Preferential Oxidation of Carbon Monoxide
journal, February 2012
- Lin, Jian; Qiao, Botao; Liu, Jingyue
- Angewandte Chemie International Edition, Vol. 51, Issue 12
Water-Gas Shift Activity of Atomically Dispersed Cationic Platinum versus Metallic Platinum Clusters on Titania Supports
journal, December 2016
- Ammal, Salai Cheettu; Heyden, Andreas
- ACS Catalysis, Vol. 7, Issue 1
Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina
journal, September 2014
- Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen
- Nature Communications, Vol. 5, Issue 1
Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts
journal, December 2018
- Lu, Yubing; Wang, Jiamin; Yu, Liang
- Nature Catalysis, Vol. 2, Issue 2
The statistics of surface atoms and surface sites on metal crystals
journal, June 1969
- Van Hardeveld, R.; Hartog, F.
- Surface Science, Vol. 15, Issue 2
Colloidal nanoparticle size control: experimental and kinetic modeling investigation of the ligand–metal binding role in controlling the nucleation and growth kinetics
journal, January 2017
- Mozaffari, Saeed; Li, Wenhui; Thompson, Coogan
- Nanoscale, Vol. 9, Issue 36
Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis
journal, August 2012
- An, Kwangjin; Somorjai, Gabor A.
- ChemCatChem, Vol. 4, Issue 10
In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol
journal, September 2012
- Karim, Ayman M.; Howard, Christopher; Roberts, Benjamin
- ACS Catalysis, Vol. 2, Issue 11
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
IFEFFIT : interactive XAFS analysis and FEFF fitting
journal, March 2001
- Newville, Matthew
- Journal of Synchrotron Radiation, Vol. 8, Issue 2
Multiple-scattering calculations of x-ray-absorption spectra
journal, July 1995
- Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A.
- Physical Review B, Vol. 52, Issue 4
A diagnostic test of the kinetic regime in a packed bed reactor
journal, March 1967
- Koros, R. M.; Nowak, E. J.
- Chemical Engineering Science, Vol. 22, Issue 3
Experimental criterion for the absence of artifacts in the measurement of rates of heterogeneous catalytic reactions
journal, November 1982
- Madon, Rostam J.; Boudart, Michel
- Industrial & Engineering Chemistry Fundamentals, Vol. 21, Issue 4, p. 438-447
A General Mechanism for Stabilizing the Small Sizes of Precious Metal Nanoparticles on Oxide Supports
journal, September 2014
- Li, Wei-Zhen; Kovarik, Libor; Mei, Donghai
- Chemistry of Materials, Vol. 26, Issue 19
First-Principles Thermodynamics Study of Spinel MgAl 2 O 4 Surface Stability
journal, August 2016
- Cai, Qiuxia; Wang, Jian-guo; Wang, Yong
- The Journal of Physical Chemistry C, Vol. 120, Issue 34
Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming: A combined experimental and theoretical study
journal, July 2014
- Mei, Donghai; Glezakou, Vassiliki-Alexandra; Lebarbier, Vanessa
- Journal of Catalysis, Vol. 316
Oxide- and Zeolite-Supported Isostructural Ir(C 2 H 4 ) 2 Complexes: Molecular-Level Observations of Electronic Effects of Supports as Ligands
journal, August 2012
- Lu, Jing; Aydin, Ceren; Browning, Nigel D.
- Langmuir, Vol. 28, Issue 35
Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands
journal, October 2011
- Lu, Jing; Serna, Pedro; Aydin, Ceren
- Journal of the American Chemical Society, Vol. 133, Issue 40
Metal Atoms and Particles on Oxide Supports: Probing Structure and Charge by Infrared Spectroscopy
journal, September 2001
- Frank, Martin; Bäumer, Marcus; Kühnemuth, Ralf
- The Journal of Physical Chemistry B, Vol. 105, Issue 36
The effect of particle size in the adsorption of carbon monoxide on iridium: An infrared investigation
journal, July 1983
- Toolenaar, F.
- Journal of Catalysis, Vol. 82, Issue 1
A 13 C NMR study of the adsorbed states of CO on Rh dispersed on Al 2 O 3
journal, July 1980
- Duncan, T. M.; Yates, J. T.; Vaughan, R. W.
- The Journal of Chemical Physics, Vol. 73, Issue 2
Quantitative determination of (3-aminopropyl)triethoxysilane on silica gel surface using diffuse reflectance infrared Fourier transform spectrometry
journal, May 1986
- Murthy, R. S. Shreedhara.; Leyden, D. E.
- Analytical Chemistry, Vol. 58, Issue 6
New Contributions to the Optics of Intensely Light-Scattering Materials Part I
journal, January 1948
- Kubelka, Paul
- Journal of the Optical Society of America, Vol. 38, Issue 5
Diffuse reflectance measurements by infrared Fourier transform spectrometry
journal, November 1978
- Fuller, Michael P.; Griffiths, Peter R.
- Analytical Chemistry, Vol. 50, Issue 13
Deconvolution and Curve Fitting of IR Spectra for CO Adsorbed on Pt/K-LTL: Potassium Promoter Effect and Adsorption Site Distribution
journal, January 1996
- Kappers, M. J.; Miller, J. T.; Koningsberger, D. C.
- The Journal of Physical Chemistry, Vol. 100, Issue 8
CO2 chemisorption and evidence of the CO oxidation–chemisorption mechanisms on sodium cobaltate
journal, July 2015
- Vera, Elizabeth; Alcántar-Vázquez, Brenda; Pfeiffer, Heriberto
- Chemical Engineering Journal, Vol. 271
Utilizing Quantitative in Situ FTIR Spectroscopy To Identify Well-Coordinated Pt Atoms as the Active Site for CO Oxidation on Al 2 O 3 -Supported Pt Catalysts
journal, July 2016
- Kale, Matthew J.; Christopher, Phillip
- ACS Catalysis, Vol. 6, Issue 8
Electronic Structure of IrO 2 : The Role of the Metal d Orbitals
journal, May 2015
- Ping, Yuan; Galli, Giulia; Goddard, William A.
- The Journal of Physical Chemistry C, Vol. 119, Issue 21
Site-Resolved Cu 2 O Catalysis in the Oxidation of CO
journal, February 2019
- Zhang, Zhenhua; Wu, Hong; Yu, Zongyou
- Angewandte Chemie International Edition, Vol. 58, Issue 13
Study of CO Oxidation Kinetics on Rh/Ceria
journal, November 1995
- Bunluesin, T.; Cordatos, H.; Gorte, R. J.
- Journal of Catalysis, Vol. 157, Issue 1
Structure sensitivity via decoration of low-coordination exposed metal atoms: CO oxidation catalysis on Pt clusters
journal, May 2013
- García-Diéguez, Mónica; Iglesia, Enrique
- Journal of Catalysis, Vol. 301
Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters
journal, March 2011
- Allian, Ayman D.; Takanabe, Kazuhiro; Fujdala, Kyle L.
- Journal of the American Chemical Society, Vol. 133, Issue 12
Works referencing / citing this record:
Origin of the High CO Oxidation Activity on CeO 2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?
journal, March 2020
- Lu, Yubing; Thompson, Coogan; Kunwar, Deepak
- ChemCatChem, Vol. 12, Issue 6