Activation of Lattice and Adatom Oxygen by Highly Stable Ceria-Supported Cu Single Atoms

García-Vargas, Carlos E.; Collinge, Gregory; Yun, Dongmin; Lee, Mal-Soon; Muravev, Valery; Su, Ya-Qiong; Pereira-Hernández, Xavier Isidro; Jiang, Dong; Glezakou, Vassiliki-Alexandra; Hensen, Emiel J. M.; Rousseau, Roger; Datye, Abhaya K.; Wang, Yong

doi:10.1021/acscatal.2c04001

Title: Activation of Lattice and Adatom Oxygen by Highly Stable Ceria-Supported Cu Single Atoms

Journal Article · Tue Oct 25 00:00:00 UTC 2022 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.2c04001 · OSTI ID:1900519

^[1];

^[2]; Yun, Dongmin ^[3];

^[2];

^[4]; Su, Ya-Qiong ^[4];

^[5];

^[3];

^[2];

^[4];

^[2];

^[6];

^[5]

Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
Washington State Univ., Pullman, WA (United States)
Eindhoven Univ. of Technology (Netherlands)
Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
Univ. of New Mexico, Albuquerque, NM (United States)

Requiring catalysts to be both active yet stable over long periods of time under variable reaction conditions including high and low temperatures is a daunting challenge due to the almost mutual exclusivity of these constraints. Using CO oxidation as a probe reaction, in this work we demonstrate that thermally stable single atom copper catalysts prepared by high temperature synthesis (atom trapping) on ceria can achieve this feat by allowing modulation of the Cu charge state through facile charge transfer between active site and support. This provides the catalysts with an ability to activate either lattice or adatom oxygen atoms, accessing additional reaction channels depending on the reaction conditions. Such adaptability allows dynamic response of catalysts enabling them to remain active under variable reaction conditions. The inherent stability of the catalyst arises from the enhanced strength of the Cu-O interactions from high temperature synthesis that exist even when Cu oxidation state varies, which retards sintering and deactivation. As we show here, one can circumvent the dilemma of designing catalysts that are simultaneously active and stable by matching the redox properties of the active site and support and establishing an environmental adaptability around the active sites.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1900519

Report Number(s):: PNNL-SA-169472

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 21 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (67)

Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria** Kim, Yongseon; Collinge, Greg; Lee, Mal‐Soon Angewandte Chemie International Edition, Vol. 60, Issue 42 https://doi.org/10.1002/ANIE.202105750	journal	July 2021
Optimum Balance of Cu ⁺ and Oxygen Vacancies of CuO _x -CeO ₂ Composites for CO Oxidation Based on Thermal Treatment: Optimum Balance of Cu ⁺ and Oxygen Vacancies of CuO _x -CeO ₂ Composites for CO Oxidation Based on Thermal Treatment Liu, Baolin; Li, Yizhao; Cao, Yali European Journal of Inorganic Chemistry, Vol. 2019, Issue 13 https://doi.org/10.1002/ejic.201801451	journal	March 2019
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
cp2k: atomistic simulations of condensed matter systems Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1159	journal	June 2013
Total Oxidation of Carbon-Monoxide and Methane over Transition Metal Fluorite Oxide Composite Catalysts Liu, W.; Flytzanistephanopoulos, M. Journal of Catalysis, Vol. 153, Issue 2 https://doi.org/10.1006/JCAT.1995.1133	journal	May 1995
Aftertreatment Protocols for Catalyst Characterization and Performance Evaluation: Low-Temperature Oxidation, Storage, Three-Way, and NH3-SCR Catalyst Test Protocols Rappé, Kenneth G.; DiMaggio, Craig; Pihl, Josh A. Emission Control Science and Technology, Vol. 5, Issue 2 https://doi.org/10.1007/s40825-019-00120-7	journal	April 2019
Temperature-programmed reduction. Parametric sensitivity and estimation of kinetic parameters Monti, D. Journal of Catalysis, Vol. 83, Issue 2 https://doi.org/10.1016/0021-9517(83)90058-1	journal	October 1983
Influence of adsorption and mass transfer effects on temperature-programmed desorption from porous catalysts Rieck, J. Journal of Catalysis, Vol. 85, Issue 1 https://doi.org/10.1016/0021-9517(84)90118-0	journal	January 1984
On the role of redox properties of CuO/CeO2 catalysts in the preferential oxidation of CO in H2-rich gases Caputo, Tiziana; Lisi, Luciana; Pirone, Raffaele Applied Catalysis A: General, Vol. 348, Issue 1 https://doi.org/10.1016/J.APCATA.2008.06.025	journal	September 2008
Atomically Dispersed Dopants for Stabilizing Ceria Surface Area Alcala, Ryan; DeLaRiva, Andrew; Peterson, Eric J. Applied Catalysis B: Environmental, Vol. 284 https://doi.org/10.1016/J.APCATB.2020.119722	journal	May 2021
Quantum Theory of Atoms in Molecules–Dalton Revisited Bader, R. F. W.; Nguyen-Dang, T. T. Advances in Quantum Chemistry https://doi.org/10.1016/S0065-3276(08)60326-3	book	January 1981
Transition metal-promoted oxidation catalysis by fluorite oxides: A study of CO oxidation over CuCeO2 Liu, Wei; Flytzani-Stephanopoulos, Maria The Chemical Engineering Journal and the Biochemical Engineering Journal, Vol. 64, Issue 2 https://doi.org/10.1016/S0923-0467(96)03135-1	journal	November 1996
Electronic and geometric structure of the copper-ceria interface on Cu/CeO2 catalysts Zhou, Yan; Chen, Aling; Ning, Jing Chinese Journal of Catalysis, Vol. 41, Issue 6 https://doi.org/10.1016/S1872-2067(20)63540-9	journal	June 2020
Effect of moisture on the active species in Cu–CeO2 catalyst Zhang, W. J.; PalDey, S.; Deevi, S. Applied Catalysis A: General, Vol. 295, Issue 2 https://doi.org/10.1016/j.apcata.2005.08.020	journal	November 2005
Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O Lee, Hyun Chan; Kim, Dong Hyun Catalysis Today, Vol. 132, Issue 1-4 https://doi.org/10.1016/j.cattod.2007.12.028	journal	March 2008
Catalytic control of emissions from cars Twigg, Martyn V. Catalysis Today, Vol. 163, Issue 1 https://doi.org/10.1016/j.cattod.2010.12.044	journal	April 2011
Preferential oxidation of CO in excess H2 over CuO/CeO2 catalysts: Performance as a function of the copper coverage and exposed face present in the CeO2 support Monte, M.; Gamarra, D.; López Cámara, A. Catalysis Today, Vol. 229 https://doi.org/10.1016/j.cattod.2013.10.078	journal	June 2014
Dispersion of copper on ceria for the low-temperature water-gas shift reaction Ning, Jing; Zhou, Yan; Chen, Aling Catalysis Today, Vol. 357 https://doi.org/10.1016/j.cattod.2019.07.048	journal	November 2020
Empirical correlations for axial dispersion coefficient and Peclet number in fixed-bed columns Rastegar, Seyed Omid; Gu, Tingyue Journal of Chromatography A, Vol. 1490 https://doi.org/10.1016/j.chroma.2017.02.026	journal	March 2017
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi Computer Physics Communications, Vol. 167, Issue 2 https://doi.org/10.1016/j.cpc.2004.12.014	journal	April 2005
Cerium oxide stoichiometry alteration via Sn deposition: Influence of temperature Skála, Tomáš; Šutara, František; Prince, Kevin C. Journal of Electron Spectroscopy and Related Phenomena, Vol. 169, Issue 1 https://doi.org/10.1016/j.elspec.2008.10.003	journal	January 2009
CO oxidation over CuO/Ce1−xCuxO2−δ and Ce1−xCuxO2−δ catalysts: Synergetic effects and kinetic study Jia, Ai-Ping; Hu, Geng-Shen; Meng, Lian Journal of Catalysis, Vol. 289 https://doi.org/10.1016/j.jcat.2012.02.010	journal	May 2012
The surface chemistry of cerium oxide Mullins, David R. Surface Science Reports, Vol. 70, Issue 1 https://doi.org/10.1016/j.surfrep.2014.12.001	journal	March 2015
Adsorption and desorption of CO on Pt(111): a comprehensive analysis McEwen, J. -S.; Payne, S. H.; Kreuzer, H. J. Surface Science, Vol. 545, Issue 1-2 https://doi.org/10.1016/j.susc.2003.08.040	journal	November 2003
Adsorption and desorption of CO on Ru(0001): A comprehensive analysis Payne, S. H.; McEwen, J. -S.; Kreuzer, H. J. Surface Science, Vol. 594, Issue 1-3 https://doi.org/10.1016/j.susc.2005.07.031	journal	December 2005
Lateral interactions and nonequilibrium in adsorption and desorption. Part 2. A kinetic lattice gas model for (2×2)-(3O+NO)/Ru(001) Payne, S. H.; McEwen, J. -S.; Kreuzer, H. J. Surface Science, Vol. 600, Issue 19 https://doi.org/10.1016/j.susc.2006.07.019	journal	October 2006
Morphology and defect structure of the CeO2(111) films grown on Ru(0001) as studied by scanning tunneling microscopy Lu, J. -L.; Gao, H. -J.; Shaikhutdinov, S. Surface Science, Vol. 600, Issue 22 https://doi.org/10.1016/j.susc.2006.08.023	journal	November 2006
Study of active surface centers of Pt/CeO2 catalysts prepared using radio-frequency plasma sputtering technique Stadnichenko, Andrey I.; Muravev, Valerii V.; Koscheev, Sergey V. Surface Science, Vol. 679 https://doi.org/10.1016/j.susc.2018.10.002	journal	January 2019
Interactions among supported copper-based catalyst components and their effects on performance: A review Dong, Lin; Yao, Xiaojiang; Chen, Yi Chinese Journal of Catalysis, Vol. 34, Issue 5 https://doi.org/10.1016/s1872-2067(12)60592-0	journal	May 2013
Norm-Conserving Pseudopotentials and Basis Sets To Explore Lanthanide Chemistry in Complex Environments Lu, Jun-Bo; Cantu, David C.; Nguyen, Manh-Thuong Journal of Chemical Theory and Computation, Vol. 15, Issue 11 https://doi.org/10.1021/acs.jctc.9b00553	journal	October 2019
Microkinetic Modeling of the CO ₂ Desorption from Supported Multifaceted Ni Catalysts Kreitz, Bjarne; Wehinger, Gregor D.; Goldsmith, C. Franklin The Journal of Physical Chemistry C, Vol. 125, Issue 5 https://doi.org/10.1021/acs.jpcc.0c09985	journal	February 2021
Structures and Catalytic Properties of Cr–Cu Embedded CeO₂ Surfaces with Different Cr/Cu Ratios Yoshida, Hiroshi; Okabe, Yuri; Misumi, Satoshi The Journal of Physical Chemistry C, Vol. 120, Issue 47 https://doi.org/10.1021/acs.jpcc.6b08785	journal	November 2016
Introducing Time Resolution to Detect Ce ³⁺ Catalytically Active Sites at the Pt/CeO ₂ Interface through Ambient Pressure X-ray Photoelectron Spectroscopy Artiglia, Luca; Orlando, Fabrizio; Roy, Kanak The Journal of Physical Chemistry Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acs.jpclett.6b02314	journal	December 2016
Design Aspects of Doped CeO₂ for Low-Temperature Catalytic CO Oxidation: Transient Kinetics and DFT Approach Polychronopoulou, Kyriaki; AlKhoori, Ayesha A.; Efstathiou, Angelos M. ACS Applied Materials & Interfaces, Vol. 13, Issue 19 https://doi.org/10.1021/acsami.1c02934	journal	April 2021
Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations Collinge, Greg; Yuk, Simuck F.; Nguyen, Manh-Thuong ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c01501	journal	July 2020
Elucidation of the Active Sites in Single-Atom Pd ₁ /CeO ₂ Catalysts for Low-Temperature CO Oxidation Jiang, Dong; Wan, Gang; García-Vargas, Carlos E. ACS Catalysis, Vol. 10, Issue 19 https://doi.org/10.1021/acscatal.0c02480	journal	August 2020
Nature of Active Sites on Cu–CeO ₂ Catalysts Activated by High-Temperature Thermal Aging Wang, Beibei; Zhang, Hui; Xu, Wei ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c03188	journal	September 2020
Reduction of Nitric Oxide with Hydrogen on Catalysts of Singly Dispersed Bimetallic Sites Pt ₁ Co _m and Pd ₁ Co _n Nguyen, Luan; Zhang, Shiran; Wang, Lei ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b00842	journal	January 2016
Nanoshaped CuO/CeO ₂ Materials: Effect of the Exposed Ceria Surfaces on Catalytic Activity in N ₂ O Decomposition Reaction Zabilskiy, Maxim; Djinović, Petar; Tchernychova, Elena ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01044	journal	August 2015
A Thermally Stable Cr–Cu Nanostructure Embedded in the CeO₂ Surface as a Substitute for Platinum-Group Metal Catalysts Yoshida, Hiroshi; Yamashita, Noriko; Ijichi, Shota ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01847	journal	October 2015
Elucidating the Nature of the Active Phase in Copper/Ceria Catalysts for CO Oxidation Elias, Joseph S.; Artrith, Nongnuch; Bugnet, Matthieu ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02666	journal	February 2016
In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01600	journal	September 2017
Stabilizing High Metal Loadings of Thermally Stable Platinum Single Atoms on an Industrial Catalyst Support Kunwar, Deepak; Zhou, Shulan; DeLaRiva, Andrew ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.8b04885	journal	February 2019
Catalytic NO _x Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies Granger, Pascal; Parvulescu, Vasile I. Chemical Reviews, Vol. 111, Issue 5 https://doi.org/10.1021/cr100168g	journal	May 2011
Unraveling the Dynamic Nature of a CuO/CeO ₂ Catalyst for CO Oxidation in Operando : A Combined Study of XANES (Fluorescence) and DRIFTS Yao, Siyu; Mudiyanselage, Kumudu; Xu, Wenqian ACS Catalysis, Vol. 4, Issue 6 https://doi.org/10.1021/cs500148e	journal	April 2014
Properties of atoms in molecules: atomic volumes Bader, Richard F. W.; Carroll, Marshall T.; Cheeseman, James R. Journal of the American Chemical Society, Vol. 109, Issue 26 https://doi.org/10.1021/ja00260a006	journal	December 1987
The Entropies of Adsorbed Molecules Campbell, Charles T.; Sellers, Jason R. V. Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3080117	journal	October 2012
The Role of Reducible Oxide–Metal Cluster Charge Transfer in Catalytic Processes: New Insights on the Catalytic Mechanism of CO Oxidation on Au/TiO ₂ from ab Initio Molecular Dynamics Wang, Yang-Gang; Yoon, Yeohoon; Glezakou, Vassiliki-Alexandra Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja402063v	journal	July 2013
Construction of Active Site in a Sintered Copper–Ceria Nanorod Catalyst Yu, Wen-Zhu; Wang, Wei-Wei; Li, Shan-Qing Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b05419	journal	October 2019
Formation of One-Dimensional Electronic States along the Step Edges of CeO ₂ (111) Nilius, Niklas; Kozlov, Sergey M.; Jerratsch, Jan-Frederick ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn2036472	journal	January 2012
Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/NCOMMS7511	journal	March 2015
Creating single-atom Pt-ceria catalysts by surface step decoration Dvořák, Filip; Farnesi Camellone, Matteo; Tovt, Andrii Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10801	journal	February 2016
Carbon monoxide-induced adatom sintering in a Pd–Fe3O4 model catalyst Parkinson, Gareth S.; Novotny, Zbynek; Argentero, Giacomo Nature Materials, Vol. 12, Issue 8 https://doi.org/10.1038/nmat3667	journal	June 2013
Tuning Pt-CeO2 interactions by high-temperature vapor-phase synthesis for improved reducibility of lattice oxygen Pereira-Hernández, Xavier Isidro; DeLaRiva, Andrew; Muravev, Valery Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09308-5	journal	March 2019
Quantitative depth profiling of Ce ³⁺ in Pt/CeO ₂ by in situ high-energy XPS in a hydrogen atmosphere Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas Physical Chemistry Chemical Physics, Vol. 17, Issue 7 https://doi.org/10.1039/C4CP05643D	journal	January 2015
The selection of experimental conditions in temperature-programmed reduction experiments Malet, Pilar; Caballero, Alfonso Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 84, Issue 7 https://doi.org/10.1039/F19888402369	journal	January 1988
Single atom detachment from Cu clusters, and diffusion and trapping on CeO ₂ (111): implications in Ostwald ripening and atomic redispersion Wan, Qiang; Wei, Fenfei; Wang, Yingqi Nanoscale, Vol. 10, Issue 37 https://doi.org/10.1039/c8nr06232c	journal	January 2018
Accurate and efficient algorithm for Bader charge integration Yu, Min; Trinkle, Dallas R. The Journal of Chemical Physics, Vol. 134, Issue 6 https://doi.org/10.1063/1.3553716	journal	February 2011
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis Nguyen, Luan; Tao, Franklin (Feng) Review of Scientific Instruments, Vol. 87, Issue 6 https://doi.org/10.1063/1.4946877	journal	June 2016
Computer Simulation of Liquids Allen, Michael P.; Tildesley, Dominic J. https://doi.org/10.1093/oso/9780198803195.001.0001	book	June 2017
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Separable dual-space Gaussian pseudopotentials Goedecker, S.; Teter, M.; Hutter, J. Physical Review B, Vol. 54, Issue 3 https://doi.org/10.1103/PhysRevB.54.1703	journal	July 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping Jones, J.; Xiong, H.; DeLaRiva, A. T. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf8800	journal	July 2016

Similar Records

Direct alcohol synthesis reactions on cobalt modified methanol catalysts. Technical progress report

Technical Report · Mon Jun 30 04:00:00 UTC 1986 · OSTI ID:5282691

Study of the catalytically active copper species in the synthesis of methanol over Cu-Cr oxide

Journal Article · Fri Mar 01 04:00:00 UTC 1985 · J. Catal.; (United States) · OSTI ID:5872459

Monnier, J R; Hanrahan, M J; Apai, G

Dynamic Interplay between Copper Tetramers and Iron Oxide Boosting CO2 Conversion to Methanol and Hydrocarbons under Mild Conditions.

Journal Article · Tue Sep 03 04:00:00 UTC 2019 · ACS Sustainable Chemistry and Engineering · OSTI ID:1577248

Yang, Bing; Yu, Xin; Halder, Avik; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Activation of Lattice and Adatom Oxygen by Highly Stable Ceria-Supported Cu Single Atoms

Citation Formats

References (67)

Similar Records

Related Subjects