Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria

Kim, Yongseon; Collinge, Greg B.; Lee, Mal‐Soon; Khivantsev, Konstantin; Cho, Sung June; Glezakou, Vassiliki‐Alexandra; Rousseau, Roger J.; Szanyi, Janos; Kwak, Ja Hun

doi:10.1002/anie.202105750

Title: Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria

Journal Article · Mon Jun 28 00:00:00 UTC 2021 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202105750 · OSTI ID:1807590

Kim, Yongseon ^[1];

^[2];

^[2]; Khivantsev, Konstantin ^[2]; Cho, Sung June ^[3];

^[2]; Rousseau, Roger J. ^[2];

^[2];

^[1]

Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Chonnam National Univ., Gwangju (Korea, Republic of)

The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. Here we provide evidence that this prediction is not necessarily true. As a case in point, we show that the specific activity over ceria-supported single Pd atoms linearly increases with metal atom density, originating from the cumulative enhancement of CeO₂ reducibility. The long-range electrostatic footprints (≈1.5 nm) around each Pd site overlap with each other as surface Pd density increases, resulting in an observed deviation from constant specific activity. These cooperative effects exhaust previously active O atoms above a certain Pd density, leading to their permanent removal and a consequent drop in reaction rate. The findings of our combined experimental and computational study show that the specific catalytic activity of reducible oxide-supported single-atom catalysts can be tuned by varying the surface density of single metal atoms.

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

Sponsoring Organization:: National Research Foundation of Korea (NRF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1807590

Report Number(s):: PNNL-SA-159438

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 42 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Fabrication of Single-Atom Catalysts with Precise Structure and High Metal Loading Wang, Jing; Li, Zhijun; Wu, Yuen Advanced Materials, Vol. 30, Issue 48 https://doi.org/10.1002/adma.201801649	journal	October 2018
Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis Li, Xuning; Yang, Xiaofeng; Huang, Yanqiang Advanced Materials, Vol. 31, Issue 50 https://doi.org/10.1002/adma.201902031	journal	July 2019
FeO _x supported single‐atom Pd bifunctional catalyst for water gas shift reaction Sun, Xiucheng; Lin, Jian; Zhou, Yanliang AIChE Journal, Vol. 63, Issue 9 https://doi.org/10.1002/aic.15759	journal	May 2017
Die facettenreiche Reaktivität heterogener Einzelatom‐Katalysatoren Mitchell, Sharon; Vorobyeva, Evgeniya; Pérez‐Ramírez, Javier Angewandte Chemie, Vol. 130, Issue 47 https://doi.org/10.1002/ange.201806936	journal	November 2018
Ultrahigh‐Loading Zinc Single‐Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media Li, Jia; Chen, Siguo; Yang, Na Angewandte Chemie, Vol. 131, Issue 21 https://doi.org/10.1002/ange.201902109	journal	April 2019
Coordination Tunes Selectivity: Two‐Electron Oxygen Reduction on High‐Loading Molybdenum Single‐Atom Catalysts Tang, Cheng; Jiao, Yan; Shi, Bingyang Angewandte Chemie, Vol. 132, Issue 23 https://doi.org/10.1002/ange.202003842	journal	April 2020
The Multifaceted Reactivity of Single-Atom Heterogeneous Catalysts Mitchell, Sharon; Vorobyeva, Evgeniya; Pérez-Ramírez, Javier Angewandte Chemie International Edition, Vol. 57, Issue 47 https://doi.org/10.1002/anie.201806936	journal	October 2018
Ultrahigh‐Loading Zinc Single‐Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media Li, Jia; Chen, Siguo; Yang, Na Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902109	journal	May 2019
Coordination Tunes Selectivity: Two‐Electron Oxygen Reduction on High‐Loading Molybdenum Single‐Atom Catalysts Tang, Cheng; Jiao, Yan; Shi, Bingyang Angewandte Chemie International Edition, Vol. 59, Issue 23 https://doi.org/10.1002/anie.202003842	journal	April 2020
Direct Evidence for the Participation of Oxygen Vacancies in the Oxidation of Carbon Monoxide over Ceria-Supported Gold Catalysts by using Operando Raman Spectroscopy Lohrenscheit, Marno; Hess, Christian ChemCatChem, Vol. 8, Issue 3 https://doi.org/10.1002/cctc.201501129	journal	December 2015
CO Oxidation on Au Nanoparticles Supported on ZrO ₂ : Role of Metal/Oxide Interface and Oxide Reducibility Puigdollers, Antonio Ruiz; Pacchioni, Gianfranco ChemCatChem, Vol. 9, Issue 6 https://doi.org/10.1002/cctc.201601486	journal	February 2017
A Theoretical Investigation on CO Oxidation by Single-Atom Catalysts M ₁ /γ-Al ₂ O ₃ (M=Pd, Fe, Co, and Ni) Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo ChemCatChem, Vol. 9, Issue 7 https://doi.org/10.1002/cctc.201601713	journal	March 2017
Densely Populated Single Atom Catalysts Wu, Jiabin; Xiong, Liukang; Zhao, Bote Small Methods, Vol. 4, Issue 2 https://doi.org/10.1002/smtd.201900540	journal	November 2019
Flame-made Alumina Supported Pd–Pt Nanoparticles: Structural Properties and Catalytic Behavior in Methane Combustion Strobel, Reto; Grunwaldt, Jan-Dierk; Camenzind, Adrian Catalysis Letters, Vol. 104, Issue 1-2 https://doi.org/10.1007/s10562-005-7429-y	journal	October 2005
A density functional study of oxygen vacancy formation on α-Fe2O3(0001) surface and the effect of supported Au nanoparticles Hoh, Soon Wen; Thomas, Liam; Jones, Glenn Research on Chemical Intermediates, Vol. 41, Issue 12 https://doi.org/10.1007/s11164-015-1984-7	journal	March 2015
Ultrastable single-atom gold catalysts with strong covalent metal-support interaction (CMSI) Qiao, Botao; Liang, Jin-Xia; Wang, Aiqin Nano Research, Vol. 8, Issue 9 https://doi.org/10.1007/s12274-015-0796-9	journal	July 2015
Highly active Au1/Co3O4 single-atom catalyst for CO oxidation at room temperature Qiao, Botao; Lin, Jian; Wang, Aiqin Chinese Journal of Catalysis, Vol. 36, Issue 9 https://doi.org/10.1016/S1872-2067(15)60889-0	journal	September 2015
Characterization of active sites of Pd/Al2O3 model catalysts with low Pd content by luminescence, EPR and ethane hydrogenolysis Vedyagin, Aleksey A.; Volodin, Alexander M.; Stoyanovskii, Vladimir O. Applied Catalysis B: Environmental, Vol. 103, Issue 3-4 https://doi.org/10.1016/j.apcatb.2011.02.002	journal	April 2011
CO oxidation by Pd supported on CeO2(100) and CeO2(111) facets Spezzati, Giulia; Benavidez, Angelica D.; DeLaRiva, Andrew T. Applied Catalysis B: Environmental, Vol. 243 https://doi.org/10.1016/j.apcatb.2018.10.015	journal	April 2019
Redox properties and metal–support interaction of Pd/Ce0.67Zr0.33O2–Al2O3 catalyst for CO, HC and NOx elimination Lin, Siyu; Yang, Linyan; Yang, Xue Applied Surface Science, Vol. 305 https://doi.org/10.1016/j.apsusc.2014.03.153	journal	June 2014
Structural properties of alumina supported Ce–Mn solid solutions and their markedly enhanced catalytic activity for CO oxidation Venkataswamy, Perala; Jampaiah, Deshetti; Lin, Fangjian Applied Surface Science, Vol. 349 https://doi.org/10.1016/j.apsusc.2015.04.220	journal	September 2015
Investigation of palladium interaction with cerium oxide and its state in catalysts for low-temperature CO oxidation Boronin, A. I.; Slavinskaya, E. M.; Danilova, I. G. Catalysis Today, Vol. 144, Issue 3-4 https://doi.org/10.1016/j.cattod.2009.01.035	journal	June 2009
On the structure dependence of CO oxidation over CeO2 nanocrystals with well-defined surface planes Wu, Zili; Li, Meijun; Overbury, Steven H. Journal of Catalysis, Vol. 285, Issue 1 https://doi.org/10.1016/j.jcat.2011.09.011	journal	January 2012
CO Oxidation on Metal Oxide Supported Single Pt atoms: The Role of the Support Lou, Yang; Liu, Jingyue Industrial & Engineering Chemistry Research, Vol. 56, Issue 24 https://doi.org/10.1021/acs.iecr.7b01477	journal	June 2017
Changes in Surface Oxygen Vacancy Formation Energy at Metal/Oxide Perimeter Sites: A Systematic Study on Metal Nanoparticles Deposited on an In ₂ O ₃ (111) Support Hinuma, Yoyo; Toyao, Takashi; Hamamoto, Nobutsugu The Journal of Physical Chemistry C, Vol. 124, Issue 50 https://doi.org/10.1021/acs.jpcc.0c10010	journal	December 2020
Interfacial Effects of CeO ₂ -Supported Pd Nanorod in Catalytic CO Oxidation: A Theoretical Study Liu, Bing; Liu, Jian; Li, Teng The Journal of Physical Chemistry C, Vol. 119, Issue 23 https://doi.org/10.1021/acs.jpcc.5b00267	journal	May 2015
Ceria and Its Defect Structure: New Insights from a Combined Spectroscopic Approach Filtschew, Anastasia; Hofmann, Kathrin; Hess, Christian The Journal of Physical Chemistry C, Vol. 120, Issue 12 https://doi.org/10.1021/acs.jpcc.6b00959	journal	March 2016
Experimental and Theoretical Study on the Nature of Adsorbed Oxygen Species on Shaped Ceria Nanoparticles Schilling, Christian; Ganduglia-Pirovano, M. Verónica; Hess, Christian The Journal of Physical Chemistry Letters, Vol. 9, Issue 22 https://doi.org/10.1021/acs.jpclett.8b02728	journal	October 2018
Effect of Ceria Crystal Plane on the Physicochemical and Catalytic Properties of Pd/Ceria for CO and Propane Oxidation Hu, Zong; Liu, Xiaofei; Meng, Dongmei ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02617	journal	March 2016
Promoting Effects of Hydrothermal Treatment on the Activity and Durability of Pd/CeO ₂ Catalysts for CO Oxidation Jeong, Hojin; Bae, Junemin; Han, Jeong Woo ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01810	journal	September 2017
Atomically Dispersed Pd–O Species on CeO ₂ (111) as Highly Active Sites for Low-Temperature CO Oxidation Spezzati, Giulia; Su, Yaqiong; Hofmann, Jan P. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b02001	journal	September 2017
CO Oxidation on a Au/TiO ₂ Nanoparticle Catalyst via the Au-Assisted Mars–van Krevelen Mechanism Schlexer, Philomena; Widmann, Daniel; Behm, R. Jürgen ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b01751	journal	May 2018
Catalytic CO Oxidation over Au Nanoparticles Supported on CeO 2 Nanocrystals: Effect of the Au–CeO 2 Interface Ha, Hyunwoo; Yoon, Sinmyung; An, Kwangjin ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b03539	journal	October 2018
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
Dynamics of Single Pt Atoms on Alumina during CO Oxidation Monitored by Operando X-ray and Infrared Spectroscopies Dessal, Caroline; Len, Thomas; Morfin, Franck ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b00903	journal	May 2019
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300361m	journal	April 2013
Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO Sarma, Bidyut B.; Plessow, Philipp N.; Agostini, Giovanni Journal of the American Chemical Society, Vol. 142, Issue 35 https://doi.org/10.1021/jacs.0c03627	journal	August 2020
CO Oxidation on Au/TiO ₂ : Condition-Dependent Active Sites and Mechanistic Pathways Wang, Yang-Gang; Cantu, David C.; Lee, Mal-Soon Journal of the American Chemical Society, Vol. 138, Issue 33 https://doi.org/10.1021/jacs.6b04187	journal	August 2016
A Linear Scaling Relation for CO Oxidation on CeO ₂ -Supported Pd Liu, Jin-Xun; Su, Yaqiong; Filot, Ivo A. W. Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.7b13624	journal	March 2018
Constructing High-Loading Single-Atom/Cluster Catalysts via an Electrochemical Potential Window Strategy Liu, Jin-Cheng; Xiao, Hai; Li, Jun Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b06808	journal	January 2020
Unique Role of Anchoring Penta-Coordinated Al ³⁺ Sites in the Sintering of γ-Al ₂ O ₃ -Supported Pt Catalysts Mei, Donghai; Kwak, Ja Hun; Hu, Jianzhi The Journal of Physical Chemistry Letters, Vol. 1, Issue 18 https://doi.org/10.1021/jz101073p	journal	August 2010
Probing Defect Sites on CeO ₂ Nanocrystals with Well-Defined Surface Planes by Raman Spectroscopy and O ₂ Adsorption ^† Wu, Zili; Li, Meijun; Howe, Jane Langmuir, Vol. 26, Issue 21 https://doi.org/10.1021/la101723w	journal	November 2010
Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts Lin, Lili; Zhou, Wu; Gao, Rui Nature, Vol. 544, Issue 7648 https://doi.org/10.1038/nature21672	journal	March 2017
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation Zhang, Zailei; Zhu, Yihan; Asakura, Hiroyuki Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms16100	journal	July 2017
Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5885	journal	September 2014
Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts Zhao, Lu; Zhang, Yun; Huang, Lin-Bo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09290-y	journal	March 2019
A stable low-temperature H2-production catalyst by crowding Pt on α-MoC Zhang, Xiao; Zhang, Mengtao; Deng, Yuchen Nature, Vol. 589, Issue 7842 https://doi.org/10.1038/s41586-020-03130-6	journal	January 2021
An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation Therrien, Andrew J.; Hensley, Alyssa J. R.; Marcinkowski, Matthew D. Nature Catalysis, Vol. 1, Issue 3 https://doi.org/10.1038/s41929-018-0028-2	journal	March 2018
Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts Cui, Xinjiang; Li, Wu; Ryabchuk, Pavel Nature Catalysis, Vol. 1, Issue 6 https://doi.org/10.1038/s41929-018-0090-9	journal	June 2018
Highly durable metal ensemble catalysts with full dispersion for automotive applications beyond single-atom catalysts Jeong, Hojin; Kwon, Ohmin; Kim, Beom-Sik Nature Catalysis, Vol. 3, Issue 4 https://doi.org/10.1038/s41929-020-0427-z	journal	February 2020
Metal–support interaction in Pd/CeO ₂ model catalysts for CO oxidation: from pulsed laser-ablated nanoparticles to highly active state of the catalyst Slavinskaya, E. M.; Kardash, T. Yu.; Stonkus, O. A. Catalysis Science & Technology, Vol. 6, Issue 17 https://doi.org/10.1039/C6CY00319B	journal	January 2016
Low-temperature catalytic oxidation of CO over highly active mesoporous Pd/CeO ₂ –ZrO ₂ –Al ₂ O ₃ catalyst Liu, Xin; Ning, Ping; Xu, Lisi RSC Advances, Vol. 6, Issue 47 https://doi.org/10.1039/C6RA05193F	journal	January 2016
A Ti-anchored Ti ₂ CO ₂ monolayer (MXene) as a single-atom catalyst for CO oxidation Zhang, Xu; Lei, Jincheng; Wu, Dihua Journal of Materials Chemistry A, Vol. 4, Issue 13 https://doi.org/10.1039/C6TA00554C	journal	January 2016
On the active site in heterogeneous palladium selox catalysts Lee, Adam F.; Hackett, Simon F. J.; Hargreaves, Justin S. J. Green Chemistry, Vol. 8, Issue 6 https://doi.org/10.1039/b601984f	journal	January 2006
Selective acetylene hydrogenation over single metal atoms supported on Fe ₃ O ₄ (001): A first-principle study Yuk, Simuck F.; Collinge, Greg; Nguyen, Manh-Thuong The Journal of Chemical Physics, Vol. 152, Issue 15 https://doi.org/10.1063/1.5142748	journal	April 2020
CO Oxidation on a Single Pd Atom Supported on Magnesia Abbet, S.; Heiz, U.; Häkkinen, H. Physical Review Letters, Vol. 86, Issue 26 https://doi.org/10.1103/PhysRevLett.86.5950	journal	June 2001
Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R. Science, Vol. 341, Issue 6147 https://doi.org/10.1126/science.1240148	journal	July 2013
Catalytically active Au-O(OH) _x - species stabilized by alkali ions on zeolites and mesoporous oxides Yang, Ming; Li, Sha; Wang, Yuan Science, Vol. 346, Issue 6216 https://doi.org/10.1126/science.1260526	journal	November 2014
Activation of surface lattice oxygen in single-atom Pt/CeO ₂ for low-temperature CO oxidation Nie, Lei; Mei, Donghai; Xiong, Haifeng Science, Vol. 358, Issue 6369 https://doi.org/10.1126/science.aao2109	journal	December 2017

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