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

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

doi:10.1002/anie.202105750

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

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

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. 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.

Original language	English
Pages (from-to)	22769-22775
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	42
DOIs	https://doi.org/10.1002/anie.202105750
State	Published - Oct 11 2021
Externally published	Yes

Funding

We acknowledge the financial support from the National Research Foundation (NRF) (No. 2016R1A5A1009405, 2017R1A2B4007310). Work at the Pacific Northwest National Laboratory (PNNL) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. Computational Resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkley National Laboratory (LBNL). We acknowledge the financial support from the National Research Foundation (NRF) (No. 2016R1A5A1009405, 2017R1A2B4007310). Work at the Pacific Northwest National Laboratory (PNNL) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE‐AC05‐76RL01830. Computational Resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkley National Laboratory (LBNL).

Funders	Funder number
U.S. Department of Energy
Battelle	DE‐AC05‐76RL01830
Office of Science
Basic Energy Sciences
Lawrence Berkeley National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division
National Research Foundation of Korea	2017R1A2B4007310, 2016R1A5A1009405

Keywords

CO oxidation
Pd/CeO
electrostatic effects
reducible oxide supports

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10.1002/anie.202105750

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title = "Surface Density Dependent Catalytic Activity of Single Palladium Atoms Supported on Ceria**",

abstract = "The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. 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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AU - Kim, Yongseon

AU - Collinge, Greg

AU - Lee, Mal Soon

AU - Khivantsev, Konstantin

AU - Cho, Sung June

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Szanyi, Janos

AU - Kwak, Ja Hun

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Y1 - 2021/10/11

N2 - The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. 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.

AB - The analogy between single-atom catalysts (SACs) and molecular catalysts predicts that the specific catalytic activity of these systems is constant. 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.

KW - CO oxidation

KW - Pd/CeO

KW - electrostatic effects

KW - reducible oxide supports

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ER -

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

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