Enhanced CO Oxidation on PtOx Raft Species Synthesized via Citric Acid-Assisted Electrostatic Adsorption

Jiaorong Yan; Qiguang Dai; Hui Wang; Zhi Qiang Wang; Jihang Yu; Sheng Dai; Matteo Monai; Bert M. Weckhuysen; Wangcheng Zhan

doi:10.1002/anie.202520136

Enhanced CO Oxidation on PtO_x Raft Species Synthesized via Citric Acid-Assisted Electrostatic Adsorption

Jiaorong Yan
, Qiguang Dai
, Hui Wang
, Zhi Qiang Wang
, Jihang Yu
, Sheng Dai
, Matteo Monai
, Bert M. Weckhuysen
, Wangcheng Zhan

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

Abstract

Platinum-based catalysts have attracted considerable attention for CO oxidation, with their activity critically dependent on the nanostructures of Pt species. Herein, raft-structured PtO_x species on CeO₂ support (Pt/CeO₂-CA) were successfully prepared via a citric acid-assisted strong electrostatic adsorption (SEA) method, which leveraged competitive adsorption between noble metal precursors and organic compounds. The Pt/CeO₂-CA catalyst exhibits a T₅₀ (temperature for 50% CO conversion) over 120 °C lower than those of Pt single atoms and PtO_x clusters-based catalysts, and the lowest apparent activation energy among the catalysts investigated, as well as reported analogues, demonstrating its excellent activity in CO oxidation. Combined catalyst characterization and density functional theory (DFT) calculations demonstrate enhanced CO adsorption on PtO_x rafts with respect to Pt/CeO₂ reference catalysts composed of Pt single atoms or PtO_x clusters, and favored CO interaction with O* atoms from PtO_x rafts and the CeO₂ surface. We propose that this mitigates CO poisoning effects by circumventing competitive adsorption with O₂, thereby accelerating the catalytic reaction. Our findings highlight promising design strategies for tuning the morphology of supported noble metal (oxide) nanostructures to further enhance their catalytic performances.

Original language	English
Article number	e20136
Journal	Angewandte Chemie - International Edition
Volume	65
Issue number	2
DOIs	https://doi.org/10.1002/anie.202520136
State	Published - Jan 9 2026
Externally published	Yes

Funding

This work was supported by the National Key Research and Development Program (2022YFB3504200, 2023YFA1508500), the National Natural Science Foundation of China (22076047, 22376061, 22106101, U21A20326), and Fundamental Research Funds for the Central Universities. M.M. and B.M.W. (Utrecht University, UU) acknowledge the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC) for funding. The authors thank the European Synchrotron Radiation Facility (ESRF) for beamtime allocation (ID24 beamline) and Dr. Kirill Lomachenko for their support and help during the X-ray absorption spectroscopy (XAS) measurements. Thanks to Joëlle Siewe (UU), Angela Melcherts (UU), and Mariangela Biggiero (UU) for their help with the XAS measurements. The authors thank Bram Kappé (UU) for the Python script to analyze the operando infrared spectroscopy data. J.Y. (ECUST and UU) and H.W. (UU) acknowledge the China Scholarship Council (CSC) for financial support. This work was supported by the National Key Research and Development Program (2022YFB3504200, 2023YFA1508500), the National Natural Science Foundation of China (22076047, 22376061, 22106101, U21A20326), and Fundamental Research Funds for the Central Universities. M.M. and B.M.W. (Utrecht University, UU) acknowledge the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC) for funding. The authors thank the European Synchrotron Radiation Facility (ESRF) for beamtime allocation (ID24 beamline) and Dr. Kirill Lomachenko for their support and help during the X‐ray absorption spectroscopy (XAS) measurements. Thanks to Joëlle Siewe (UU), Angela Melcherts (UU), and Mariangela Biggiero (UU) for their help with the XAS measurements. The authors thank Bram Kappé (UU) for the Python script to analyze the infrared spectroscopy data. J.Y. (ECUST and UU) and H.W. (UU) acknowledge the China Scholarship Council (CSC) for financial support. operando

Keywords

CO oxidation
Heterogeneous catalysis
Operando infrared spectroscopy
Platinum
X-ray absorption spectroscopy

Access to Document

10.1002/anie.202520136

Cite this

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title = "Enhanced CO Oxidation on PtOx Raft Species Synthesized via Citric Acid-Assisted Electrostatic Adsorption",

abstract = "Platinum-based catalysts have attracted considerable attention for CO oxidation, with their activity critically dependent on the nanostructures of Pt species. Herein, raft-structured PtOx species on CeO2 support (Pt/CeO2-CA) were successfully prepared via a citric acid-assisted strong electrostatic adsorption (SEA) method, which leveraged competitive adsorption between noble metal precursors and organic compounds. The Pt/CeO2-CA catalyst exhibits a T50 (temperature for 50\% CO conversion) over 120 °C lower than those of Pt single atoms and PtOx clusters-based catalysts, and the lowest apparent activation energy among the catalysts investigated, as well as reported analogues, demonstrating its excellent activity in CO oxidation. Combined catalyst characterization and density functional theory (DFT) calculations demonstrate enhanced CO adsorption on PtOx rafts with respect to Pt/CeO2 reference catalysts composed of Pt single atoms or PtOx clusters, and favored CO interaction with O* atoms from PtOx rafts and the CeO2 surface. We propose that this mitigates CO poisoning effects by circumventing competitive adsorption with O2, thereby accelerating the catalytic reaction. Our findings highlight promising design strategies for tuning the morphology of supported noble metal (oxide) nanostructures to further enhance their catalytic performances.",

keywords = "CO oxidation, Heterogeneous catalysis, Operando infrared spectroscopy, Platinum, X-ray absorption spectroscopy",

author = "Jiaorong Yan and Qiguang Dai and Hui Wang and Wang, \{Zhi Qiang\} and Jihang Yu and Sheng Dai and Matteo Monai and Weckhuysen, \{Bert M.\} and Wangcheng Zhan",

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T1 - Enhanced CO Oxidation on PtOx Raft Species Synthesized via Citric Acid-Assisted Electrostatic Adsorption

AU - Yan, Jiaorong

AU - Dai, Qiguang

AU - Wang, Hui

AU - Wang, Zhi Qiang

AU - Yu, Jihang

AU - Dai, Sheng

AU - Monai, Matteo

AU - Weckhuysen, Bert M.

AU - Zhan, Wangcheng

PY - 2026/1/9

Y1 - 2026/1/9

N2 - Platinum-based catalysts have attracted considerable attention for CO oxidation, with their activity critically dependent on the nanostructures of Pt species. Herein, raft-structured PtOx species on CeO2 support (Pt/CeO2-CA) were successfully prepared via a citric acid-assisted strong electrostatic adsorption (SEA) method, which leveraged competitive adsorption between noble metal precursors and organic compounds. The Pt/CeO2-CA catalyst exhibits a T50 (temperature for 50% CO conversion) over 120 °C lower than those of Pt single atoms and PtOx clusters-based catalysts, and the lowest apparent activation energy among the catalysts investigated, as well as reported analogues, demonstrating its excellent activity in CO oxidation. Combined catalyst characterization and density functional theory (DFT) calculations demonstrate enhanced CO adsorption on PtOx rafts with respect to Pt/CeO2 reference catalysts composed of Pt single atoms or PtOx clusters, and favored CO interaction with O* atoms from PtOx rafts and the CeO2 surface. We propose that this mitigates CO poisoning effects by circumventing competitive adsorption with O2, thereby accelerating the catalytic reaction. Our findings highlight promising design strategies for tuning the morphology of supported noble metal (oxide) nanostructures to further enhance their catalytic performances.

AB - Platinum-based catalysts have attracted considerable attention for CO oxidation, with their activity critically dependent on the nanostructures of Pt species. Herein, raft-structured PtOx species on CeO2 support (Pt/CeO2-CA) were successfully prepared via a citric acid-assisted strong electrostatic adsorption (SEA) method, which leveraged competitive adsorption between noble metal precursors and organic compounds. The Pt/CeO2-CA catalyst exhibits a T50 (temperature for 50% CO conversion) over 120 °C lower than those of Pt single atoms and PtOx clusters-based catalysts, and the lowest apparent activation energy among the catalysts investigated, as well as reported analogues, demonstrating its excellent activity in CO oxidation. Combined catalyst characterization and density functional theory (DFT) calculations demonstrate enhanced CO adsorption on PtOx rafts with respect to Pt/CeO2 reference catalysts composed of Pt single atoms or PtOx clusters, and favored CO interaction with O* atoms from PtOx rafts and the CeO2 surface. We propose that this mitigates CO poisoning effects by circumventing competitive adsorption with O2, thereby accelerating the catalytic reaction. Our findings highlight promising design strategies for tuning the morphology of supported noble metal (oxide) nanostructures to further enhance their catalytic performances.

KW - CO oxidation

KW - Heterogeneous catalysis

KW - Operando infrared spectroscopy

KW - Platinum

KW - X-ray absorption spectroscopy

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