Defect-Enhanced Low-Temperature CO Oxidation on Graphene-Supported Pt-Au Nanoclusters
Abstract
The catalytic properties of bimetallic nanoclusters are governed by a complex interplay of their size, composition, chemical ordering, and support interaction. Here, we perform a comprehensive datadriven computational study of Pt-Au nanoclusters (up to 24 atoms) using the USPEX evolutionary algorithm for global structure prediction, followed by high-throughput screening of O and CO adsorption energies with MACE foundation model and simulations of chemical reactor. We combine about 12000 DFT calculations with a machine-learning workflow that adds over 80000 additional data points, enabling extensive sampling of both ground-state and metastable isomer structures. Our analysis reveals that adsorption energies are primarily determined by the local atomic composition of the active site, not by the precise global-minimum structure. Consequently, a representative set of low-energy isomers provides the same adsorption information as the most stable clusters, a finding crucial for experiment where monodisperse samples are difficult to achieve. We further demonstrate that a graphene substrate with a single carbon monovacancy strongly anchors the cluster, enhances O 2 adsorption, and lowers CO oxidation barriers by activating traditionally inert Au atoms. Molecular dynamics simulations of CO saturation show that the supported cluster undergoes an adsorption-induced reconstruction, with Pt atoms segregating to the surface, and that the support significantly alters the saturation profile compared to the free-standing cluster. This work establishes that rational design of bimetallic catalysts must account for local site chemistry, the dynamic synergy with the support, and the practical relevance of isomer ensembles.
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BibTeX
@article{chepkasov2026defectenhanced,
title = {{Defect-Enhanced Low-Temperature CO Oxidation on Graphene-Supported Pt-Au Nanoclusters}},
author = {Ilya V Chepkasov and Viktor S Ab and Aleksandra D Radina and Michail M Lukanov and Vladimir S Baturin and Mikhail Lazarev and Nikita V Ter-Oganessian and Alexey S Galushko and Mikhail N Khrizanforov and Valentine P Ananikov and Alexander G Kvashnin},
journal = {Small},
year = {2026},
month = sep,
doi = {10.1002/smll.75835},
url = {https://hal.science/hal-05768396v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Defect-Enhanced Low-Temperature CO Oxidation on Graphene-Supported Pt-Au Nanoclusters
AU - Ilya V Chepkasov
AU - Viktor S Ab
AU - Aleksandra D Radina
AU - Michail M Lukanov
AU - Vladimir S Baturin
AU - Mikhail Lazarev
AU - Nikita V Ter-Oganessian
AU - Alexey S Galushko
AU - Mikhail N Khrizanforov
AU - Valentine P Ananikov
AU - Alexander G Kvashnin
PY - 2026
DA - 2026/09/24
JO - Small
DO - 10.1002/smll.75835
UR - https://hal.science/hal-05768396v1
AB - The catalytic properties of bimetallic nanoclusters are governed by a complex interplay of their size, composition, chemical ordering, and support interaction. Here, we perform a comprehensive datadriven computational study of Pt-Au nanoclusters (up to 24 atoms) using the USPEX evolutionary algorithm for global structure prediction, followed by high-throughput screening of O and CO adsorption energies with MACE foundation model and simulations of chemical reactor. We combine about 12000 DFT calculations with a machine-learning workflow that adds over 80000 additional data points, enabling extensive sampling of both ground-state and metastable isomer structures. Our analysis reveals that adsorption energies are primarily determined by the local atomic composition of the active site, not by the precise global-minimum structure. Consequently, a representative set of low-energy isomers provides the same adsorption information as the most stable clusters, a finding crucial for experiment where monodisperse samples are difficult to achieve. We further demonstrate that a graphene substrate with a single carbon monovacancy strongly anchors the cluster, enhances O 2 adsorption, and lowers CO oxidation barriers by activating traditionally inert Au atoms. Molecular dynamics simulations of CO saturation show that the supported cluster undergoes an adsorption-induced reconstruction, with Pt atoms segregating to the surface, and that the support significantly alters the saturation profile compared to the free-standing cluster. This work establishes that rational design of bimetallic catalysts must account for local site chemistry, the dynamic synergy with the support, and the practical relevance of isomer ensembles.
SN - 1613-6810
SN - 1613-6829
ER -