Theoretical Study on the Regulation of CO Preferential Oxidation Performance of Pt1@FeOx Single-Atom Catalysts by Selective Orbital Coupling

Xiuhui Zheng; Yaqian Li; Jianlin Cao; Sheng Wei; Defu Yin; Hao Yan; Yongxiao Tuo; Xiang Feng; Chaohe Yang; De Chen

doi:10.1007/s12209-026-00489-x

Transactions of Tianjin University ›› :1 -16. DOI: 10.1007/s12209-026-00489-x

Research Article

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Theoretical Study on the Regulation of CO Preferential Oxidation Performance of Pt₁@FeO_x Single-Atom Catalysts by Selective Orbital Coupling

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¹State Key Lab of Heavy Oil Processing, China University of Petroleum, 266580, Qingdao, China

²Department of Chemical Engineering, Norwegian University of Science and Technology, 7591, Trondheim, Norway

^a xiangfeng@upc.edu.cn

^b de.chen@ntnu.no

Xiuhui Zheng

Xiuhui Zheng received his B.S. degree from China University of Petroleum (East China) in 2019 and is currently a Ph.D. candidate at China University of Petroleum (East China). His research focuses on transition metal oxide catalysts and DFT/microkinetic calculation.

Yaqian Li

Yaqian Li received her Master’s degree from China University of Petroleum (East China) in 2025 and is currently a Ph.D. candidate at China University of Petroleum (East China). Her research focuses on DFT calculation and machine learning.

Jianlin Cao

Jianlin Cao received his Ph.D. degree from China University of Petroleum (East China) in 2024 and is currently a lecturer at China University of Petroleum (East China). His research focuses on CO preferential oxidation and heterogeneous catalysis.

Sheng Wei

Sheng Wei received his Master’s degree from Qingdao University of Science and Technology in 2023 and is currently a Ph.D. candidate at China University of Petroleum (East China). His research focuses on CO preferential oxidation and heterogeneous catalysis.

Defu Yin

Defu Yin received his Ph.D. degree from China University of Petroleum (East China) in 2026. His research focuses on epoxidation of olefins and catalytic activity and diffusion performance.

Hao Yan

Hao Yan received his Ph.D. degree from China University of Petroleum (East China) in 2020. He is currently a Professor at the College of Chemical Engineering, China University of Petroleum (East China). His research focuses on alcohol synthesis and upgrading, and high-value utilization of waste plastics.

Yongxiao Tuo

Yongxiao Tuo received his Ph.D. degree from East China University of Science and Technology in 2018. He is currently a Professor at the College of Chemical Engineering, China University of Petroleum (East China). His research focuses on efficient, safe, and petrochemical infrastructure-compatible organic liquid hydrogen storage and distributed hydrogen production technologies.

Xiang Feng

Xiang Feng received his Ph.D. degree from East China University of Science and Technology in 2015. He is currently a Professor at the College of Chemical Engineering, China University of Petroleum (East China). His research focuses on micro-nano structural regulation of industrial catalysts, developing high-efficiency stabilized catalysts with industrial scalability, particularly for energy and petrochemical applications.

Chaohe Yang

Chaohe Yang received his Ph.D. degree from China University of Petroleum (Beijing) in 1997. He is currently a Professor at the College of Chemical Engineering, China University of Petroleum (East China). His research spans energy chemical engineering (petrochemical and biomass conversion), materials chemical engineering (catalytic materials and functional monomers), and chemical engineering (reaction engineering, multiphase catalysis, and process intensification).

De Chen

De Chen De Chen received his Ph.D. degree from the Norwegian University of Science and Technology (NTNU) in 1998. He is currently a Full Professor at the Department of Chemical Engineering, NTNU, and has been elected as a member of the Norwegian Academy of Technological Sciences, the Norwegian Academy of Science and Letters, and Academia Europaea. His research focuses on atomic-scale engineering of industrial catalytic materials and process optimization for energy conversion, developing efficient heterogeneous catalysts for biomass transformation, CO₂ utilization, and clean hydrogen production, with a strong emphasis on industrial deployment of sustainable chemical technologies.

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Abstract

Preferential oxidation of CO (CO-PROX) is essential for H₂ purification in proton-exchange membrane fuel cells. Understanding the intrinsic electronic structural factors that influence catalytic performance is key to rational catalyst design. Using Pt single-atom catalysts supported on Fe₂O₃ and Fe₃O₄ as model systems, this work systematically investigates the relationship between structure and performance, focusing on the strength of selective orbital coupling and CO-PROX activity. On both supports, Pt single atoms are stabilized in an embedded form by substituting lattice Fe sites (Pt₁@FeO_x). Furthermore, CO and H₂ are preferentially activated at Pt-lattice O bridge sites, while O₂ activation occurs at Pt sites. Compared to the Pt₁@Fe₃O₄ system, the Pt₁@Fe₂O₃ system exhibits higher theoretical activity and selectivity, with energy barriers of 0.28 eV for CO oxidation and 0.87 eV for H₂ oxidation. The enhanced performance of Pt₁@Fe₂O₃ stems from its higher lattice O redox activity and an optimal selective orbital coupling strength, measured by the descriptor Σ|Δε| (the absolute value sum of band‑center shifts for the dominant interacting orbitals). This creates a clear energetic preference for activating CO over H₂. This study establishes a semiquantitative structure–activity relationship linking electronic structure, adsorption strength, and catalytic performance, providing concrete theoretical guidance for experimental design of high-performance CO-PROX catalysts.

Keywords

CO preferential oxidation / Pt₁@FeO_x catalysts / Theoretical study / Reaction performance regulation / Lattice O activity / Selective orbital coupling

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Xiuhui Zheng, Yaqian Li, Jianlin Cao, Sheng Wei, Defu Yin, Hao Yan, Yongxiao Tuo, Xiang Feng, Chaohe Yang, De Chen. Theoretical Study on the Regulation of CO Preferential Oxidation Performance of Pt₁@FeO_x Single-Atom Catalysts by Selective Orbital Coupling. Transactions of Tianjin University 1-16 DOI:10.1007/s12209-026-00489-x

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