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Research Article | Open Access

Engineering the asymmetric active moiety of Ce-N3P for efficient selective oxidation of aromatic C–H bonds

Peng Zhu1,§, Aolin Li2,§, Huan Liu3 ( ), Fangping Ouyang2, Da Yang4 ( ), Zhen Zhou1,5( )
Interdisciplinary Research Center for Sustainable Energy Science and Engineering (IRC4SE2), School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
School of Physics Science and Technology, and Xinjiang Key Laboratory of Solid-State Physics and Devices, Xinjiang University, Urumqi 830046, China
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
College of Chemistry and Chemical Engineering, China University of Petroleum, Qingdao 266580, China
National Key Laboratory of Special Rare Metal Materials, Zhengzhou University, Zhengzhou 450001, China

§ Peng Zhu and Aolin Li contributed equally to this work.

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Graphical Abstract

Asymmetric N, P co-coordinated Ce single-atom sites were constructed for the activation of aromatic C–H bond. The partly substitution of coordinated N with P atom breaks the symmetry of active moiety, and raises the electron density of Ce center, then promoting the subsequent free radical reaction, thereby boosting the catalytic performance.

Abstract

Developing an effective catalyst for the selective oxidation of hydrocarbon to high value-added compounds remains as a challenge in terms of the growing global concerns about green chemistry and environmental sustainability. Herein, asymmetric nitrogen and phosphorus co-coordinated Ce single-atom sites (Ce-N3P-C) were constructed for the activation of aromatic C–H bond. Ce-N3P-C demonstrates excellent catalytic performance for efficient solvent-free aerobic oxidation of aromatic C–H bonds, especially for oxidation of ethylbenzene with 97% selectivity of acetophenone and high stability. The turnover frequency (TOF) value is 536 h−1, which is the highest level among reported non-precious-metal catalysts in a similar system. The partial substitution of coordinated N with P atom breaks the symmetry of the active moiety of Ce and raises the electron density of Ce center. The reduced valence state of metallic Ce indicates that more electrons could transfer to the antibonding π-orbital of the adsorbed O2, thus promoting the subsequent free radical reaction and accelerating the rate-determining step. The breaking of coordination symmetry of single-atom site catalyst by introducing heteroatoms to tune its active moiety paves a way to boost the catalytic performance of similar catalysts.

Keywords

heterogeneous catalysissingle-atom site catalystC–H bonds activationzeolite imidazolate framework-8 (ZIF-8)asymmetric active moiety

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Nano Research
Volume 18 Issue 6,
June 2025
Article number: 94907533
DOI: 10.26599/NR.2025.94907533
Cite this article:
Zhu P, Li A, Liu H, et al. Engineering the asymmetric active moiety of Ce-N3P for efficient selective oxidation of aromatic C–H bonds. Nano Research, 2025, 18(6): 94907533. https://doi.org/10.26599/NR.2025.94907533
Topics:
Catalytic oxidation

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Received: 24 March 2025
Revised: 30 April 2025
Accepted: 01 May 2025
Published: 19 June 2025
© The Author(s) 2025. Published by Tsinghua University Press.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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