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Direct Conversion of Methane to Methanol by CuN3 Supported on Graphene

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Abstract

Reaction mechanisms of direct conversion of methane to methanol (DCMM) catalyzed by single vacancy graphene supported single Cu atoms (Cu/C3-Gr and Cu/N3-Gr) were investigated using first principles calculations, taking N2O as the oxidant. The catalytic performance was tuned drastically by replacing three coordinated carbon atoms of active center Cu (Cu/C3-Gr) with three nitrogen atoms (Cu/N3-Gr). For Cu/N3-Gr catalyzing DCMM, a crossing between potential energy profiles of the triplet state and the singlet state occurs after transition state of C–H activation. It makes the reaction energy profile downhill and the free energy barrier of C–H activation is only 0.4 eV. The calculation results indicate that Cu/N3-Gr is likely to be an excellent catalyst for DCMM at room temperature, more superior to Cu/C3-Gr.

Graphical Abstract

By modulating micro-coordination environment of single atom Cu, both reactivity and selectivity of DCMM were improved remarkably.

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Acknowledgements

The authors acknowledge the National Key Research and Development Program of China (Grants Nos. 2016YFA0200604, 2018YFA0208600), NSFC-Henan Joint Fund (No. U2004196), Anhui Initiative in Quantum Information Technologies (Grant No. AHY090400).

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Authors and Affiliations

  1. School of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450002, Henan, China

    Jinyun Yuan, Yonghui Zhang & Junli Chen

  2. Institutes of Physical Science and Information Technology, Anhui University, Hefei, 230601, Anhui, China

    Qiquan Luo

  3. Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, Anhui, China

    Wenhua Zhang & Jinlong Yang

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  1. Jinyun Yuan
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  2. Qiquan Luo
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  3. Yonghui Zhang
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  4. Junli Chen
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  5. Wenhua Zhang
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  6. Jinlong Yang
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Yuan, J., Luo, Q., Zhang, Y. et al. Direct Conversion of Methane to Methanol by CuN3 Supported on Graphene. Catal Lett 154, 1351–1358 (2024). https://doi.org/10.1007/s10562-023-04447-3

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  • DOI: https://doi.org/10.1007/s10562-023-04447-3

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