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Mild Oxidation of Methane to Oxygenates with O2 and CO on Fluorine Modified TS-1 Supported Rh Single-Atom Catalyst in a Flow Reactor

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Abstract

Direct catalytic conversion of methane to liquid oxygenates under mild conditions remains a challenge due to high bond energy of symmetric CH4. Isolated Rh atoms were supported on hydrophobic fluorine modified TS-1 (FTS-1). Single-atom Rh on FTS-1 catalyst was characterized with Ac-HAADF/STEM and CO adsorption FTIR. The aerobic selective conversion of methane to oxygenates was carried out in a fixed bed continuous flow reactor upon co-feeding CO and H2O at 423 K under relative low pressure (42.3 kPa CH4, 21.1 kPa CO, 10.6 kPa O2, 0.476 MPa H2O). Hydrophobic Rh/FTS-1 catalyst exhibits higher activity (151.9 molproducts/(molmetalh)) than the activity (36.4 molproducts/(molmetalh)) over hydrophilic Rh-ZSM-5 (Si/Al = 15) under such reaction conditions. Hydrophobicity of different catalysts were compared by water adsorption test. The catalytic activity of F modified TS-1 supported single-atom Rh (Rh/FTS-1) is higher than that of unmodified Rh/TS-1 which is due to its higher Lewis acidity as shown by pyridine adsorption FTIR and NH3-TPD.

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Acknowledgements

We gratefully acknowledge financial support from the NSFC of China (20567004), and technical support from the Analytical and Testing Centre of Yunnan University.

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Authors and Affiliations

  1. School of Chemistry, Yunnan University, Kunming, 650091, People’s Republic of China

    Honglin Wang, Wenyu Xin, Xiangdong Zheng, Quan Wang, Ruqin Pei & Xianjiang Dong

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  1. Honglin Wang
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  2. Wenyu Xin
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  3. Xiangdong Zheng
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Contributions

RP and XD carried out the synthesis of catalysts and catalytic reactions and wrote the first draft. WX carried out measurements, common characterization and data collection. XZ and QW carried out special characterization and data collection. HW formulated the research plan, provided core guidance, and made the revision of the manuscript.

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Correspondence to Honglin Wang.

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Wang, H., Xin, W., Zheng, X. et al. Mild Oxidation of Methane to Oxygenates with O2 and CO on Fluorine Modified TS-1 Supported Rh Single-Atom Catalyst in a Flow Reactor. Catal Lett 154, 259–269 (2024). https://doi.org/10.1007/s10562-023-04298-y

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