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Activation of light alkanes at room temperature and ambient pressure

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Abstract

Light alkane activation under mild conditions remains a substantial challenge. Here we report an aqueous reaction system capable of selectively converting light alkanes into corresponding olefins and oxygenates at room temperature and ambient pressure using Cu powder as the catalyst and O2 as the oxidant. In ethane activation, we achieved a combined production of ethylene and acetic acid at a rate of 2.27 mmol gCu−1 h−1, with a combined selectivity up to 97%. Propane is converted to propylene with a selectivity up to 94% and a production rate up to 1.83 mmol gCu−1 h−1, while methane is converted mainly to carbon dioxide, methanol and acetic acid. On the basis of catalytic experiments, isotopic labelling experiments, spectroscopic insights and density functional theory calculations, we put forward mechanistic understandings in which the C–H bond is activated by the surface oxide species generated during the oxidation process, forming alkyl groups as key reaction intermediates.

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Fig. 1: Light alkane activation with different O2 mole fractions in the feed at room temperature.
Fig. 2: Isotopic labelling investigation of ethane activation.
Fig. 3: Rate and product distribution of ethane activation.
Fig. 4: In situ SERS of ethane, propane and methane activation.
Fig. 5: Theoretical investigations on the mechanism for ethane activation.

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Data availability

The data supporting the findings of this study are available within the paper and its supplementary information files. All data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

H.Z., C.L., W.L. and Q.L. acknowledge the financial support from the State Key Laboratory of Chemical Engineering (no. SKL-ChE-23T02) and the Tsinghua University Initiative Scientific Research Program (20211080099). B.X. acknowledges the financial support from Beijing National Laboratory for Molecular Sciences. M.-J.C. acknowledges financial support from the Ministry of Science and Technology of the Republic of China under grant no. MOST 109-2113-M-006-009. W.A.G. acknowledges National Science Foundation (CBET-2005250). All NMR experiments were carried out at the BioNMR Facility, Tsinghua University Branch of China National Center for Protein Sciences (Beijing). We thank N. Xu for the assistance in the NMR data collection. We thank K. Zhao for the insightful discussion on the reaction mechanism. We thank J. Zhang for editing the paper.

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Author notes

  1. These authors contributed equally: Haochen Zhang, Chunsong Li.

Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Haochen Zhang, Chunsong Li, Wenxuan Liu, Guangsheng Luo & Qi Lu

  2. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA

    William A. Goddard III

  3. Department of Chemistry, National Cheng Kung University, Tainan, Taiwan

    Mu-Jeng Cheng

  4. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Bingjun Xu

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  1. Haochen Zhang
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Contributions

H.Z., B.X. and Q.L. designed the project and wrote the paper. H.Z., W.L. and C.L. performed alkane activation experiments and physical characterizations. C.L. and H.Z. conducted the in situ SERS experiments. H.Z. and M.-J.C. performed DFT calculations and MD simulations. W.A.G. and G.L. contributed to data analysis and discussion. Q.L. supervised the entire project.

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Correspondence to Bingjun Xu or Qi Lu.

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Competing interests

A patent application (2022100080937) on the alkane activation system based on these results has been filed by Tsinghua University and Peking University with Q.L., H.C., C.L., G.L. and B.X. as inventors.

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Nature Catalysis thanks Wenzhen Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–30 and Supplementary Tables 1–11.

Supplementary Data 1

Atomic coordinates of optimized computational models.

Supplementary Data 2

Atomic coordinates of the initial and final states of MD simulations.

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Zhang, H., Li, C., Liu, W. et al. Activation of light alkanes at room temperature and ambient pressure. Nat Catal 6, 666–675 (2023). https://doi.org/10.1038/s41929-023-00990-9

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