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Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions

Nature Energy volume 7, pages 1042–1051 (2022)Cite this article

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Abstract

Direct non-oxidative dehydrogenation of alkanes produces useful carbon feedstocks and hydrogen fuel. However, breaking the C–H bonds in alkanes typically requires high temperature, stoichiometric oxidants or high-energy ultraviolet light; processes that operate under milder conditions are attractive but tend to have poor efficiency. Here we report Pt/black TiO2 photocatalysts in which Pt species are close to each other but not directly bonded, exhibiting high performance for alkane dehydrogenation in visible to near-infrared light at room temperature. For cyclohexane dehydrogenation, the turnover number for H2 production exceeded 100,000 without any deactivation over 80 reaction cycles, far beyond thermal reactions. For methane, 8.2% conversion was achieved with 65% selectivity to propane, rather than the more common ethane. We propose that methane undergoes intramolecular dehydrogenation to produce a methylene intermediate. For C2+ alkanes, fast dehydrogenation (up to 1,440 µmol g−1 h−1) to the corresponding olefins was realized. Distinct from isolated Pt+ monomers, the collections of Pt+ monomers give better photocatalytic activity and selectivity.

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Fig. 1: Preparation and characterization of catalyst.
Fig. 2: Photocatalytic dehydrogenation of cyclohexane.
Fig. 3: Kinetic and stability test.
Fig. 4: Photocatalytic dehydrogenation of methane and light alkanes.
Fig. 5: Difference between Pt+ and Pt2+.
Fig. 6: Illustration for the dehydrogenation of different alkanes.

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Data availability

All data supporting the findings of this study are available within the paper and Supplementary Information files. Atomic coordinates of the computational studies are provided as Supplementary Data 1. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant number 92061105, 21875090), Natural Science Foundation of Jilin Province (20210101121JC, 20210509035RQ) and the Fundamental Research Funds for the Central Universities. The XAFS experiments were conducted in 1W1B beam line of Beijing Synchrotron Radiation Facility. We thank Y. Zhao at Beijing University of Chemical Technology for help with XAFS experiments.

Author information

Author notes

  1. These authors contributed equally: Lili Zhang, Le Liu, Ziye Pan.

Authors and Affiliations

  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, China

    Lili Zhang, Le Liu, Ziye Pan, Zhuoyang Gao, Guangming Wang, Keke Huang, Xiaoyue Mu & Lu Li

  2. College of Chemistry, Jilin University, Changchun, China

    Lili Zhang, Le Liu, Ziye Pan, Rui Zhang, Zhuoyang Gao, Guangming Wang, Keke Huang, Xiaoyue Mu, Fuquan Bai & Lu Li

  3. Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun, China

    Rui Zhang & Fuquan Bai

  4. Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials and Electron Microscopy Center, Jilin University, Changchun, China

    Yan Wang & Wei Zhang

  5. Institute of Atomic and Molecular Physics, Jilin University, Changchun, China

    Zhonghua Cui

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  1. Lili Zhang
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Contributions

L.Z. performed the catalyst design, synthesis, characterization, methane and cyclohexane conversion tests and data analysis. L. Liu. participated in the catalyst preparation and C2+ alkane tests. Z.G. and G.W. participated in the characterization. X.M. and K.H. provided helpful discussion. Z.P., R.Z., F.B. and Z.C. performed the DFT calculations. Y.W. and W.Z. performed the AC-HAADF-STEM measurements. L. Li. designed the study, analysed the data and wrote the paper.

Corresponding author

Correspondence to Lu Li.

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Nature Energy thanks Jier Huang, Ding Ma, Hisao Yoshida and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes, Figs. 1–44, Tables 1–8 and refs. 1–11.

Supplementary Data

Atomic coordinates for the Pt–Cl doping and Pt–O doping slabs.

Source data

Source Data Fig. 2

Data for Fig. 2a and statistical source data for Fig. 2b–d.

Source Data Fig. 3

Data for Fig. 3.

Source Data Fig. 4

Data for Fig. 4.

Source Data Fig. 5

Data for Fig. 5.

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Zhang, L., Liu, L., Pan, Z. et al. Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions. Nat Energy 7, 1042–1051 (2022). https://doi.org/10.1038/s41560-022-01127-1

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