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Zeolite-catalysed olefin carbonylation based on tuning spatial confinement

Nature作者：Liang Qi2026年10月21日查看原文 ↗

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Acknowledgements

We thank Y. Ma, Y. Yang, S. Gao and D. Fan for assistance with infrared spectroscopy testing and analysis, P. Gao, S. Li and S. Xu for assistance with NMR data analysis and discussion and H. Hu for assistance with BET testing and analysis, all from Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Funding

This work was supported by the National Natural Science Foundation of China (22288101, 22378388, 22472173, 22372169), the National Key R&D Program of China (2021YFA1502600) and the Youth Innovation Promotion Association, the Chinese Academy of Sciences (2023193).

Author information

Author notes

  1. These authors contributed equally: Liang Qi, Yingying Sheng, Wenna Zhang

Authors and Affiliations

  1. National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Liang Qi, Yingying Sheng, Wenna Zhang, Youming Ni, Linhai He, Bin Li, Wenliang Zhu & Zhongmin Liu

  2. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China

    Yingying Sheng & Anjie Wang

  3. University of Chinese Academy of Sciences, Beijing, China

    Linhai He, Bin Li & Zhongmin Liu

  4. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, CA, USA

    Alexis T. Bell

Authors

  1. Liang Qi
  2. Yingying Sheng
  3. Wenna Zhang
  4. Youming Ni
  5. Linhai He
  6. Bin Li
  7. Anjie Wang
  8. Wenliang Zhu
  9. Alexis T. Bell
  10. Zhongmin Liu

Contributions

L.Q., Y.S. and Y.N. made the initial discovery, designed and conducted the experiments and collected carbonylation reaction data. W. Zhang carried out DFT calculations. L.H. carried out NMR analysis. B.L. and A.W. provided experimental assistance and helpful suggestions. L.Q. and Y.S. wrote the original draft. L.Q., Y.S., Y.N., A.T.B. and Z.L. reviewed and edited the manuscript. W. Zhu and Z.L. supervised the whole project. All authors approved the final version of the manuscript.

Corresponding authors

Correspondence to Wenliang Zhu, Alexis T. Bell or Zhongmin Liu.

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Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature thanks Yue Liu, Maricruz Sanchez-Sanchez and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Detailed product distribution and yields of carbonylation products.

a,b, Products distribution and yields in propylene (a) and ethylene (b) carbonylation reactions catalysed by zeolites with different topologies. Reaction conditions: 5 MPa total pressure, PCO = 4.68 × 103 kPa, \({P}_{{{\rm{C}}}_{3}{{\rm{H}}}_{6}/{{\rm{C}}}_{2}{{\rm{H}}}_{4}}\) = 13.01 kPa, \({P}_{{{\rm{H}}}_{2}{\rm{O}}}\) = 56.2 kPa, N2 as balance gas. a, 493 K, WHSV = 0.028 g gcat−1 h−1. b, 513 K, WHSV = 0.019 g gcat−1 h−1, except for FER, which is 0.075 g gcat−1 h−1, FER is H-FER-A. WHSV, weight hourly space velocity.

Source data

Extended Data Fig. 2 Influence of CO/C3H6 partial pressure and H2O/C3H6 ratios on propylene carbonylation over FER-A.

Reaction conditions: a, 2 MPa total pressure, 473 K, PCO = 0.34–1.69 × 103 kPa, \({P}_{{{\rm{C}}}_{3}{{\rm{H}}}_{6}}\) = 14.1 kPa, \({P}_{{{\rm{H}}}_{2}{\rm{O}}}\) = 29.6 kPa, WHSV = 0.337 g gcat−1 h−1, N2 as balance gas. b, 2 MPa total pressure, 473 K, PCO = 0.98 × 103 kPa, \({P}_{{{\rm{C}}}_{3}{{\rm{H}}}_{6}}\) = 3.9–22.7 kPa, \({P}_{{{\rm{H}}}_{2}{\rm{O}}}\) = 29.6 kPa, WHSV = 0.09–0.517 g gcat−1 h−1, N2 as balance gas. c, 2 MPa total pressure, 473 K, PCO = 1.51 × 103 kPa, \({P}_{{{\rm{C}}}_{3}{{\rm{H}}}_{6}}\) = 22.6 kPa, \({P}_{{{\rm{H}}}_{2}{\rm{O}}}\) = 19.8–76.9 kPa, H2O/C3H6 mole ratio = 0.9–3.4, WHSV = 0.337 g gcat−1 h−1, N2 as balance gas.

Source data

Extended Data Fig. 3 Elementary reaction steps of ethylene and propylene carbonylation and dimerization over zeolite catalysts.

The proposed catalytic cycle of ethylene and propylene carbonylation in this work over zeolite. For both processes, the reaction proceeds with three steps: protonation of olefins to generate alkyl species, CO attack to alkyl species to form acylium cation species and H2O attack to acylium cation species to generate acids and regenerate H+. Dimerization as representative side processes are also demonstrated, which proceeds by olefins attacking to alkyl species.

Extended Data Fig. 4 XRD, thermal analysis and retained species analysis for FER catalysts after long-term carbonylation reactions over FER-A.

a,b, XRD profiles of fresh and spent H-FER-A catalysts after the propylene (a) and ethylene (b) carbonylation reactions. c,d, Thermal analysis of spent H-FER-A catalysts on the propylene (c) and ethylene (d) carbonylation reactions. e, GC-MS analysis of the species retained in the FER channels.

Source data

Extended Data Fig. 5 All of the Brønsted acid distributions in the H-FER framework.

The FER structure comprises 10-MR channels along the c-axis and FER cavities with 8-ring pore openings along the b-axis. The T1, T2 and T3 sites are accessible through the 10-ring channels (T1-O1/-O2, T2-O2/-O6, T3-O1) or the FER cavities (T1-O3/-O4, T2-O5, T3-O7/-O8). The T4 site is only accessible through the FER cavities (T4-O5/-O7).

Extended Data Fig. 6 Characterization of Brønsted acid distributions in the H-FER framework.

a–f, Fourier transform infrared spectroscopy spectra of d3-acetonitrile (FER-A (a), FER-B (b), FER-C (c), FER-D (d)), pyridine (e) and 2,6-di-tert-butyl-pyridine (f) adsorbed on the different FER samples.

Source data

Extended Data Fig. 8 DFT calculation results for ethylene and propylene carbonylation.

a, Ethylene carbonylation. b, Propylene carbonylation. The free energy barriers for propionyl and isobutyryl cation formation through carbonylation of ethyl on all T-O sites and the carbonylation of isopropyl cation on all T-O sites in 10-MRs.

Source data

Extended Data Fig. 9 Free energy profile for olefins carbonylation to acids over favourable T-O sites.

a, The free energy profile for ethylene carbonylation to PA over T2-O5 at 553 K. b, The free energy profile for propylene carbonylation to IBA over T3-O1 at 473 K.

Source data

Extended Data Fig. 10 DFT calculation results for ethylene and propylene dimerization.

a, The free energy profile for C4H9+ formation of ethylene dimerization. b, The free energy profile for C6H13+ formation of propylene dimerization.

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Supplementary information

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Qi, L., Sheng, Y., Zhang, W. et al. Zeolite-catalysed olefin carbonylation based on tuning spatial confinement. Nature (2026). https://doi.org/10.1038/s41586-026-11183-2

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