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References
Zhang, X. et al. Regioselective hydroformylation of propene catalysed by rhodium-zeolite. Nature 629, 597–602 (2024).
Yu, Z. et al. Suppressing metal leaching and sintering in hydroformylation reaction by modulating the coordination of Rh single atoms with reactants. J. Am. Chem. Soc. 146, 11955–11967 (2024).
Dou, X. et al. Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite. Nat. Catal. 7, 666–677 (2024).
Franke, R., Selent, D. & Börner, A. Applied hydroformylation. Chem. Rev. 112, 5675–5732 (2012).
Ro, I. et al. Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts. Nature 609, 287–292 (2022).
Yang, C. et al. Increased productivity in ethylene carbonylation by zeolite-supported molybdenum carbonyls. J. Catal. 338, 313–320 (2016).
Yang, C., Kilos, B. A., Barton, D. G., Weitz, E. & Notestein, J. M. The role of iodide promoters and the mechanism of ethylene carbonylation catalyzed by molybdenum hexacarbonyl. J. Catal. 319, 211–219 (2014).
Fan, B. et al. Elucidation of hemilabile-coordination-induced tunable regioselectivity in single-site Rh-catalyzed heterogeneous hydroformylation. Nat. Commun. 15, 6967 (2024).
Yang, J. et al. Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes. Science 366, 1514–1517 (2019).
Wang, X. et al. Carbonylation of ethane with carbon monoxide over Zn-modified ZSM-5 zeolites studied by in situ solid-state NMR spectroscopy. J. Catal. 345, 228–235 (2017).
Zoeller, J. R., Blakely, E. M., Moncier, R. M. & Dickson, T. J. Molybdenum catalyzed carbonylation of ethylene to propionic acid and anhydride. Catal. Today 36, 227–241 (1997).
Peng, J., Geng, H. & Wu, X. The chemistry of CO: carbonylation. Chem 5, 526–552 (2019).
Koch, H. & Möller, K. E. Process for producing carboxylic acids from olefins, carbon monoxide and water. US patent 3,061,621 (1962).
Li, T., Tsumori, N., Souma, Y. & Xu, Q. Highly active and stable performance of catalytic vapor phase Koch-type carbonylation of tert-butyl alcohol over H-zeolites. Chem. Commun. 21, 2070–2071 (2003).
Luzgin, M. V., Romannikov, V. N., Stepanov, A. G. & Zamaraev, K. I. Interaction of olefins with carbon monoxide on zeolite H-ZSM-5. NMR observation of the Friedel−Crafts acylation of alkenes at ambient temperature. J. Am. Chem. Soc. 118, 10890–10891 (1996).
Fujimoto, K., Shikada, T., Omata, K. & Tominaga, H.-o. Vapor phase carbonylation of methanol with solid acid catalysts. Chem. Lett. 13, 2047–2050 (1984).
Stepanov, A. G., Luzgin, M. V., Romannikov, V. N., Sidelnikov, V. N. & Zamaraev, K. I. Formation of carboxylic acids from alcohols and olefins in zeolite H-ZSM-5 under mild conditions via trapping of alkyl carbenium ions with carbon monoxide: an in situ 13C solid state NMR study. J. Catal. 164, 411–421 (1996).
Stepanov, A. G., Luzgin, M. V., Romannikov, V. N. & Zamaraev, K. I. NMR observation of the Koch reaction in zeolite H-ZSM-5 under mild conditions. J. Am. Chem. Soc. 117, 3615–3616 (1995).
Celik, F. E., Kim, T., Mlinar, A. N. & Bell, A. T. An investigation into the mechanism and kinetics of dimethoxymethane carbonylation over FAU and MFI zeolites. J. Catal. 274, 150–162 (2010).
Celik, F. E., Kim, T. J. & Bell, A. T. Vapor-phase carbonylation of dimethoxymethane over H-Faujasite. Angew. Chem. Int. Ed. 48, 4813–4815 (2009).
Boronat, M., Martínez-Sánchez, C., Law, D. & Corma, A. Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO. J. Am. Chem. Soc. 130, 16316–16323 (2008).
Bhan, A., Allian, A. D., Sunley, G. J., Law, D. J. & Iglesia, E. Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls. J. Am. Chem. Soc. 129, 4919–4924 (2007).
Cheung, P., Bhan, A., Sunley, G. J. & Iglesia, E. Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites. Angew. Chem. Int. Ed. 45, 1617–1620 (2006).
Baerlocher, Ch., Meier, W. M. & Olson, D. H. Atlas of Zeolite Framework Types (Elsevier, 2001).
Pinar, A. B. et al. Pinpointing and quantifying the aluminum distribution in zeolite catalysts using anomalous scattering at the Al absorption edge. J. Am. Chem. Soc. 143, 17926–17930 (2021).
Dedecek, J. et al. Complex analysis of the aluminum siting in the framework of silicon-rich zeolites. A case study on ferrierites. J. Phys. Chem. C 115, 11056–11064 (2011).
Gong, X. et al. First-generation organic reaction intermediates in zeolite chemistry and catalysis. Chem. Rev. 122, 14275–14345 (2022).
Tamura, M., Shimizu, K.-i. & Satsuma, A. Comprehensive IR study on acid/base properties of metal oxides. Appl. Catal. A Gen. 433–434, 135–145 (2012).
Wichterlová, B., Tvarůžková, Z., Sobalík, Z. & Sar, P. Determination and properties of acid sites in H-ferrierite: a comparison of ferrierite and MFI structures. Microporous Mesoporous Mater. 24, 223–233 (1998).
Lakiss, L. et al. Probing the Brønsted acidity of the external surface of Faujasite-type zeolites. ChemPhysChem 21, 1873–1881 (2020).
Lesthaeghe, D., De Sterck, B., Van Speybroeck, V., Marin, G. B. & Waroquier, M. Zeolite shape-selectivity in the gem-methylation of aromatic hydrocarbons. Angew. Chem. Int. Ed. 46, 1311–1314 (2007).
Chai, J.-D. & Head-Gordon, M. Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections. Phys. Chem. Chem. Phys. 10, 6615–6620 (2008).
Frisch, M. J. et al. Gaussian 09, Revision B.01 (Gaussian, Inc., 2010).
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).
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Author notes
These authors contributed equally: Liang Qi, Yingying Sheng, Wenna Zhang
Authors and Affiliations
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
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China
Yingying Sheng & Anjie Wang
University of Chinese Academy of Sciences, Beijing, China
Linhai He, Bin Li & Zhongmin Liu
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, CA, USA
Alexis T. Bell
Authors
- Liang Qi
- Yingying Sheng
- Wenna Zhang
- Youming Ni
- Linhai He
- Bin Li
- Anjie Wang
- Wenliang Zhu
- Alexis T. Bell
- 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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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.
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.
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.
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.
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.
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.
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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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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DOI: https://doi.org/10.1038/s41586-026-11183-2