Abstract
Hydroformylation is an industrial process for the production of aldehydes from alkenes1,2. Regioselective hydroformylation of propene to high-value n-butanal is particularly important, owing to a wide range of bulk applications of n-butanal in the manufacture of various necessities in human daily life3. Supported rhodium (Rh) hydroformylation catalysts, which often excel in catalyst recyclability, ease of separation and adaptability for continuous-flow processes, have been greatly exploited4. Nonetheless, they usually consist of rotationally flexible and sterically unconstrained Rh hydride dicarbonyl centres, only affording limited regioselectivity to n-butanal5,6,7,8. Here we show that proper encapsulation of Rh species comprising Rh(I)-gem-dicarbonyl centres within a MEL zeolite framework allows the breaking of the above model. The optimized catalyst exhibits more than 99% regioselectivity to n-butanal and more than 99% selectivity to aldehydes at a product formation turnover frequency (TOF) of 6,500 h−1, surpassing the performance of all heterogeneous and most homogeneous catalysts developed so far. Our comprehensive studies show that the zeolite framework can act as a scaffold to steer the reaction pathway of the intermediates confined in the space between the zeolite framework and Rh centres towards the exclusive formation of n-butanal.
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Data availability
The authors declare that all the data supporting the findings of this study are available within the paper and its Supplementary Information files and are also available from the corresponding author on reasonable request. Source data are provided with this paper.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (nos. 21972161 and 22172186), Major Science and Technology Project of Ordos City (no. 2022EEDSKJZDZX001), Autonomous Research Project of State Key Laboratory of Coal Conversion (no. 2022BWZ009), Inner Mongolia Key Research and Development Program (no. 2023YFHH0009), Institute of Coal Chemistry, Chinese Academy of Sciences and Synfuels China Technology Co., Ltd. We also acknowledge the Shanghai Synchrotron Radiation Facility (SSRF) for providing the facility for XAS measurements and the Centre for High-resolution Electron Microscopy (CħEM) for the TEM tests.
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Z.C., Y.Y. and H.W. conceived the project and designed the study. X.Zha. and T.Y. conducted synthesis work, catalytic tests and other characterizations. J.Y. performed the theoretical calculations. H.H., F.S., Y.W. and Q.Z. conducted the structural characterizations. X.S., M.D., W.F., J.W., Y.S., X.Zho., K.W. and Y.L. helped with the data analysis. Z.C. and H.W. wrote the manuscript. All authors discussed the results and commented on the manuscript.
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Zhang, X., Yan, T., Hou, H. et al. Regioselective hydroformylation of propene catalysed by rhodium-zeolite. Nature (2024). https://doi.org/10.1038/s41586-024-07342-y
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DOI: https://doi.org/10.1038/s41586-024-07342-y
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