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Pickering emulsion droplets and solid microspheres acting synergistically for continuous-flow cascade reactions

Nature Catalysis volume 7, pages 295–306 (2024)Cite this article

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Abstract

Integration of multiple incompatible catalysts in one continuous-flow reaction system is of paramount significance for green synthetic chemistry. Here we develop a continuous-flow cascade catalytic system by co-packing micrometre-sized Pickering emulsion droplets and solid microspheres in a column reactor. This co-packed system can not only provide the optimum microenvironments for each incompatible catalyst but also enables them to work synergistically through directional transfer of reaction intermediates. The success of the concept is based on a phenomenon found here, namely coexistence of Pickering emulsion droplets and solid microspheres without droplet disruption even under flow and high pressure due to specific interfacial effects. As proof of concept, two chemoenzymatic cascade reactions for synthesis of chiral cyanohydrins and chiral esters were examined; both these reactions exhibited 7-fold to 77-fold enhanced catalysis efficiency compared with their batch reactions, 99% enantioselectivity and long-term operational stability (240 h).

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Fig. 1: Illustration of the co-packing of PEDs and SMs.
Fig. 2: Investigation of the interactions between liquid droplets and SMs.
Fig. 3: Chemoenzymatic cascade synthesis of cyanohydrin.
Fig. 4: Directional transport effect.
Fig. 5: Chemoenzymatic cascade synthesis of chiral esters.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work is supported by the Natural Science Foundation of China (21925203, 22332002 and 21902093), the National Key Research and Development Program of China (2021YFC2101900), the Natural Science Research Foundation of Shanxi Province (202303021211016), the 100 Talent Project of Shanxi Province, the Fund for Shanxi ‘1331 Project’ and the Foundation of State Key Laboratory of Coal Conversion (grant number J24-25-909).

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Authors and Affiliations

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi Key Laboratory of Coal-based Value-added Chemicals Green Catalysis Synthesis, Shanxi University, Taiyuan, China

    Ming Zhang, Ting Li, Jianqin Yang, Lianlian Dong, Nan Xue & Hengquan Yang

  2. Shanxi Research Institute of Huairou Laboratory, Taiyuan, China

    Ming Zhang & Hengquan Yang

  3. Food Colloids Group, School of Food Science and Nutrition, University of Leeds, Leeds, UK

    Rammile Ettelaie

  4. Department of Chemistry, University of Hull, Hull, UK

    Bernard P. Binks

  5. Institute of Resources and Environment Engineering, Shanxi University, Taiyuan, China

    Fangqin Cheng

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Contributions

H.Y. conceived and supervised the project. M.Z. executed the experiments and collected the data. T.L., J.Y and L.D. helped M.Z. to conduct part of the experiments. R.E. conducted the theoretical calculations. N.X. contributed to preparing some of the figures. B.P.B. and F.C. suggested varying the hydrophobicity of the SMs and analyzed the findings. H.Y. and M.Z. wrote the paper. All authors edited the paper.

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Correspondence to Hengquan Yang.

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Nature Catalysis thanks Yuanhai Su, Ana Jurinjak Tusek and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhang, M., Ettelaie, R., Li, T. et al. Pickering emulsion droplets and solid microspheres acting synergistically for continuous-flow cascade reactions. Nat Catal 7, 295–306 (2024). https://doi.org/10.1038/s41929-024-01110-x

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