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Rh<sup>3+</sup> stabilized in KRh@MFI catalyses regioselective hydroformylation

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Abstract

Hydroformylation has been a cornerstone of industrial organometallic catalysis, with regioselectivity being a critical aspect in this process1,2. Present industrial systems use homogeneous Rh-based catalysts with expensive and toxic phosphine-containing ligands, underscoring the need to develop alternative heterogeneous catalysts that could compete with the actual homogeneous ones3. In this direction, atomically dispersed Rh catalysts have been proposed as promising candidates for hydroformylation4,5. However, achieving high regioselectivity at high conversion is still a big challenge. Here subnanometre Rh2O3 clusters are confined inside the channels of the MFI zeolite, which under reaction conditions disrupt into isolated Rh3+ and Rh+ species. Density functional theory (DFT) investigations combined with spectroscopic and catalytic studies demonstrate that Rh3+-mediated hydroformylation is energetically plausibly similar to Rh+, with Rh3+ being intrinsically more selective for hydroformylation and less selective for double-bond isomerization than Rh+. In the coexistence of both Rh3+ and Rh+ species, we demonstrate the possibility to selectively inhibit Rh+ sites through the addition of N-containing molecules such as N-methylpyrrolidine (MP) or 1-methyl-2-pyrrolidone (NMP), which preferentially coordinate to Rh+ inside MFI zeolite channel, thereby suppressing its isomerization function while leaving Rh3+ sites catalytically accessible. This strategy results in a notable enhancement of regioselectivity, with a state-of-the-art reported highest linear to branched aldehydes (l/b) ratio of 817 with 96% undecanal selectivity at 99.8% 1-decene conversion, using NMP as additive.

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Data availability

All data generated in this study are provided in the Supplementary Information and the most relevant are included in the Source Data files. All relevant data are available from the corresponding authors on request. Source data are provided with this paper.

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Acknowledgements

XAS measurements were performed at the BL-22 CLÆSS beamline of the ALBA Synchrotron with the support of ALBA staff. High-resolution HAADF-STEM and iDPC characterizations were carried out at the DME-UCA node of the Spanish Singular Infrastructure for Electron Microscopy of Materials (ICTS ELECMI). We thank J. M. Salas Sánchez for assistance with infrared measurements, V. Martin-Diaconescu for support with XAS data analysis and E. Carmona for insightful discussions. In memory of our friend and colleague M. A. Miranda.

Funding

The authors thank the ‘Severo Ochoa Programme’ of ITQ (CEX-2021-001230-S). P.C. is grateful for the financial support from the Ministerio de Ciencia, Innovación y Universidades (PID2021-1262350B-C31), the Generalitat Valenciana (CIAICO/2021/2138) and the Advanced Materials programme supported by MCIN/EU Next Generation EU (PRTR-C17.11; TED2021-130756B-C32) and Generalitat Valenciana (MFA/2022/016). M.Z. acknowledges the China Scholarship Council (CSC) for a PhD fellowship (CSC no. 202006440003). M.L.H. and J.J.C. acknowledge support from projects PID2023-150437OB-I00 and PID2022-142312NB-I00 financed by MICIU/AEI/10.13030/501100011033, MCIN/AEI/10.13039/501100011033 and ERDF (‘A way of making Europe’), as well as the Programa Operativo FEDER Andalucía 2021-2027 and the Consejería de Universidad, Investigación e Innovación, Junta de Andalucía (projects FEDER– UCA-2024-A2-26 and DGP-PIDI-2024-00685).

Author information

Authors and Affiliations

  1. Instituto de Tecnología Química (ITQ), Consejo Superior de Investigaciones Científicas, Universitat Politècnica de València, Valencia, Spain

    Minjie Zhao, Reisel Millán, Patricia Concepción & Avelino Corma

  2. CELLS - ALBA Synchrotron Radiation Facility, Cerdanyola del Vallès, Spain

    Alina Skorynina & Laura Simonelli

  3. Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad Ciencias, Universidad de Cádiz, Campus Rio San Pedro, Puerto Real, Cádiz, Spain

    Miguel Lopez Haro & José Juan Calvino

  4. Instituto de Investigación en Microscopía Electrónica y Materiales de la Universidad de Cádiz (IMEYMAT), Facultad de Ciencias, Campus Rio San Pedro, Puerto Real, Cádiz, Spain

    Miguel Lopez Haro & José Juan Calvino

Authors

  1. Minjie Zhao
  2. Reisel Millán
  3. Alina Skorynina
  4. Laura Simonelli
  5. Miguel Lopez Haro
  6. José Juan Calvino
  7. Patricia Concepción
  8. Avelino Corma

Contributions

A.C., P.C. and M.Z. designed the studies and wrote the paper. M.Z. synthesized the catalysts and carried out the catalytic testing. A.S. and L.S. performed the XAS experiments and interpretation. M.L.H. and J.J.C. carried out the microscopic studies and analysis. R.M. performed the theoretical calculations and wrote the paper, together with the rest of the authors. All authors discussed the results.

Corresponding authors

Correspondence to Patricia Concepción or Avelino Corma.

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Nature thanks Christophe Copéret and Landong Li for their contribution to the peer review of this work. Peer reviewer reports are available.

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Zhao, M., Millán, R., Skorynina, A. et al. Rh3+ stabilized in KRh@MFI catalyses regioselective hydroformylation. Nature (2026). https://doi.org/10.1038/s41586-026-11136-9

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  • DOI: https://doi.org/10.1038/s41586-026-11136-9