Anchoring molecular catalysts on electrode surfaces combines the high selectivity and activity of molecular systems with the practicality of heterogeneous systems. Molecular catalysts, however, are far less stable than traditional heterogeneous electrocatalysts, and therefore a method to easily replace anchored molecular catalysts that have degraded could make such electrosynthetic systems more attractive. Here we applied a non-covalent ‘click’ chemistry approach to reversibly bind molecular electrocatalysts to electrode surfaces through host–guest complexation with surface-anchored cyclodextrins. The host–guest interaction is remarkably strong and enables the flow of electrons between the electrode and the guest catalyst. Electrosynthesis in both organic and aqueous media was demonstrated on metal oxide electrodes, with stability on the order of hours. The catalytic surfaces can be recycled by controlled release of the guest from the host cavities and the readsorption of fresh guest.
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The source data for the figures in the main text and Supplementary Information are available on DataDryad (https://doi.org/10.5061/dryad.6t1g1jwxr). Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 1996726 (2), 1996727 (3) and 1976728 (4). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.
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S.D.T. thanks the University of Zurich, the University Research Priority Program LightChEC and the Swiss National Science Foundation (PYAPP2 160586) for funding. J.O. also acknowledges funding from the LightChEC. G.T., C.C., F.B.N. and M.I. thank the Swiss National Supercomputing Centre (CSCS) for generous resources under the Project IDs uzh1 and s965. C.C. thanks the INSPIRE potential master fellowship supported by the SNSF NCCR-MARVEL. G.T. thanks the Swiss National Science Foundation (Sinergia Grant No. CRSII2_160801). The authors thank T. Fox for the measurements of the solid-state NMR spectra. T. Moehl is thanked for assistance and fitting of the impedance data.
The authors declare no competing interests.
Peer review information Nature Chemistry thanks Arnold Rheingold, Javier Concepcion and the other anonymous reviewer(s) for their contribution to the peer review of this work.
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Sévery, L., Szczerbiński, J., Taskin, M. et al. Immobilization of molecular catalysts on electrode surfaces using host–guest interactions. Nat. Chem. 13, 523–529 (2021). https://doi.org/10.1038/s41557-021-00652-y
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