Cyclopalladation of a covalent organic framework for near-infrared-light-driven photocatalytic hydrogen peroxide production
Abstract Covalent organic frameworks (COFs) have been developed as photosensitizers for photocatalytic energy conversion over the past decade; however, COF photocatalysts have yet to demonstrate the ability to harvest near-infrared light (above 760 nm, approximately 53% of the solar spectrum) for fuel or chemical conversion. In this work we introduce a post-synthetic functionalization strategy for COFs by incorporating a palladacycle directly into the COF backbone, extending the light absorption of an azobenzene-based COF into the near-infrared region. This approach enables homogeneous, atomically distributed palladium functionalization with a high loading of 12 wt% and without noticeable formation of palladium nanoparticles. The cyclopalladated COF, TpAzo-CPd, was used as a catalyst for photocatalytic hydrogen peroxide production under 810 nm illumination. This study demonstrates the use of COFs for near-infrared photocatalysis and opens the door to palladium-single-site COF catalysts for a wide range of chemical transformations.
Authors
- Elio Rico
- Néstor Guijarro (ORCID: https://orcid.org/0000-0002-3277-8816)
- Andrés Rodríguez‐Camargo (ORCID: https://orcid.org/0000-0003-1325-7238)
- Christian Ochsenfeld (ORCID: https://orcid.org/0000-0002-4189-6558)
- Bettina Valeska Lotsch (ORCID: https://orcid.org/0000-0002-3094-303X)
- Liang Yao (ORCID: https://orcid.org/0000-0002-5415-6540)
- Viola Düppel (ORCID: https://orcid.org/0000-0003-2952-816X)
- Martin Etter (ORCID: https://orcid.org/0000-0002-5183-3585)
- Igor Moudrakovski (ORCID: https://orcid.org/0000-0002-8919-4766)
- Robert E. Dinnebier (ORCID: https://orcid.org/0000-0003-2778-2113)
- Daniel Gräf (ORCID: https://orcid.org/0000-0002-7640-4162)
- Maxwell W. Terban (ORCID: https://orcid.org/0000-0002-7094-1266)
- Martina Paetsch (ORCID: https://orcid.org/0009-0003-2209-4458)
- Radhika Hirpara
Institutions
- University of Stuttgart (DE)
- University of Alicante (ES)
- Deutsches Elektronen-Synchrotron DESY (DE)
- Max Planck Institute for Solid State Research (DE)
- Ludwig-Maximilians-Universität München (DE)
- South China University of Technology (CN)
Publication Details
- Journal
- Nature Synthesis
- Published
- 2025-02-10
- DOI
- https://doi.org/10.1038/s44160-024-00731-1
- Citations
- 42
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 21.75
Funders
- Solar Technologies go Hybrid
- European Commission
- Deutsche Forschungsgemeinschaft
- Max-Planck-Gesellschaft
- Deutsches Elektronen-Synchrotron
- Agencia Estatal de Investigación