Cobalt-Embedded Metal–Covalent Organic Frameworks for CO<sub>2</sub> Photoreduction
With the pressing urgency to reduce carbon footprint, photocatalytic carbon dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering the important role of catalytic active sites (CASs) in the catalytic processes, control and design of the density and environment of CASs could enhance the catalyst performance. Herein, we report a novel metal-covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts and conjugation through a covalently bonded backbone. MCOF-Co-315 showed a CO production rate of 1616 μmol g<sup>-1</sup> h<sup>-1</sup> utilizing Ru(bpy)<sub>3</sub>Cl<sub>2</sub> as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor with a 1.5 AM filter, vis mirror module (390-740 nm), and irradiation intensity adjusted to 1 sun and an especially outstanding apparent quantum yield (AQY) of 9.13% at 450 nm. The photocatalytic reaction was studied with electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), and in situ synchrotron Fourier Transform Infrared (FT-IR) spectroscopy, and an underlying mechanism is proposed.
Authors
- Wanpeng Lu (ORCID: https://orcid.org/0000-0003-3403-667X)
- Fabien Ceugniet
- Claudia E. Tait (ORCID: https://orcid.org/0000-0002-6337-9324)
- Agamemnon E. Crumpton (ORCID: https://orcid.org/0000-0002-0786-5205)
- Gökay Avcı (ORCID: https://orcid.org/0000-0003-4032-4088)
- Mark D. Frogley (ORCID: https://orcid.org/0000-0002-0742-5007)
- Xian’e Li (ORCID: https://orcid.org/0000-0002-9174-7593)
- Iain McCulloch (ORCID: https://orcid.org/0000-0002-6340-7217)
- Donato Decarolis (ORCID: https://orcid.org/0000-0001-5512-7090)
- Yuyun Yao
- Paul Shao (ORCID: https://orcid.org/0000-0003-2154-1407)
- Kim E. Jelfs (ORCID: https://orcid.org/0000-0001-7683-7630)
- Catherine M. Aitchison (ORCID: https://orcid.org/0000-0003-1437-8314)
- Nan Yao (ORCID: https://orcid.org/0000-0002-4081-1495)
Institutions
- Linköping University (SE)
- Princeton University (US)
- Diamond Light Source (GB)
- University of Oxford (GB)
- Dillinger Hütte (Germany) (DE)
- Imperial College London (GB)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-03-07
- DOI
- https://doi.org/10.1021/jacs.4c18450
- Citations
- 26
- Primary Topic
- Covalent Organic Framework Applications
- Type
- article
- Field-Weighted Citation Impact
- 13.46
Funders
- King Abdullah University of Science and Technology
- Vetenskapsrådet
- Engineering and Physical Sciences Research Council
- Division of Materials Research
- H2020 Energy