Abstract
Metal–organic frameworks (MOFs) are a promising platform for assembling large concentrations of molecular catalysts on surfaces to drive the electroreduction of CO2. Yet until now, these MOF-based systems were shown to produce only 2-electron/proton products, i.e., CO or formic acid. Herein, it is demonstrated that a cobalt 5,10,15,20-tetra(4-carboxyphenyl) porphyrin (CoTCPP)-based MOF can produce significant quantities of an 8-electron/proton CH4, via a photo-assisted electrocatalytic approach. Specifically, detailed electrochemical and spectro-electrochemical analyses show that the addition of light illumination during electrocatalysis promotes the stabilization of a catalyst-bound CO intermediate, allowing its further reduction to the final product, CH4. Using the photo-assisted electrocatalysis method, maximum CH4 Faradaic efficiency of 14% was obtained at a low potential of −0.49 V NHE. Hence, the presented concept provides an additional step toward the design of more efficient MOF-based electrocatalytic systems.
| Original language | English |
|---|---|
| Article number | 2201068 |
| Journal | Solar RRL |
| Volume | 7 |
| Issue number | 5 |
| DOIs | |
| State | Published - Mar 2023 |
| Externally published | Yes |
Bibliographical note
Publisher Copyright:© 2023 The Authors. Solar RRL published by Wiley-VCH GmbH.
Funding
The authors thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support in material characterization. The project leading to this application has received funding from European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme under grant agreement no. 947655. This work was also partially funded by the Israel Science Foundation (ISF) (Grant No. 1267/22). R.I. thanks the Arianne de Rothschild scholarship for female Ph.D. students from the Rothschild Caesarea Foundation, and the Negev scholarship from the Ben‐Gurion University of the Negev for financial support. S.M. is thankful for the Kreitman postdoctoral fellowship. The authors thank Nitzan Shauloff for the graphic design of the TOC figure. The authors thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support in material characterization. The project leading to this application has received funding from European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme under grant agreement no. 947655. This work was also partially funded by the Israel Science Foundation (ISF) (Grant No. 1267/22). R.I. thanks the Arianne de Rothschild scholarship for female Ph.D. students from the Rothschild Caesarea Foundation, and the Negev scholarship from the Ben-Gurion University of the Negev for financial support. S.M. is thankful for the Kreitman postdoctoral fellowship. The authors thank Nitzan Shauloff for the graphic design of the TOC figure.
| Funders | Funder number |
|---|---|
| Arianne de Rothschild | |
| Ilse Katz Institute for Nanoscale Science and Technology | |
| European Commission | |
| Rothschild Caesarea Foundation | |
| Israel Science Foundation | 1267/22 |
| Ben-Gurion University of the Negev | |
| Horizon 2020 | 947655 |
Keywords
- CO reduction reaction (CORR)
- electrocatalysis
- metal–organic frameworks (MOFs)
- molecular catalysts