Abstract
Metal–organic frameworks (MOFs) are promising platforms for heterogeneous tethering of molecular CO2 reduction electrocatalysts. Yet, to further understand electrocatalytic MOF systems, one also needs to consider their capability to fine-tune the immediate chemical environment of the active site, and thus affect its overall catalytic operation. Here, we show that electrostatic secondary-sphere functionalities enable substantial improvement of CO2-to-CO conversion activity and selectivity. In situ Raman analysis reveal that immobilization of pendent positively-charged groups adjacent to MOF-residing Fe-porphyrin catalysts, stabilize weakly-bound CO intermediates, allowing their rapid release as catalytic products. Also, by varying the electrolyte's ionic strength, systematic regulation of electrostatic field magnitude was achieved, resulting in essentially 100 % CO selectivity. Thus, this concept provides a sensitive molecular-handle that adjust heterogeneous electrocatalysis on demand.
Original language | English |
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Article number | e202206085 |
Journal | Angewandte Chemie - International Edition |
Volume | 61 |
Issue number | 32 |
DOIs | |
State | Published - 8 Aug 2022 |
Externally published | Yes |
Bibliographical note
Publisher Copyright:© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Funding
We thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support in material characterization. This research was supported by the Israel Science Foundation (ISF) (grant No. 306/18), and by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 947655). L. Zhang acknowledges financial support from National Natural Science Foundation of China (nos. 22176036, 21976030). R. Shimoni thanks the Kreitman's PhD. Fellowship. We thank the Ilse Katz Institute for Nanoscale Science and Technology for the technical support in material characterization. This research was supported by the Israel Science Foundation (ISF) (grant No. 306/18), and by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No. 947655). L. Zhang acknowledges financial support from National Natural Science Foundation of China (nos. 22176036, 21976030). R. Shimoni thanks the Kreitman's PhD. Fellowship.
Funders | Funder number |
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Ilse Katz Institute for Nanoscale Science and Technology | |
Horizon 2020 Framework Programme | |
European Commission | |
National Natural Science Foundation of China | 22176036, 21976030 |
Israel Science Foundation | 306/18 |
Horizon 2020 | 947655 |
Keywords
- CO Reduction
- Electrocatalysts
- Fe-Porphyrin
- Metal–Organic Frameworks
- Secondary-Sphere