Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 32, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202206085
Keywords
CO2 Reduction; Electrocatalysts; Fe-Porphyrin; Metal-Organic Frameworks; Secondary-Sphere
Categories
Funding
- Israel Science Foundation (ISF) [306/18]
- European Research Council (ERC) under the European Union [947655]
- National Natural Science Foundation of China [22176036, 21976030]
- Kreitman's PhD. Fellowship
- European Research Council (ERC) [947655] Funding Source: European Research Council (ERC)
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This study demonstrates the significant enhancement of CO2 reduction activity and selectivity by electrostatic secondary-sphere functionalities in MOF materials. In situ Raman analysis reveals that immobilizing pendent positively-charged groups adjacent to MOF-residing Fe-porphyrin catalysts stabilizes weakly-bound CO intermediates and allows for control of the catalytic reaction by varying the ionic strength of the electrolyte.
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.
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