Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins
Abstract
Abstract Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second‐sphere contributions that stem from each type of interaction. Fe‐ ortho ‐im(H) , which poises imidazolium units featuring both positive charge and hydrogen‐bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25‐fold and CO 2 RR activity by 2000‐fold relative to the parent Fe tetraphenylporphyrin ( Fe‐TPP ). Comparison with monofunctional analogs reveals that through‐space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH); USDOE
- OSTI Identifier:
- 1963460
- Alternate Identifier(s):
- OSTI ID: 1885609
- Grant/Contract Number:
- AC02-05CH11231; NIH S10OD023532; NIH S10OD024998
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 61; Journal Issue: 37; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Carbon Dioxide Capture; Electrochemical Carbon Dioxide Reduction; Imidazolium; Iron Porphyrin; Second-Sphere Effect
Citation Formats
Narouz, Mina R., De La Torre, Patricia, An, Lun, and Chang, Christopher J. Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins. United States: N. p., 2022.
Web. doi:10.1002/anie.202207666.
Narouz, Mina R., De La Torre, Patricia, An, Lun, & Chang, Christopher J. Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins. United States. https://doi.org/10.1002/anie.202207666
Narouz, Mina R., De La Torre, Patricia, An, Lun, and Chang, Christopher J. Mon .
"Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins". United States. https://doi.org/10.1002/anie.202207666. https://www.osti.gov/servlets/purl/1963460.
@article{osti_1963460,
title = {Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins},
author = {Narouz, Mina R. and De La Torre, Patricia and An, Lun and Chang, Christopher J.},
abstractNote = {Abstract Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second‐sphere contributions that stem from each type of interaction. Fe‐ ortho ‐im(H) , which poises imidazolium units featuring both positive charge and hydrogen‐bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25‐fold and CO 2 RR activity by 2000‐fold relative to the parent Fe tetraphenylporphyrin ( Fe‐TPP ). Comparison with monofunctional analogs reveals that through‐space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.},
doi = {10.1002/anie.202207666},
journal = {Angewandte Chemie (International Edition)},
number = 37,
volume = 61,
place = {United States},
year = {Mon Jul 25 00:00:00 EDT 2022},
month = {Mon Jul 25 00:00:00 EDT 2022}
}
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