Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential
Abstract To efficiently capture, activate, and transform small molecules, metalloenzymes have evolved to integrate a well‐organized pocket around the active metal center. Within this cavity, second coordination sphere functionalities are precisely positioned to optimize the rate, selectivity, and en...
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| Format: | Article |
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Wiley
2025-03-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202500482 |
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| author | Adrien Smith Philipp Gotico Régis Guillot Stéphane Le Gac Winfried Leibl Ally Aukauloo Bernard Boitrel Marie Sircoglou Zakaria Halime |
| author_facet | Adrien Smith Philipp Gotico Régis Guillot Stéphane Le Gac Winfried Leibl Ally Aukauloo Bernard Boitrel Marie Sircoglou Zakaria Halime |
| author_sort | Adrien Smith |
| collection | DOAJ |
| description | Abstract To efficiently capture, activate, and transform small molecules, metalloenzymes have evolved to integrate a well‐organized pocket around the active metal center. Within this cavity, second coordination sphere functionalities are precisely positioned to optimize the rate, selectivity, and energy cost of catalytic reactions. Inspired by this strategy, an artificial distal pocket defined by a preorganized 3D strap is introduced on an iron‐porphyrin catalyst (sc‐Fe) for the CO2‐to‐CO electrocatalytic reduction. Combined electrochemical, kinetic, and computational studies demonstrate that the adequate positioning of a carboxylate/carboxylic group acting in synergy with a trapped water molecule within this distal pocket remarkably enhances the reaction turnover frequency (TOF) by four orders of magnitude compared to the perfluorinated iron‐tetraphenylporphyrin catalyst (F20Fe) operating at a similar low overpotential. A proton‐coupled electron transfer (PCET) is found to be the key process responsible for the unexpected protonation of the coordinating carboxylate, which, upon CO2 insertion, shifts from the first to the second coordination sphere to play a possible secondary role as a proton relay. |
| format | Article |
| id | doaj-art-2cbcc5a098c94118a2a4737fb2aebdbd |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-2cbcc5a098c94118a2a4737fb2aebdbd2025-08-20T02:24:47ZengWileyAdvanced Science2198-38442025-03-011211n/an/a10.1002/advs.202500482Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low OverpotentialAdrien Smith0Philipp Gotico1Régis Guillot2Stéphane Le Gac3Winfried Leibl4Ally Aukauloo5Bernard Boitrel6Marie Sircoglou7Zakaria Halime8Université Paris‐Saclay CNRS Institut de Chimie Moléculaire et des Matériaux d'Orsay Orsay 91400 FranceInstitute for Integrative Biology of the Cell CEA CNRS Université Paris‐Saclay Gif‐sur‐Yvette 91191 FranceUniversité Paris‐Saclay CNRS Institut de Chimie Moléculaire et des Matériaux d'Orsay Orsay 91400 FranceUniv Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)‐UMR 6226 Rennes 35000 FranceInstitute for Integrative Biology of the Cell CEA CNRS Université Paris‐Saclay Gif‐sur‐Yvette 91191 FranceUniversité Paris‐Saclay CNRS Institut de Chimie Moléculaire et des Matériaux d'Orsay Orsay 91400 FranceUniv Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes)‐UMR 6226 Rennes 35000 FranceUniversité Paris‐Saclay CNRS Institut de Chimie Moléculaire et des Matériaux d'Orsay Orsay 91400 FranceUniversité Paris‐Saclay CNRS Institut de Chimie Moléculaire et des Matériaux d'Orsay Orsay 91400 FranceAbstract To efficiently capture, activate, and transform small molecules, metalloenzymes have evolved to integrate a well‐organized pocket around the active metal center. Within this cavity, second coordination sphere functionalities are precisely positioned to optimize the rate, selectivity, and energy cost of catalytic reactions. Inspired by this strategy, an artificial distal pocket defined by a preorganized 3D strap is introduced on an iron‐porphyrin catalyst (sc‐Fe) for the CO2‐to‐CO electrocatalytic reduction. Combined electrochemical, kinetic, and computational studies demonstrate that the adequate positioning of a carboxylate/carboxylic group acting in synergy with a trapped water molecule within this distal pocket remarkably enhances the reaction turnover frequency (TOF) by four orders of magnitude compared to the perfluorinated iron‐tetraphenylporphyrin catalyst (F20Fe) operating at a similar low overpotential. A proton‐coupled electron transfer (PCET) is found to be the key process responsible for the unexpected protonation of the coordinating carboxylate, which, upon CO2 insertion, shifts from the first to the second coordination sphere to play a possible secondary role as a proton relay.https://doi.org/10.1002/advs.202500482artificial distal pocketbiomimeticcarbon dioxideelectrocatalysishydrogen bonding |
| spellingShingle | Adrien Smith Philipp Gotico Régis Guillot Stéphane Le Gac Winfried Leibl Ally Aukauloo Bernard Boitrel Marie Sircoglou Zakaria Halime Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential Advanced Science artificial distal pocket biomimetic carbon dioxide electrocatalysis hydrogen bonding |
| title | Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential |
| title_full | Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential |
| title_fullStr | Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential |
| title_full_unstemmed | Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential |
| title_short | Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO2 Electroreduction at Low Overpotential |
| title_sort | hinged carboxylate in the artificial distal pocket of an iron porphyrin enhances co2 electroreduction at low overpotential |
| topic | artificial distal pocket biomimetic carbon dioxide electrocatalysis hydrogen bonding |
| url | https://doi.org/10.1002/advs.202500482 |
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