@article{1549f50b5b044066b13bf1a30c3379a4,
title = "Mechanistic Elucidations of Highly Dispersed Metalloporphyrin Metal-Organic Framework Catalysts for CO2 Electroreduction",
abstract = "Immobilization of porphyrin complexes into crystalline metal–organic frameworks (MOFs) enables high exposure of porphyrin active sites for CO2 electroreduction. Herein, well-dispersed iron-porphyrin-based MOF (PCN-222(Fe)) on carbon-based electrodes revealed optimal turnover frequencies for CO2 electroreduction to CO at 1 wt.% catalyst loading, beyond which the intrinsic catalyst activity declined due to CO2 mass transport limitations. In situ Raman suggested that PCN-222(Fe) maintained its structure under electrochemical bias, permitting mechanistic investigations. These revealed a stepwise electron transfer-proton transfer mechanism for CO2 electroreduction on PCN-222(Fe) electrodes, which followed a shift from a rate-limiting electron transfer to CO2 mass transfer as the potential increased from −0.6 V to −1.0 V vs. RHE. Our results demonstrate how intrinsic catalytic investigations and in situ spectroscopy are needed to elucidate CO2 electroreduction mechanisms on PCN-222(Fe) MOFs.",
keywords = "Electrocatalysis, Immobilization, Metal–Organic Framework, Reaction Mechanism, Spectroscopy",
author = "Smith, {Michael R.} and Martin, {Clare B.} and Sonia Arumuganainar and Ari Gilman and Koel, {Bruce E.} and Sarazen, {Michele L.}",
note = "Funding Information: This work was supported by the Lidow Senior Thesis Award and the DuPont Senior Thesis Fellowship Grant in memory of Michelle Goudie'93. We also acknowledge the use of Princeton's Imaging and Analysis Center, which is partially supported through the Princeton Center for Complex Materials (PCCM), a National Science Foundation (NSF)-MRSEC program (DMR-2011750). We also acknowledge Istvan Pelzer and Kenneth Conover at the NMR Facility at Princeton University. Funding Information: This work was supported by the Lidow Senior Thesis Award and the DuPont Senior Thesis Fellowship Grant in memory of Michelle Goudie'93. We also acknowledge the use of Princeton's Imaging and Analysis Center, which is partially supported through the Princeton Center for Complex Materials (PCCM), a National Science Foundation (NSF)‐MRSEC program (DMR‐2011750). We also acknowledge Istvan Pelzer and Kenneth Conover at the NMR Facility at Princeton University. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",
year = "2023",
month = feb,
day = "13",
doi = "10.1002/anie.202218208",
language = "English (US)",
volume = "62",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "8",
}