Interplay Between Charge Accumulation and Oxygen Reduction Catalysis in Nanostructured TiO2 Electrodes Functionalized with a Molecular Catalyst
| العنوان: | Interplay Between Charge Accumulation and Oxygen Reduction Catalysis in Nanostructured TiO2 Electrodes Functionalized with a Molecular Catalyst |
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| المؤلفون: | Véronique Balland, Yee-Seul Kim, Alla Bessmertnykh-Lejeune, Kenneth D. M. Harris, Benoît Limoges, Sebastien Kriegel |
| المساهمون: | Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), University of Alberta, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| المصدر: | ChemElectroChem ChemElectroChem, Weinheim : Wiley-VCH, In press, ⟨10.1002/celc.202100424⟩ ChemElectroChem, In press, ⟨10.1002/celc.202100424⟩ |
| بيانات النشر: | HAL CCSD, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Materials science, 010405 organic chemistry, Oxide, Selective catalytic reduction, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Electrochemistry, Electrocatalyst, 01 natural sciences, Porphyrin, Catalysis, 0104 chemical sciences, Electron transfer, chemistry.chemical_compound, chemistry, Chemical engineering, Electrode, [CHIM.OTHE]Chemical Sciences/Other |
| الوصف: | International audience; The catalytic reduction of O2 by a manganese(III) porphyrin immobilized in a nanostructured semiconductive transparent TiO2 electrode is here investigated by UV-Vis spectroelectrochemistry in an aqueous buffered medium. Analysis of the operando spectroelectrochemical data, collected for both the immobilized catalyst and the TiO2 matrix, demonstrates the coexistence of two faradaic electrochemical processes, namely (i) irreversible interfacial electron transfer from TiO2 to the immobilized porphyrin triggering the catalytic reduction of O2, and (ii) reversible proton-coupled electrochemical reduction of TiO2 leading to the accumulation of electrons in the TiO2 bulk. The competition between these two processes is modulated by the local concentration of O2, which itself varies with the rate of the catalysis. Indeed, when O2 is locally strongly depleted by catalysis, the process switches from catalysis to charge storage, like a battery. As a result, the electrons stored in TiO2 were observed to pursue the catalysis even after the electrode polarization was switched-off (i.e., under open circuit). This is an overlooked phenomenon that we believe is important to consider in applications relying on metal oxide-based photoelectrodes operating in aqueous media. |
| اللغة: | English |
| تدمد: | 2196-0216 |
| DOI: | 10.1002/celc.202100424⟩ |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::0b9f5ea285c5cc5109679605b9a4ccbc https://hal.archives-ouvertes.fr/hal-03272209/file/Kim_AcceptedManuscript_HAL.pdf |
| Rights: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....0b9f5ea285c5cc5109679605b9a4ccbc |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 21960216 |
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| DOI: | 10.1002/celc.202100424⟩ |