Academic Journal
Rhodium-Based Metal-Organic Polyhedra Assemblies for Selective CO2 Photoreduction
| العنوان: | Rhodium-Based Metal-Organic Polyhedra Assemblies for Selective CO2 Photoreduction |
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| المؤلفون: | Ghosh, A., Legrand, A., Rajapaksha, R., Craig, G., Sassoye, C., Balazs, G., Farrusseng, D., Furukawa, S., Canivet, J., Wisser, F. |
| المساهمون: | Sorbonne Université (SU) |
| المصدر: | ISSN: 0002-7863. |
| بيانات النشر: | HAL CCSD American Chemical Society |
| سنة النشر: | 2022 |
| مصطلحات موضوعية: | [CHIM.CATA]Chemical Sciences/Catalysis, [SDE.ES]Environmental Sciences/Environment and Society |
| الوصف: | International audience ; Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOPs) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organised around an inner cavity, making them appealing candidates for catalytic applications. Here we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within a MOP (Rh-MOP) and its three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid. Surprisingly, the catalytic activity per Rh atom is higher in the supramolecular structures than in its molecular subunit Rh-MOP or in Rh-MOF, and yields turnover frequencies of up to 60 h-1 and production rates of approx. 76 mmole formic acid per gram of catalyst per hour, unprecedented in heterogeneous photocatalysis, demonstrating the high potential of MOPs as catalysts for the photoreduction of CO2. This opens new perspectives for the electronic design of discrete molecular architectures with accessible metal sites for the production of solar fuels. The enhanced catalytic activity is investigated by XPS spectroscopy and electrochemical characterization, showing that self-assembly into supramolecular polymers increases the electron density on the active site, making the overall reaction thermodynamically more favourable. The catalyst can be recycled without loss of activity and with no change of its molecular structure as shown by pair distribution function analysis. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| Relation: | hal-03636819; https://hal.science/hal-03636819; https://hal.science/hal-03636819/document; https://hal.science/hal-03636819/file/RhMOP%20preprint.pdf |
| DOI: | 10.1021/jacs.1c12631 |
| الاتاحة: | https://hal.science/hal-03636819 https://hal.science/hal-03636819/document https://hal.science/hal-03636819/file/RhMOP%20preprint.pdf https://doi.org/10.1021/jacs.1c12631 |
| Rights: | info:eu-repo/semantics/OpenAccess |
| رقم الانضمام: | edsbas.2CDD8D46 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/jacs.1c12631 |
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