Academic Journal
Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO
| العنوان: | Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO |
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| المؤلفون: | Lu, Xiaofei, Ait Ahsaine, Hassan, Dereli, Busra, Garcia Esparza, Angel T., Reinhard, Marco, Shinagawa, Tatsuya, Li, Duanxing, Adil, Karim, Tchalala, Mohammed, Kroll, Thomas, Eddaoudi, Mohamed, Sokaras, Dimosthenis, Cavallo, Luigi, Takanabe, Kazuhiro |
| المساهمون: | Advanced Membranes and Porous Materials Research Center, Chemical Science Program, Functional Materials Design, Discovery and Development (FMD3), KAUST Catalysis Center (KCC), Physical Science and Engineering (PSE) Division, Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan, Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States |
| بيانات النشر: | American Chemical Society (ACS) |
| سنة النشر: | 2021 |
| المجموعة: | King Abdullah University of Science and Technology: KAUST Repository |
| الوصف: | Iron porphyrin-based molecular catalysts can electrocatalyze CO2 reduction to CO at nearly 100% selectivity in water. Nevertheless, the associated active sites and reaction mechanisms remain debatable, impeding the establishment of design guidelines for effective catalysts. This study reports coupling in operando experiments and theoretical calculations for immobilized 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin Fe(III) chloride (FeF20TPP) for electrocatalytic CO2 reduction in an aqueous phase. In operando UV–vis and X-ray absorption near-edge structure spectra indicated the persisting presence of Fe(II) species during the cathodic reaction, acting as catalytic sites that accommodate CO as Fe(II)–CO adducts. Consistently, the density functional calculations pointed out that the ligand-reduced state with oxidized Fe, namely, [Fe(II)F20(TPP•)]−, prevails in the catalytic cycle prior to the rate-controlling step. This work provides the conclusive representation related to the working states of Fe-based molecular catalysts under reaction conditions. ; A part of this work was supported by the JSPS KAKENHI (grant number 19KK0126) and King Abdullah University of Science and Technology (KAUST) AMPM research center under collaborative funding. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | application/pdf |
| اللغة: | unknown |
| تدمد: | 2155-5435 |
| Relation: | https://www.osti.gov/biblio/1807742; Lu, X., Ahsaine, H. A., Dereli, B., Garcia-Esparza, A. T., Reinhard, M., Shinagawa, T., … Takanabe, K. (2021). Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO. ACS Catalysis, 6499–6509. doi:10.1021/acscatal.1c01157; ACS Catalysis; http://hdl.handle.net/10754/669321 |
| DOI: | 10.1021/acscatal.1c01157 |
| الاتاحة: | http://hdl.handle.net/10754/669321 https://doi.org/10.1021/acscatal.1c01157 |
| Rights: | Archived with thanks to American Chemical Society (ACS) under a Creative Commons license, details at: https://creativecommons.org/licenses/by-nc-nd/4.0/ ; This file is an open access version redistributed from: https://www.osti.gov/biblio/1807742 ; 2022-05-19 ; https://creativecommons.org/licenses/by-nc-nd/4.0/ |
| رقم الانضمام: | edsbas.EB2B6FE4 |
| قاعدة البيانات: | BASE |
| تدمد: | 21555435 |
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| DOI: | 10.1021/acscatal.1c01157 |