Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO
Type
ArticleAuthors
Lu, XiaofeiAit 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

KAUST Department
Advanced Membranes and Porous Materials Research CenterChemical Science Program
Functional Materials Design, Discovery and Development (FMD3)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2021-05-19Online Publication Date
2021-05-19Print Publication Date
2021-06-04Embargo End Date
2022-05-19Submitted Date
2021-03-13Permanent link to this record
http://hdl.handle.net/10754/669321
Metadata
Show full item recordAbstract
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.Citation
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.1c01157Sponsors
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.Publisher
American Chemical Society (ACS)Journal
ACS CatalysisAdditional Links
https://pubs.acs.org/doi/10.1021/acscatal.1c01157https://www.osti.gov/biblio/1807742
ae974a485f413a2113503eed53cd6c53
10.1021/acscatal.1c01157
Scopus Count
Except where otherwise noted, this item's license is described as Archived with thanks to American Chemical Society (ACS) under a Creative Commons license, details at: https://creativecommons.org/licenses/by-nc-nd/4.0/