Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO
Ait Ahsaine, Hassan
Garcia Esparza, Angel T.
KAUST DepartmentPhysical Science and Engineering (PSE) Division
KAUST Catalysis Center (KCC)
Advanced Membranes and Porous Materials Research Center
Chemical Science Program
Embargo End Date2022-05-19
Permanent link to this recordhttp://hdl.handle.net/10754/669321
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AbstractIron 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.
CitationLu, 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
SponsorsA 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.
PublisherAmerican Chemical Society (ACS)
Except where otherwise noted, this item's license is described as This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acscatal.1c01157.