Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO

Xiaofei Lu, Hassan Ait Ahsaine, Busra Dereli, Angel T. Garcia Esparza, Marco Reinhard, Tatsuya Shinagawa, Duanxing Li, Karim Adil, Mohammed Tchalala, Thomas Kroll, Mohamed Eddaoudi, Dimosthenis Sokaras, Luigi Cavallo, Kazuhiro Takanabe

Research output: Contribution to journalArticlepeer-review

Abstract

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.
Original languageEnglish (US)
Pages (from-to)6499-6509
Number of pages11
JournalACS Catalysis
Volume11
Issue number11
DOIs
StatePublished - May 19 2021

ASJC Scopus subject areas

  • Catalysis

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