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

doi:10.1021/acscatal.1c01157

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 journal › Article › peer-review

32 Scopus citations

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 language	English (US)
Pages (from-to)	6499-6509
Number of pages	11
Journal	ACS Catalysis
Volume	11
Issue number	11
DOIs	https://doi.org/10.1021/acscatal.1c01157
State	Published - May 19 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-11-24
Acknowledgements: 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.

ASJC Scopus subject areas

Catalysis

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10.1021/acscatal.1c01157

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Lu, X., Ait Ahsaine, H., Dereli, B., Garcia Esparza, A. T., Reinhard, M., Shinagawa, T., Li, D., Adil, K., Tchalala, M., Kroll, T., Eddaoudi, M., Sokaras, D., Cavallo, L., & Takanabe, K. (2021). Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO. ACS Catalysis, 11(11), 6499-6509. https://doi.org/10.1021/acscatal.1c01157

@article{b20b13a491a941adae726ee3ab8cc90f,

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

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.",

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

note = "KAUST Repository Item: Exported on 2021-11-24 Acknowledgements: 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.",

year = "2021",

month = may,

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doi = "10.1021/acscatal.1c01157",

language = "English (US)",

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Lu, X, Ait Ahsaine, H, Dereli, B, Garcia Esparza, AT, Reinhard, M, Shinagawa, T, Li, D, Adil, K, Tchalala, M, Kroll, T, Eddaoudi, M, Sokaras, D, Cavallo, L & Takanabe, K 2021, 'Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO', ACS Catalysis, vol. 11, no. 11, pp. 6499-6509. https://doi.org/10.1021/acscatal.1c01157

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T1 - Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO

AU - Lu, Xiaofei

AU - Ait Ahsaine, Hassan

AU - Dereli, Busra

AU - Garcia Esparza, Angel T.

AU - Reinhard, Marco

AU - Shinagawa, Tatsuya

AU - Li, Duanxing

AU - Adil, Karim

AU - Tchalala, Mohammed

AU - Kroll, Thomas

AU - Eddaoudi, Mohamed

AU - Sokaras, Dimosthenis

AU - Cavallo, Luigi

AU - Takanabe, Kazuhiro

N1 - KAUST Repository Item: Exported on 2021-11-24 Acknowledgements: 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.

PY - 2021/5/19

Y1 - 2021/5/19

N2 - 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.

AB - 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.

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UR - https://pubs.acs.org/doi/10.1021/acscatal.1c01157

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U2 - 10.1021/acscatal.1c01157

DO - 10.1021/acscatal.1c01157

M3 - Article

SN - 2155-5435

VL - 11

SP - 6499

EP - 6509

JO - ACS Catalysis

JF - ACS Catalysis

IS - 11

ER -

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

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