Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction

Andrea Zitolo; Nastaran Ranjbar-Sahraie; Tzonka Mineva; Jingkun Li; Qingying Jia; Serban Stamatin; George F. Harrington; Stephen Mathew Lyth; Petr Krtil; Sanjeev Mukerjee; Emiliano Fonda; Frédéric Jaouen

doi:10.1038/s41467-017-01100-7

Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction

Andrea Zitolo^*
, Nastaran Ranjbar-Sahraie
, Tzonka Mineva
, Jingkun Li
, Qingying Jia
, Serban Stamatin
, George F. Harrington
, Stephen Mathew Lyth
, Petr Krtil
, Sanjeev Mukerjee
, Emiliano Fonda
, Frédéric Jaouen

^*Corresponding author for this work

Chemical And Process Engineering

Research output: Contribution to journal › Article › peer-review

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Abstract

Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN₄C₁₂, CoN₃C_10,porp and CoN₂C₅. The O₂ electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O₂-adsorption strength, we conclude that cobalt-based moieties bind O₂ too weakly for efficient O₂ reduction.

Original language	English
Article number	957
Pages (from-to)	1-11
Number of pages	11
Journal	Nature Communications
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41467-017-01100-7
Publication status	Published - 16 Oct 2017

Funding

This research was supported by ANR under contract 2011 CHEX 004 01 and by the Project ‘PEMFC-SUDOE’ -SOE1/P1/E0293 which is co-financed by the European Regional Development Fund in the framework of the Interreg Sudoe programme. We also acknowledge Synchrotron SOLEIL (Gif-sur Yvette, France) for provision of synchrotron radiation facilities at beamline SAMBA (proposal numbers 20120701 and 20150913), Valérie Briois for valuable discussions and Álvaro Reyes-Carmona (formerly at Université Montpellier, now at ICIQ, Spain) for sharing the benchmark IrO2 polarization curve.

Keywords

fuel cell
electrocatalysis
single-atom catalysts
atomically dispersed cobalt ions
cobalt-nitrogen carbon materials
catalysis
redox potentia
identification method

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10.1038/s41467-017-01100-7Licence: CC BY 4.0

Zitolo-etal-NC2017-Identification-catalytic-sites-cobalt-nitrogen-carbon-materials-oxygen-reduction-reactionFinal published version, 1.36 MBLicence: CC BY 4.0

Cite this

@article{49f2847096ba42a68f12ad4404db6c4f,

title = "Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction",

abstract = "Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.",

keywords = "fuel cell, electrocatalysis, single-atom catalysts, atomically dispersed cobalt ions, cobalt-nitrogen carbon materials, catalysis, redox potentia, identification method",

author = "Andrea Zitolo and Nastaran Ranjbar-Sahraie and Tzonka Mineva and Jingkun Li and Qingying Jia and Serban Stamatin and Harrington, \{George F.\} and Lyth, \{Stephen Mathew\} and Petr Krtil and Sanjeev Mukerjee and Emiliano Fonda and Fr{\'e}d{\'e}ric Jaouen",

note = "Funding Information: This research was supported by ANR under contract 2011 CHEX 004 01 and by the Project {\textquoteleft}PEMFC-SUDOE{\textquoteright} -SOE1/P1/E0293 which is co-financed by the European Regional Development Fund in the framework of the Interreg Sudoe programme. We also acknowledge Synchrotron SOLEIL (Gif-sur Yvette, France) for provision of synchrotron radiation facilities at beamline SAMBA (proposal numbers 20120701 and 20150913), Val{\'e}rie Briois for valuable discussions and {\'A}lvaro Reyes-Carmona (formerly at Universit{\'e} Montpellier, now at ICIQ, Spain) for sharing the benchmark IrO2 polarization curve. Publisher Copyright: {\textcopyright} 2017 The Author(s). Zitolo, A., Ranjbar-Sahraie, N., Mineva, T. et al. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nat Commun 8, 957 (2017). https://doi.org/10.1038/s41467-017-01100-7",

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doi = "10.1038/s41467-017-01100-7",

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T1 - Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction

AU - Zitolo, Andrea

AU - Ranjbar-Sahraie, Nastaran

AU - Mineva, Tzonka

AU - Li, Jingkun

AU - Jia, Qingying

AU - Stamatin, Serban

AU - Harrington, George F.

AU - Lyth, Stephen Mathew

AU - Krtil, Petr

AU - Mukerjee, Sanjeev

AU - Fonda, Emiliano

AU - Jaouen, Frédéric

N1 - Funding Information: This research was supported by ANR under contract 2011 CHEX 004 01 and by the Project ‘PEMFC-SUDOE’ -SOE1/P1/E0293 which is co-financed by the European Regional Development Fund in the framework of the Interreg Sudoe programme. We also acknowledge Synchrotron SOLEIL (Gif-sur Yvette, France) for provision of synchrotron radiation facilities at beamline SAMBA (proposal numbers 20120701 and 20150913), Valérie Briois for valuable discussions and Álvaro Reyes-Carmona (formerly at Université Montpellier, now at ICIQ, Spain) for sharing the benchmark IrO2 polarization curve. Publisher Copyright: © 2017 The Author(s). Zitolo, A., Ranjbar-Sahraie, N., Mineva, T. et al. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nat Commun 8, 957 (2017). https://doi.org/10.1038/s41467-017-01100-7

PY - 2017/10/16

Y1 - 2017/10/16

N2 - Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.

AB - Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.

KW - fuel cell

KW - electrocatalysis

KW - single-atom catalysts

KW - atomically dispersed cobalt ions

KW - cobalt-nitrogen carbon materials

KW - catalysis

KW - redox potentia

KW - identification method

UR - https://www.scopus.com/pages/publications/85031813002

U2 - 10.1038/s41467-017-01100-7

DO - 10.1038/s41467-017-01100-7

M3 - Article

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AN - SCOPUS:85031813002

SN - 2041-1723

VL - 8

SP - 1

EP - 11

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 957

ER -

Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction

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