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 Matthew Lyth, Petr Krtil, Sanjeev Mukerjee, Emiliano Fonda, Frédéric Jaouen

Research output: Contribution to journalArticle

82 Citations (Scopus)

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.

Original languageEnglish
Article number1100
JournalNature communications
Volume8
Issue number1
DOIs
Publication statusPublished - Dec 1 2017

Fingerprint

Cobalt
Catalytic Domain
Nitrogen
cobalt
Carbon
Electronic states
Oxygen
nitrogen
catalysts
Catalysts
Density functional theory
carbon
oxygen
X-Ray Absorption Spectroscopy
Metals
density functional theory
Atoms
X ray absorption spectroscopy
X ray absorption
Catalysis

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Zitolo, A., Ranjbar-Sahraie, N., Mineva, T., Li, J., Jia, Q., Stamatin, S., ... Jaouen, F. (2017). Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature communications, 8(1), [1100]. https://doi.org/10.1038/s41467-017-01100-7

Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. / Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F.; Lyth, Stephen Matthew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric.

In: Nature communications, Vol. 8, No. 1, 1100, 01.12.2017.

Research output: Contribution to journalArticle

Zitolo, A, Ranjbar-Sahraie, N, Mineva, T, Li, J, Jia, Q, Stamatin, S, Harrington, GF, Lyth, SM, Krtil, P, Mukerjee, S, Fonda, E & Jaouen, F 2017, 'Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction', Nature communications, vol. 8, no. 1, 1100. https://doi.org/10.1038/s41467-017-01100-7
Zitolo, Andrea ; Ranjbar-Sahraie, Nastaran ; Mineva, Tzonka ; Li, Jingkun ; Jia, Qingying ; Stamatin, Serban ; Harrington, George F. ; Lyth, Stephen Matthew ; Krtil, Petr ; Mukerjee, Sanjeev ; Fonda, Emiliano ; Jaouen, Frédéric. / Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. In: Nature communications. 2017 ; Vol. 8, No. 1.
@article{d864130f47704303a78bfd2e975e2d63,
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.",
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 Matthew} and Petr Krtil and Sanjeev Mukerjee and Emiliano Fonda and Fr{\'e}d{\'e}ric Jaouen",
year = "2017",
month = "12",
day = "1",
doi = "10.1038/s41467-017-01100-7",
language = "English",
volume = "8",
journal = "Nature Communications",
issn = "2041-1723",
publisher = "Nature Publishing Group",
number = "1",

}

TY - JOUR

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 Matthew

AU - Krtil, Petr

AU - Mukerjee, Sanjeev

AU - Fonda, Emiliano

AU - Jaouen, Frédéric

PY - 2017/12/1

Y1 - 2017/12/1

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.

UR - http://www.scopus.com/inward/record.url?scp=85031813002&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85031813002&partnerID=8YFLogxK

U2 - 10.1038/s41467-017-01100-7

DO - 10.1038/s41467-017-01100-7

M3 - Article

C2 - 29038426

AN - SCOPUS:85031813002

VL - 8

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 1100

ER -