Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

Hadi Abroshan, Pallavi Bothra, Seoin Back, Ambarish Kulkarni, Jens K. Nørskov, Samira Siahrostami*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoNRS(100) and CoNZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.

Original languageEnglish
JournalJournal of Physical Chemistry C
Volume122
Issue number9
Pages (from-to)4783-4791
ISSN1932-7447
DOIs
Publication statusPublished - 2018
Externally publishedYes

Cite this

Abroshan, Hadi ; Bothra, Pallavi ; Back, Seoin ; Kulkarni, Ambarish ; Nørskov, Jens K. ; Siahrostami, Samira. / Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction. In: Journal of Physical Chemistry C. 2018 ; Vol. 122, No. 9. pp. 4783-4791.
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title = "Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction",
abstract = "The oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoNRS(100) and CoNZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.",
author = "Hadi Abroshan and Pallavi Bothra and Seoin Back and Ambarish Kulkarni and N{\o}rskov, {Jens K.} and Samira Siahrostami",
year = "2018",
doi = "10.1021/acs.jpcc.7b12643",
language = "English",
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Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction. / Abroshan, Hadi; Bothra, Pallavi; Back, Seoin; Kulkarni, Ambarish; Nørskov, Jens K.; Siahrostami, Samira.

In: Journal of Physical Chemistry C, Vol. 122, No. 9, 2018, p. 4783-4791.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

AU - Abroshan, Hadi

AU - Bothra, Pallavi

AU - Back, Seoin

AU - Kulkarni, Ambarish

AU - Nørskov, Jens K.

AU - Siahrostami, Samira

PY - 2018

Y1 - 2018

N2 - The oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoNRS(100) and CoNZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.

AB - The oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoNRS(100) and CoNZB(110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.

U2 - 10.1021/acs.jpcc.7b12643

DO - 10.1021/acs.jpcc.7b12643

M3 - Journal article

VL - 122

SP - 4783

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JO - The Journal of Physical Chemistry Part C

JF - The Journal of Physical Chemistry Part C

SN - 1932-7447

IS - 9

ER -