2D transition metal–TCNQ sheets as bifunctional single-atom catalysts for oxygen reduction and evolution reaction (ORR/OER)

Qingming Deng, Jiong Zhao, Tiantian Wu, Guibin Chen, Heine Anton Hansen*, Tejs Vegge

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The identification of catalytically active and stable bifunctional electrocatalysts for the oxygen reduction and evolution reaction (ORR/OER) would revolutionize rechargeable metal-air batteries and regenerative fuel cell technologies. In this study, we use density functional theory (DFT) calculations to systemically investigate 2D transition metal based tetracyanoquinodimethane (TM–TCNQ, TM = Cr-Cu, Ru-Ag, Pt, Ir) monolayers with single TM atoms catalysts (SACs) distributed periodically with high density. We calculate a lower limiting overpotential of ηlim = 0.33 V for Fe-TCNQ yielding a higher expected activity than that of Pt metal (0.48 V) for the ORR under acidic conditions. The catalytic performance of Fe-TCNQ for OER is, however, surpassed by Ni-TCNQs (ηlim = 0.46 V), which is identified as the highest among the candidates. By applying grafting axial ligands and external strain, the adsorption strength of reaction intermediates on TM reactive sites can be further optimized and enhances the activities of Mn-, Fe- and Ni-TCNQs for the ORR or the OER. Here, Fe-TCNQ-Cl (ηlim = 0.27/0.55 V), followed by Fe-TCNQ-CO (ηlim = 0.67/0.43 V), are predicted as novel, high-performance bifunctional ORR/OER catalysts with comparable limiting overpotentials to those of the best commercially used electrocatalysts, Pt (ORR: ηlim = 0.48 V) and RuO2 (OER: ηlim = 0.42 V). In addition, the recently synthesized Fe-TCNQ possess excellent conductivity with fast electron transfer during the catalytic reactions. These results show 2D TM-TCNQ monolayers are durable, low-cost, and efficient catalysts for the ORR and the OER in metal-air batteries and fuel cells.
Original languageEnglish
JournalJournal of Catalysis
Volume370
Pages (from-to)378-384
ISSN0021-9517
DOIs
Publication statusPublished - 2019

Keywords

  • Computational screening
  • Oxygen reduction reaction
  • Oxygen evolution reaction
  • Bifunctional ORR/OER catalyst
  • Density functional theory

Cite this

@article{53fa4c6d12f0475a9748c67a963e1d95,
title = "2D transition metal–TCNQ sheets as bifunctional single-atom catalysts for oxygen reduction and evolution reaction (ORR/OER)",
abstract = "The identification of catalytically active and stable bifunctional electrocatalysts for the oxygen reduction and evolution reaction (ORR/OER) would revolutionize rechargeable metal-air batteries and regenerative fuel cell technologies. In this study, we use density functional theory (DFT) calculations to systemically investigate 2D transition metal based tetracyanoquinodimethane (TM–TCNQ, TM = Cr-Cu, Ru-Ag, Pt, Ir) monolayers with single TM atoms catalysts (SACs) distributed periodically with high density. We calculate a lower limiting overpotential of ηlim = 0.33 V for Fe-TCNQ yielding a higher expected activity than that of Pt metal (0.48 V) for the ORR under acidic conditions. The catalytic performance of Fe-TCNQ for OER is, however, surpassed by Ni-TCNQs (ηlim = 0.46 V), which is identified as the highest among the candidates. By applying grafting axial ligands and external strain, the adsorption strength of reaction intermediates on TM reactive sites can be further optimized and enhances the activities of Mn-, Fe- and Ni-TCNQs for the ORR or the OER. Here, Fe-TCNQ-Cl (ηlim = 0.27/0.55 V), followed by Fe-TCNQ-CO (ηlim = 0.67/0.43 V), are predicted as novel, high-performance bifunctional ORR/OER catalysts with comparable limiting overpotentials to those of the best commercially used electrocatalysts, Pt (ORR: ηlim = 0.48 V) and RuO2 (OER: ηlim = 0.42 V). In addition, the recently synthesized Fe-TCNQ possess excellent conductivity with fast electron transfer during the catalytic reactions. These results show 2D TM-TCNQ monolayers are durable, low-cost, and efficient catalysts for the ORR and the OER in metal-air batteries and fuel cells.",
keywords = "Computational screening, Oxygen reduction reaction, Oxygen evolution reaction, Bifunctional ORR/OER catalyst, Density functional theory",
author = "Qingming Deng and Jiong Zhao and Tiantian Wu and Guibin Chen and Hansen, {Heine Anton} and Tejs Vegge",
year = "2019",
doi = "10.1016/j.jcat.2018.12.012",
language = "English",
volume = "370",
pages = "378--384",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press",

}

2D transition metal–TCNQ sheets as bifunctional single-atom catalysts for oxygen reduction and evolution reaction (ORR/OER). / Deng, Qingming; Zhao, Jiong; Wu, Tiantian; Chen, Guibin; Hansen, Heine Anton; Vegge, Tejs.

In: Journal of Catalysis, Vol. 370, 2019, p. 378-384.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - 2D transition metal–TCNQ sheets as bifunctional single-atom catalysts for oxygen reduction and evolution reaction (ORR/OER)

AU - Deng, Qingming

AU - Zhao, Jiong

AU - Wu, Tiantian

AU - Chen, Guibin

AU - Hansen, Heine Anton

AU - Vegge, Tejs

PY - 2019

Y1 - 2019

N2 - The identification of catalytically active and stable bifunctional electrocatalysts for the oxygen reduction and evolution reaction (ORR/OER) would revolutionize rechargeable metal-air batteries and regenerative fuel cell technologies. In this study, we use density functional theory (DFT) calculations to systemically investigate 2D transition metal based tetracyanoquinodimethane (TM–TCNQ, TM = Cr-Cu, Ru-Ag, Pt, Ir) monolayers with single TM atoms catalysts (SACs) distributed periodically with high density. We calculate a lower limiting overpotential of ηlim = 0.33 V for Fe-TCNQ yielding a higher expected activity than that of Pt metal (0.48 V) for the ORR under acidic conditions. The catalytic performance of Fe-TCNQ for OER is, however, surpassed by Ni-TCNQs (ηlim = 0.46 V), which is identified as the highest among the candidates. By applying grafting axial ligands and external strain, the adsorption strength of reaction intermediates on TM reactive sites can be further optimized and enhances the activities of Mn-, Fe- and Ni-TCNQs for the ORR or the OER. Here, Fe-TCNQ-Cl (ηlim = 0.27/0.55 V), followed by Fe-TCNQ-CO (ηlim = 0.67/0.43 V), are predicted as novel, high-performance bifunctional ORR/OER catalysts with comparable limiting overpotentials to those of the best commercially used electrocatalysts, Pt (ORR: ηlim = 0.48 V) and RuO2 (OER: ηlim = 0.42 V). In addition, the recently synthesized Fe-TCNQ possess excellent conductivity with fast electron transfer during the catalytic reactions. These results show 2D TM-TCNQ monolayers are durable, low-cost, and efficient catalysts for the ORR and the OER in metal-air batteries and fuel cells.

AB - The identification of catalytically active and stable bifunctional electrocatalysts for the oxygen reduction and evolution reaction (ORR/OER) would revolutionize rechargeable metal-air batteries and regenerative fuel cell technologies. In this study, we use density functional theory (DFT) calculations to systemically investigate 2D transition metal based tetracyanoquinodimethane (TM–TCNQ, TM = Cr-Cu, Ru-Ag, Pt, Ir) monolayers with single TM atoms catalysts (SACs) distributed periodically with high density. We calculate a lower limiting overpotential of ηlim = 0.33 V for Fe-TCNQ yielding a higher expected activity than that of Pt metal (0.48 V) for the ORR under acidic conditions. The catalytic performance of Fe-TCNQ for OER is, however, surpassed by Ni-TCNQs (ηlim = 0.46 V), which is identified as the highest among the candidates. By applying grafting axial ligands and external strain, the adsorption strength of reaction intermediates on TM reactive sites can be further optimized and enhances the activities of Mn-, Fe- and Ni-TCNQs for the ORR or the OER. Here, Fe-TCNQ-Cl (ηlim = 0.27/0.55 V), followed by Fe-TCNQ-CO (ηlim = 0.67/0.43 V), are predicted as novel, high-performance bifunctional ORR/OER catalysts with comparable limiting overpotentials to those of the best commercially used electrocatalysts, Pt (ORR: ηlim = 0.48 V) and RuO2 (OER: ηlim = 0.42 V). In addition, the recently synthesized Fe-TCNQ possess excellent conductivity with fast electron transfer during the catalytic reactions. These results show 2D TM-TCNQ monolayers are durable, low-cost, and efficient catalysts for the ORR and the OER in metal-air batteries and fuel cells.

KW - Computational screening

KW - Oxygen reduction reaction

KW - Oxygen evolution reaction

KW - Bifunctional ORR/OER catalyst

KW - Density functional theory

U2 - 10.1016/j.jcat.2018.12.012

DO - 10.1016/j.jcat.2018.12.012

M3 - Journal article

VL - 370

SP - 378

EP - 384

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -