Predoped Oxygenated Defects Activate Nitrogen-Doped Graphene for the Oxygen Reduction Reaction

Lin Jiang; Bas van Dijk; Longfei Wu; Clément Maheu; Jan P. Hofmann; Viorica Tudor; Marc T.M. Koper; Dennis G.H. Hetterscheid; Grégory F. Schneider

doi:10.1021/acscatal.1c03662

Predoped Oxygenated Defects Activate Nitrogen-Doped Graphene for the Oxygen Reduction Reaction

Lin Jiang
, Bas van Dijk
, Longfei Wu
, Clément Maheu
, Jan P. Hofmann
, Viorica Tudor
, Marc T.M. Koper
, Dennis G.H. Hetterscheid (Corresponding author)
, Grégory F. Schneider (Corresponding author)

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

64 Citations (Scopus)

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Abstract

The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene – a model carbon-based electrode – for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e^– pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.

Original language	English
Pages (from-to)	173-182
Number of pages	10
Journal	ACS Catalysis
Volume	12
Issue number	1
DOIs	https://doi.org/10.1021/acscatal.1c03662
Publication status	Published - 7 Jan 2022

Bibliographical note

Funding Information:
The research leading to this work has gratefully received funding from the Chinese Scholarship Council (L.J.; 201406890016), the European Research Council (ERC starting grant 637556 Cu4Energy to D.G.H.H.), the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335879 project acronym “Biographene”, and The Netherlands Organization for Scientific Research (Vidi 723.013.007, NWA route 'meten & detecteren'). L.W. and J.P.H. acknowledge funding from The Netherlands Organization for Scientific Research (NWO) and cofinancing by Shell Global Solutions International B.V. for the project 13CO2-6. L.J. thanks Nicole W. G. Smits, Koen van der Ham, and Michiel Langerman for helpful discussions.

Funding

The research leading to this work has gratefully received funding from the Chinese Scholarship Council (L.J.; 201406890016), the European Research Council (ERC starting grant 637556 Cu4Energy to D.G.H.H.), the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335879 project acronym “Biographene”, and The Netherlands Organization for Scientific Research (Vidi 723.013.007, NWA route 'meten & detecteren'). L.W. and J.P.H. acknowledge funding from The Netherlands Organization for Scientific Research (NWO) and cofinancing by Shell Global Solutions International B.V. for the project 13CO2-6. L.J. thanks Nicole W. G. Smits, Koen van der Ham, and Michiel Langerman for helpful discussions.

Keywords

monolayer graphene
nitrogen dopants
ORR activity
oxygenated vacancy defects
synergetic effect

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title = "Predoped Oxygenated Defects Activate Nitrogen-Doped Graphene for the Oxygen Reduction Reaction",

abstract = "The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene – a model carbon-based electrode – for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e– pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.",

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author = "Lin Jiang and \{van Dijk\}, Bas and Longfei Wu and Cl{\'e}ment Maheu and Hofmann, \{Jan P.\} and Viorica Tudor and Koper, \{Marc T.M.\} and Hetterscheid, \{Dennis G.H.\} and Schneider, \{Gr{\'e}gory F.\}",

note = "Funding Information: The research leading to this work has gratefully received funding from the Chinese Scholarship Council (L.J.; 201406890016), the European Research Council (ERC starting grant 637556 Cu4Energy to D.G.H.H.), the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335879 project acronym “Biographene”, and The Netherlands Organization for Scientific Research (Vidi 723.013.007, NWA route 'meten \& detecteren'). L.W. and J.P.H. acknowledge funding from The Netherlands Organization for Scientific Research (NWO) and cofinancing by Shell Global Solutions International B.V. for the project 13CO2-6. L.J. thanks Nicole W. G. Smits, Koen van der Ham, and Michiel Langerman for helpful discussions. ",

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doi = "10.1021/acscatal.1c03662",

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AU - Jiang, Lin

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AU - Wu, Longfei

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AU - Hofmann, Jan P.

AU - Tudor, Viorica

AU - Koper, Marc T.M.

AU - Hetterscheid, Dennis G.H.

AU - Schneider, Grégory F.

N1 - Funding Information: The research leading to this work has gratefully received funding from the Chinese Scholarship Council (L.J.; 201406890016), the European Research Council (ERC starting grant 637556 Cu4Energy to D.G.H.H.), the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335879 project acronym “Biographene”, and The Netherlands Organization for Scientific Research (Vidi 723.013.007, NWA route 'meten & detecteren'). L.W. and J.P.H. acknowledge funding from The Netherlands Organization for Scientific Research (NWO) and cofinancing by Shell Global Solutions International B.V. for the project 13CO2-6. L.J. thanks Nicole W. G. Smits, Koen van der Ham, and Michiel Langerman for helpful discussions.

PY - 2022/1/7

Y1 - 2022/1/7

N2 - The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene – a model carbon-based electrode – for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e– pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.

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KW - oxygenated vacancy defects

KW - synergetic effect

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SN - 2155-5435

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JO - ACS Catalysis

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ER -

Predoped Oxygenated Defects Activate Nitrogen-Doped Graphene for the Oxygen Reduction Reaction

Abstract

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Keywords

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