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High-Throughput Calculation Investigations on the Electrocatalytic Activity of Codoped Single Metal–Nitrogen Embedded in Graphene for ORR Mechanism

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Abstract

Two types of single metal atoms embedded in graphene were investigated as a potential electrocatalyst for oxygen reduction reaction (ORR) for the application in a fuel cell. ORR was considered in the four elementary reaction steps of oxygen hydrogenation, perhydroxyl production, atomic oxygen hydrogenation, and final water form. All calculations of catalytic activity were performed with the Vienna Ab Initio Simulation Package (VASP) on an M@Gra (M = Mn, Fe, Co, and Ir)–embedded structure, indicating that high-efficiency catalytic activity in the oxidation reaction takes place on the top of metal atom sites. Our calculations revealed that ORR is profiled via four-electron transfer pathway. Activity of these catalysts is closely related to the same scaling linear relations between the adsorption energies of the ORR intermediates on different catalytic surfaces; this can improve their catalytic activity for O2 reduction through a high-efficiency 4e reaction path. Mn- and Ir-doped of cell A graphene exhibited excellent ORR catalytic performance in case of their small overpotential (less than 0.23 V) and low-energy barrier (less than 0.64 eV) of the Ir-doped graphene rate-determining step. Mn@Gra and Fe@Gra of cell B monolayers showed poor ORR catalytic performance due to the strong interaction between various ORR-involved species. Based on the free energy change and activation energy of each intermediate reaction in ORR, Fe@Gra and Ir@Gra are promising catalysts for ORR processes in fuel cells. This provides useful guidance for different types of catalysts in applications to fuel cells.

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Acknowledgments

The Lichtenberg high-performance computer is gratefully acknowledged, and we are also thankful to TU Darmstadt. We also thank LetPub (www.letpub.com) for its linguistic assistance during the preparation of this manuscript.

Funding

Financial support comes from the China Scholarship Council (CSC:201808440416) of China, Research and the Arts (HMWK) of the Hessen state in Germany, and Natural Science of Foundation of Hubei Province, China (No. 2019CFB225).

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Authors and Affiliations

  1. Institute of Materials Science, TU Darmstadt, 64287, Darmstadt, Germany

    Yi Xiao

  2. School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou, 434023, People’s Republic of China

    Weibin Zhang

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  1. Yi Xiao
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Correspondence to Yi Xiao or Weibin Zhang.

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Xiao, Y., Zhang, W. High-Throughput Calculation Investigations on the Electrocatalytic Activity of Codoped Single Metal–Nitrogen Embedded in Graphene for ORR Mechanism. Electrocatalysis 11, 393–404 (2020). https://doi.org/10.1007/s12678-020-00598-8

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