University of Oulu

J. Phys. Chem. C 2023, 127, 30, 14694–14703.

Electronic origin of enhanced selectivity through the halogenation of a single Mn atom on graphitic C₃N₄ for electrocatalytic reduction of CO₂ from first-principles calculations

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Author: Shakir, Renna1; Komsa, Hannu-Pekka2; Sinha, A. S. K.3;
Organizations: 1Department of Sciences & Humanities, Rajiv Gandhi Institute of Petroleum Technology, Jais, Amethi, Uttar Pradesh 229304, India
2Microelectronics Research Unit, Faculty of Information Technology and Electrical Engineering, University of Oulu, Oulu FI-90014, Finland
3Department of Chemical & Biochemical Engineering, Rajiv Gandhi Institute of Petroleum Technology, Jais, Amethi, Uttar Pradesh 229304, India
4Department of Physics, National Institute of Technology, Durgapur, West Bengal 713209, India
Format: article
Version: accepted version
Access: embargoed
Persistent link:
Language: English
Published: American Chemical Society, 2023
Publish Date: 2024-07-21


The electrochemical reduction of CO₂ to valuable products is a critical process that can potentially address energy and environmental challenges. Single-metal atom catalysts have gained significant attention because of their high efficiency and potential to mitigate the challenges associated with traditional-metal nanocatalysts. In particular, non-precious-metal-based catalysts are of great interest because of their low cost and abundance in the Earth’s crust. This work is a comprehensive study to reveal the role of halogen X (X = F, Cl, Br, and I) in improving the CO₂ reduction activity and selectivity of single manganese atom-based active sites on a graphitic carbon nitride (g-C₃N₄) monolayer. Although previous experiments prove that halogenation improves the selectivity of a single Mn-atom-based catalyst, our calculations reveal the reason for the selectivity of the catalyst. The halogen-modified MnN6 active site on g-C₃N₄ has a high hydrogen evolution reaction (HER) tolerance. Hence, the selectivity due to the increased electronic stability originated from half-filled d orbitals of the Mn atom stabilized on g-C₃N₄. Also, we present the Gibbs free energy profile, onset potential (UMin), and overpotential (η) for various C₁ products (CO, HCOOH, CH₃OH, and CH₄) at the active sites with and without halogenation. These results suggest that the MnN₆ active site of Mn-X-decorated g-C₃N₄ is a highly efficient and selective electrocatalyst for the CO₂RR against the HER. Our study provides directions for the design of a new CO₂RR catalyst with improved selectivity and efficiency.

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Series: The journal of physical chemistry. C
ISSN: 1932-7447
ISSN-E: 1932-7455
ISSN-L: 1932-7447
Volume: 127
Issue: 30
Pages: 14694 - 14703
DOI: 10.1021/acs.jpcc.3c00597
Type of Publication: A1 Journal article – refereed
Field of Science: 216 Materials engineering
Funding: J.K. thanks the Department of Science and Technology (DST), India, for the financial support through the DST Inspire project (Sanction No: DST/INSPIRE/04/2019/000283).
Copyright information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of physical chemistry c, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see