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High-throughput screening of single-atom catalysts confined in monolayer black phosphorus for efficient nitrogen reduction reaction

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Abstract

The discovery of metal-nitrogen centers as the active sites for electrolysis has aroused significant interest in utilizing single-atom catalysts for nitrogen reduction reaction (NRR). Properly designed nanostructured catalysts that strongly interact with nitrogen molecules (N2) can promote adsorption and activation, thereby resulting in efficient catalysts with high stability, activity, and selectivity. In this study, using density functional theory calculations, we selected monolayer black phosphorus (BP) as the substrate and screened a series of single-atom transition metals confined in tri-coordinated and tetra-coordinated active centers (without and with N dopants) to electro-catalyze NRR. As a result, we have identified two promising candidates (Hf1-N1P2-1 and Tc1-N4), which exhibit not only low overpotentials of 0.56 and 0.49 V but also high thermodynamic and electrochemical stability, as well as good selectivity towards NRR over the competing hydrogen evolution reaction. We also demonstrate the ability of Hf1-N1P2-1 and Tc1-N4 to activate and hydrogenate N2 by donating electrons and regulating charge transfer. This study not only predicts new BP-based promising catalysts but also provides guidance for the rational design of high-performance NRR electrocatalysts under ambient conditions.

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Acknowledgements

We acknowledge the financial support from the National Natural Science Foundation of China (No. 11404230) and the Foundation of Science and Technology Bureau of Sichuan Province (No. 2013JY0085). We also acknowledge the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by: the Canada Foundation for Innovation; the Government of Ontario; the Ontario Research Fund-Research Excellence; and the University of Toronto. The authors also acknowledge the computing resources from the High-Performance Computing Center of Sichuan Normal University.

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  1. Xiao-Yan Li and Manyi Duan contributed equally to this work.

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, M5S 1A4, Canada

    Xiao-Yan Li & Pengfei Ou

  2. School of Physics and Electronic Engineering, Sichuan Normal University, Chengdu, 610101, China

    Manyi Duan

  3. Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA

    Pengfei Ou

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  1. Xiao-Yan Li
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Correspondence to Pengfei Ou.

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High-throughput screening of single-atom catalysts confined in monolayer black phosphorus for efficient nitrogen reduction reaction

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Li, XY., Duan, M. & Ou, P. High-throughput screening of single-atom catalysts confined in monolayer black phosphorus for efficient nitrogen reduction reaction. Nano Res. 17, 2360–2367 (2024). https://doi.org/10.1007/s12274-023-6068-1

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