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Research Article

Rational design of bimetallic atoms supported on C3N monolayer to break the linear relations for efficient electrochemical nitrogen reduction

Riming Hu1( ), Yanan Yu2, Yongcheng Li3, Yiran Wang4, Jiaxiang Shang4( ), Yong Nie1, Xuchuan Jiang1( )
Institute for Smart Materials & Engineering, University of Jinan, Jinan 250022, China
Shandong college of Tourism and Hospitality, Jinan 250200, China
Qinghai Provincial Key Laboratory of New Light Alloys, Qinghai Provincial Engineering Research Center of High-Performance Light Metal Alloys and Forming, Qinghai University, Xining 810016, China
School of Materials Science and Engineering, Beihang University, Beijing 100191, China
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Graphical Abstract

The fundamental limitation of scaling relations on limiting potentials is broken through by creating bimetallic atoms sites.

Abstract

Linear relations between the adsorption free energies of nitrogen reduction reaction (NRR) intermediates limit the catalytic activity of single atom catalysts (SACs) to reach the optimal region. Significant improvements in NRR activity require the balance of binding strength of reaction intermediates. Herein, we have investigated the C3N-supported monometallic (M/C3N) and bimetallic (M1M2/C3N) atoms for the electrochemical NRR by using density functional theory (DFT) calculations. The results show that this linear relation does exist for SACs because all the intermediates bind to the same site on M/C3N. But the synergistic effect of the two atoms in M1M2/C3N can create a more flexible adsorption site for intermediates, which results in the decoupling of adsorption free energies of key intermediates. Subsequently, the fundamental limitation of scaling relations on limiting potentials is broken through. Most notably, the optimal limiting potential is increased from −0.63 V for M/C3N to −0.20 V for M1M2/C3N. In addition, the presence of bimetallic atoms can also effectively inhibit the hydrogen evolution reaction (HER) as well as improve the stability of the catalysts. This study proposes that the introduction of bimetallic atoms into C3N is beneficial to break the linear relations and develop efficient NRR electrocatalysts.

Keywords

nitrogen reduction reactionlinear relationsbimetallic atomsC3N density functional theory

Electronic Supplementary Material

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Nano Research
Volume 15 Issue 9,
September 2022
Pages 8656-8664
DOI: 10.1007/s12274-022-4412-5
Cite this article:
Hu R, Yu Y, Li Y, et al. Rational design of bimetallic atoms supported on C3N monolayer to break the linear relations for efficient electrochemical nitrogen reduction. Nano Research, 2022, 15(9): 8656-8664. https://doi.org/10.1007/s12274-022-4412-5
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Received: 26 July 2021
Revised: 17 March 2022
Accepted: 08 April 2022
Published: 31 May 2022
© Tsinghua University Press 2022
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