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Nano Research 2021, 14(11): 4211-4219 https://doi.org/10.1007/s12274-021-3373-4
Research Article | Issue | Published: 04 March 2021

Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction

Show Author's Information Cong Fang,  Wei An( )
College of Chemistry and Chemical EngineeringShanghai University of Engineering ScienceShanghai201620China
Keywords:
single-atom catalyst, electrocatalysis, density functional theory (DFT), N2 reduction, BN nanosheet, spin state
Topics:
Electrolytic reduction
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Fang C, An W. Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction. Nano Research, 2021, 14(11): 4211-4219. https://doi.org/10.1007/s12274-021-3373-4
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Abstract Full text Electronic supplementary material About this article

Single-atom catalysts (SACs) especially supported on two-dimensional nitrogen-doped carbon substrate have been widely reported to be able to effectively promote electrocatalytic N2 reduction reaction (eNRR). The precise design of single-metal-atom active site (SMAS) calls for fundamental understanding of its working mechanism for enhanced eNRR performance. Herein, by means of density functional theory calculations, we theoretically investigate the eNRR performance of nine prototypical SMAS, namely, MN2B2 (M: transition metals of IVB, VB and VIB groups) which comprises of asymmetric ligands of N2B2 embedded in defective BN nanosheet. Our results reveal the significant role of spin state of SMAS in tuning the potential-determining steps of eNRR, in which MN2B2 site with higher spin magnetic moment (μ) is beneficial to reducing limiting potentials (UL) of eNRR. Specially, CrN2B2 (μ = 4μB), VN2B2 (μ = 3μB) and MoN2B2 (μ = 2μB) demonstrate high activity and selectivity to eNRR. The asymmetric ligands of N2B2 are deemed to be superior over mono-symmetric ligands. More importantly, our results demonstrate that breaking (or deviating) of the scaling relations between key N-containing intermediates (*N2H/*N2 and *NH2/*N2) on MN2B2 can be realized by enhancing spin state of SMAS which renders the active site a balanced N-affinity critical for efficient eNRR. This observation is validated by the calculated Sabatier volcano-shape relation between eNRR limiting potentials and N2 adsorption energy. Our study develops the guidance for catalyst design to boost eNRR performance by tuning the spin state of an active site.


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About this article

Single-metal-atom site with high-spin state embedded in defective BN nanosheet promotes electrocatalytic nitrogen reduction

Show Author's information Cong Fang, Wei An( )
College of Chemistry and Chemical EngineeringShanghai University of Engineering ScienceShanghai201620China

Abstract

Single-atom catalysts (SACs) especially supported on two-dimensional nitrogen-doped carbon substrate have been widely reported to be able to effectively promote electrocatalytic N2 reduction reaction (eNRR). The precise design of single-metal-atom active site (SMAS) calls for fundamental understanding of its working mechanism for enhanced eNRR performance. Herein, by means of density functional theory calculations, we theoretically investigate the eNRR performance of nine prototypical SMAS, namely, MN2B2 (M: transition metals of IVB, VB and VIB groups) which comprises of asymmetric ligands of N2B2 embedded in defective BN nanosheet. Our results reveal the significant role of spin state of SMAS in tuning the potential-determining steps of eNRR, in which MN2B2 site with higher spin magnetic moment (μ) is beneficial to reducing limiting potentials (UL) of eNRR. Specially, CrN2B2 (μ = 4μB), VN2B2 (μ = 3μB) and MoN2B2 (μ = 2μB) demonstrate high activity and selectivity to eNRR. The asymmetric ligands of N2B2 are deemed to be superior over mono-symmetric ligands. More importantly, our results demonstrate that breaking (or deviating) of the scaling relations between key N-containing intermediates (*N2H/*N2 and *NH2/*N2) on MN2B2 can be realized by enhancing spin state of SMAS which renders the active site a balanced N-affinity critical for efficient eNRR. This observation is validated by the calculated Sabatier volcano-shape relation between eNRR limiting potentials and N2 adsorption energy. Our study develops the guidance for catalyst design to boost eNRR performance by tuning the spin state of an active site.

Keywords: single-atom catalyst, electrocatalysis, density functional theory (DFT), N2 reduction, BN nanosheet, spin state

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Publication history
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Acknowledgements

Publication history

Received: 01 November 2020
Revised: 28 January 2021
Accepted: 31 January 2021
Published: 04 March 2021
Issue date: November 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21673137), the Science and Technology Commission of Shanghai Municipality (No. 16ZR1413900). W. A. gratefully acknowledges the support from the Program for Top Talents in Songjiang District of Shanghai. The DFT calculations were performed using resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, and the Scientific Data and Computing Center, a com­ponent of the Computational Science Initiative, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

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