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Nano Research 2023, 16(2): 2185-2191 https://doi.org/10.1007/s12274-022-4977-z
Research Article | Issue | Published: 01 October 2022

Eliminating nitrogen chemisorption barrier with single-atom supported yttrium cluster via electronic promoting effect for highly efficient ammonia synthesis

Show Author's Information Yuzhuo Jiang1,§,  Mengfan Wang2,§,  Sisi Liu2,  Lifang Zhang1( ),  Siyi Qian1,  Yufeng Cao1,  Yu Cheng1,  Tao Qian1,3( ),  Chenglin Yan2,3( )
School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China
Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry, College of Energy, Soochow University, Suzhou 215006, China
Light Industry Institute of Electrochemical Power Sources, Suzhou 215600, China

§ Yuzhuo Jiang and Mengfan Wang contributed equally to this work.

Keywords:
ammonia synthesis, rate-determining step, yttrium cluster, electronic promoting effect, nitrogen chemisorption barrier
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Catalyst activity
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Jiang Y, Wang M, Liu S, et al. Eliminating nitrogen chemisorption barrier with single-atom supported yttrium cluster via electronic promoting effect for highly efficient ammonia synthesis. Nano Research, 2023, 16(2): 2185-2191. https://doi.org/10.1007/s12274-022-4977-z
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Abstract Full text Electronic supplementary material About this article

Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions, but promoting this process remains a significant challenge. Here, by loading yttrium clusters onto a single-atom support, an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis. Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals, making the chemisorption process exothermic. Moreover, according to the “hot atom” mechanism, the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation, thereby dramatically reducing the energy barrier of the overall process. As expected, the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1 μg·h−1·mg−1 at −0.2 V versus the reversible hydrogen electrode, with a Faradaic efficiency of up to 69.7%. This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis, and provides a promising method for the development of catalysts with high catalytic activity and selectivity.


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Electronic supplementary material
About this article

Eliminating nitrogen chemisorption barrier with single-atom supported yttrium cluster via electronic promoting effect for highly efficient ammonia synthesis

Show Author's information Yuzhuo Jiang1,§, Mengfan Wang2,§, Sisi Liu2, Lifang Zhang1( ), Siyi Qian1, Yufeng Cao1, Yu Cheng1, Tao Qian1,3( ), Chenglin Yan2,3( )
School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China
Key Laboratory of Core Technology of High Specific Energy Battery and Key Materials for Petroleum and Chemical Industry, College of Energy, Soochow University, Suzhou 215006, China
Light Industry Institute of Electrochemical Power Sources, Suzhou 215600, China

§ Yuzhuo Jiang and Mengfan Wang contributed equally to this work.

Abstract

Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions, but promoting this process remains a significant challenge. Here, by loading yttrium clusters onto a single-atom support, an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis. Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals, making the chemisorption process exothermic. Moreover, according to the “hot atom” mechanism, the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation, thereby dramatically reducing the energy barrier of the overall process. As expected, the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1 μg·h−1·mg−1 at −0.2 V versus the reversible hydrogen electrode, with a Faradaic efficiency of up to 69.7%. This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis, and provides a promising method for the development of catalysts with high catalytic activity and selectivity.

Keywords: ammonia synthesis, rate-determining step, yttrium cluster, electronic promoting effect, nitrogen chemisorption barrier

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Publication history
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Acknowledgements

Publication history

Received: 11 July 2022
Revised: 26 August 2022
Accepted: 27 August 2022
Published: 01 October 2022
Issue date: February 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. U21A20332, 52103226, and 52071226), the Outstanding Youth Foundation of Jiangsu Province (No. BK20220061), the Natural Science Foundation of Jiangsu Province (No. BK20201171), the Key Research and Development Plan of Jiangsu Province (No. BE2020003-3), and the Fellowship of China Postdoctoral Science Foundation (No. 2021M702382).

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