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Nano Research 2021, 14(5): 1457-1464 https://doi.org/10.1007/s12274-020-3202-1
Research Article | Issue | Published: 02 November 2020

Theory-guided construction of electron-deficient sites via removal of lattice oxygen for the boosted electrocatalytic synthesis of ammonia

Show Author's Information Li Zhang1,§,  Shilong Jiao2,§,  Xin Tan3,§,  Yuliang Yuan1,  Yu Xiang4,  Yu-Jia Zeng2,  Jingyi Qiu4( ),  Ping Peng1( ),  Sean C. Smith3,  Hongwen Huang1( )
College of Materials Science and Engineering, Hunan University, Changsha 410082, China
College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518061, China
Integrated Materials Design Laboratory, Department of Applied Mathematics, Research School of Physics, The Australian National University, Canberra, ACT 2601, Australia
Research Institute of Chemical Defense, Beijing 100191, China
Keywords:
density functional theory, nitrogen reduction, oxygen vacancies, electron-deficient sites
Topics:
AmmoniaDensity functional theoryElectrocatalystsElectrolytesElectrolytic reduction Iron alloysLattice theoryNanocatalystsPotassium hydroxide
Cite this article:
Zhang L, Jiao S, Tan X, et al. Theory-guided construction of electron-deficient sites via removal of lattice oxygen for the boosted electrocatalytic synthesis of ammonia. Nano Research, 2021, 14(5): 1457-1464. https://doi.org/10.1007/s12274-020-3202-1
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Abstract Full text Electronic supplementary material About this article

Rational design of catalytic sites to activate the inert N≡N bond is of paramount importance to advance N2 electroreduction. Here, guided by the theoretical predictions, we construct a NiFe layered double hydroxide (NiFe-LDH) nanosheet catalyst with a high density of electron-deficient sites, which were achieved by introducing oxygen vacancies in NiFe-LDH. Density functional theory calculations indicate that the electron-deficient sites show a much lower energy barrier (0.76 eV) for the potential determining step compared with that of the pristine NiFe-LDH (2.02 eV). Benefiting from this, the NiFe-LDH with oxygen vacancies exhibits the greatly improved electrocatalytic activity, presenting a high NH3 yield rate of 19.44 µg·h-1·mgcat-1, Faradaic efficiency of 19.41% at -0.20 V vs. reversible hydrogen electrode (RHE) in 0.1 M KOH electrolyte, as well as the outstanding stability. The present work not only provides an active electrocatalyst toward N2 reduction but also offers a facile strategy to boost the N2 reduction.


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Electronic supplementary material
About this article

Theory-guided construction of electron-deficient sites via removal of lattice oxygen for the boosted electrocatalytic synthesis of ammonia

Show Author's information Li Zhang1,§, Shilong Jiao2,§, Xin Tan3,§, Yuliang Yuan1, Yu Xiang4, Yu-Jia Zeng2, Jingyi Qiu4( ), Ping Peng1( ), Sean C. Smith3, Hongwen Huang1( )
College of Materials Science and Engineering, Hunan University, Changsha 410082, China
College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518061, China
Integrated Materials Design Laboratory, Department of Applied Mathematics, Research School of Physics, The Australian National University, Canberra, ACT 2601, Australia
Research Institute of Chemical Defense, Beijing 100191, China

Abstract

Rational design of catalytic sites to activate the inert N≡N bond is of paramount importance to advance N2 electroreduction. Here, guided by the theoretical predictions, we construct a NiFe layered double hydroxide (NiFe-LDH) nanosheet catalyst with a high density of electron-deficient sites, which were achieved by introducing oxygen vacancies in NiFe-LDH. Density functional theory calculations indicate that the electron-deficient sites show a much lower energy barrier (0.76 eV) for the potential determining step compared with that of the pristine NiFe-LDH (2.02 eV). Benefiting from this, the NiFe-LDH with oxygen vacancies exhibits the greatly improved electrocatalytic activity, presenting a high NH3 yield rate of 19.44 µg·h-1·mgcat-1, Faradaic efficiency of 19.41% at -0.20 V vs. reversible hydrogen electrode (RHE) in 0.1 M KOH electrolyte, as well as the outstanding stability. The present work not only provides an active electrocatalyst toward N2 reduction but also offers a facile strategy to boost the N2 reduction.

Keywords: density functional theory, nitrogen reduction, oxygen vacancies, electron-deficient sites

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Publication history
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Acknowledgements

Publication history

Received: 07 August 2020
Revised: 23 September 2020
Accepted: 21 October 2020
Published: 02 November 2020
Issue date: May 2021

Copyright

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21603208), Shenzhen Science and Technology Project (Nos. JCYJ20170412105400428 and JCYJ20180507182246321), Shenzhen Peacock Technological Innovation Project (No. KQJSCX20170727101208249), Fundamental Research Funds for the Central Universities, the Open Project Program of the State Key Laboratory of Silicon Materials, Zhejiang University, and China Postdoctoral Science Foundation (No. 2019M663058). This research was undertaken with the assistance of resources provided by the National Computational Infrastructure (NCI) facility at the Australian National University; allocated through both the National Computational Merit Allocation Scheme supported by the Australian Government and the Australian Research Council grant LE190100021 (Sustaining and strengthening merit-based access at NCI, 2019-2021).

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