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Research Article

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

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
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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

nitrogen reductiondensity functional theoryoxygen vacancieselectron-deficient sites

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Nano Research
Volume 14 Issue 5,
May 2021
Pages 1457-1464
DOI: 10.1007/s12274-020-3202-1
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
Topics:
AmmoniaDensity functional theoryElectrocatalystsElectrolytesElectrolytic reduction Iron alloysLattice theoryNanocatalystsPotassium hydroxide

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Received: 07 August 2020
Revised: 23 September 2020
Accepted: 21 October 2020
Published: 02 November 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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