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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

density functional theorynitrogen reductionoxygen vacancieselectron-deficient sites

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References

[1]
J. C. Guo,; H. Wang,; F. Xue,; D. Yu,; L. Zhang,; S. L. Jiao,; Y. H. Liu,; Y. F. Lu,; M. C. Liu,; S. C. Ruan, et al. Tunable synthesis of multiply twinned intermetallic Pd3Pb nanowire networks toward efficient N2 to NH3 conversion. J. Mater. Chem. A 2019, 7, 20247-20253.
Google Scholar
[2]
S. L. Jiao,; X. W. Fu,; L. Zhang,; Y. J. Zeng,; H. W. Huang, Point-defect-optimized electron distribution for enhanced electrocatalysis: Towards the perfection of the imperfections. Nano Today 2020, 31, 100833.
Google Scholar
[3]
J. X. Yao,; D. Bao,; Q. Zhang,; M. M. Shi,; Y. Wang,; R. Gao,; J. M. Yan,; Q. Jiang, Tailoring oxygen vacancies of BiVO4 toward highly efficient noble-metal-free electrocatalyst for artificial N2 fixation under ambient conditions. Small Methods 2019, 3, 1800333.
Google Scholar
[4]
H. C. Tao,; C. Choi,; L. X. Ding,; Z. Jiang,; Z. S. Han,; M. W. Jia,; Q. Fan,; Y. N. Gao,; H. H. Wang,; A. W. Robertson, et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem 2019, 5, 204-214.
Google Scholar
[5]
J. Wang,; L. Yu,; L. Hu,; G. Chen,; H. L. Xin,; X. F. Feng, Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential. Nat. Commun. 2018, 9, 1795.
Google Scholar
[6]
H. Cheng,; L. X. Ding,; G. F. Chen,; L. L. Zhang,; J. Xue,; H. H. Wang, Molybdenum carbide nanodots enable efficient electrocatalytic nitrogen fixation under ambient conditions. Adv. Mater. 2018, 30, 1803694.
Google Scholar
[7]
Y. Zhang,; W. B. Qiu,; Y. J. Ma,; Y. L. Luo,; Z. Q. Tian,; G. W. Cui,; F. Y. Xie,; L. Chen,; T. S. Li,; X. P. Sun, High-performance electrohydrogenation of N2 to NH3 catalyzed by multishelled hollow Cr2O3 microspheres under ambient conditions. ACS Catal. 2018, 8, 8540-8544.
Google Scholar
[8]
D. Bao,; Q. Zhang,; F. L. Meng,; H. X. Zhong,; M. M. Shi,; Y. Zhang,; J. M. Yan,; Q. Jiang,; X. B. Zhang, Electrochemical reduction of N2 under ambient conditions for artificial N2 fixation and renewable energy storage using N2/NH3 cycle. Adv. Mater. 2017, 29, 1604799.
Google Scholar
[9]
W. B. Qiu,; X. Y. Xie,; J. D. Qiu,; W. H. Fang,; R. P. Liang,; X. Ren,; X. Q. Ji,; G. W. Cui,; A. M. Asiri,; G. L. Cui, et al. High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst. Nat. Commun. 2018, 9, 3485.
Google Scholar
[10]
C. D. Lv,; Y. M. Qian,; C. S. Yan,; Y. Ding,; Y. Y. Liu,; G. Chen,; G. H. Yu, Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions. Angew. Chem., Int. Ed. 2018, 57, 10246-10250.
Google Scholar
[11]
C. D. Lv,; C. S. Yan,; G. Chen,; Y. Ding,; J. X. Sun,; Y. S. Zhou,; G. H. Yu, An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Angew. Chem., Int. Ed. 2018, 57, 6073-6076.
Google Scholar
[12]
G. Zhang,; Q. H. Ji,; K. Zhang,; Y. Chen,; Z. H. Li,; H. J. Liu,; J. H. Li,; J. H. Qu, Triggering surface oxygen vacancies on atomic layered molybdenum dioxide for a low energy consumption path toward nitrogen fixation. Nano Energy 2019, 59, 10-16.
Google Scholar
[13]
K. Chu,; Y. P. Liu,; Y. H. Cheng,; Q. Q. Li, Synergistic boron-dopants and boron-induced oxygen vacancies in MnO2 nanosheets to promote electrocatalytic nitrogen reduction. J. Mater. Chem. A 2020, 8, 5200-5208.
Google Scholar
[14]
X. H. Zhao,; X. Zhang,; Z. M. Xue,; W. J. Chen,; Z. Zhou,; T. C. Mu, Fe nanodot-decorated MoS2 nanosheets on carbon cloth: An efficient and flexible electrode for ambient ammonia synthesis. J. Mater. Chem. A 2019, 7, 27417-27422.
Google Scholar
[15]
B. Y. Li,; X. J. Zhu,; J. W. Wang,; R. M. Xing,; Q. Liu,; X. F. Shi,; Y. L. Luo,; S. H. Liu,; X. B. Niu,; X. P. Sun, Ti3+ self-doped TiO2-x nanowires for efficient electrocatalytic N2 reduction to NH3. Chem. Commun. 2020, 56, 1074-1077.
Google Scholar
[16]
Y. H. Li,; H. J. Yu,; Z. Q. Wang,; S. L. Liu,; Y. Xu,; X. N. Li,; L. Wang,; H. J. Wang, Boron-doped silver nanosponges with enhanced performance towards electrocatalytic nitrogen reduction to ammonia. Chem. Commun. 2019, 55, 14745-14748.
Google Scholar
[17]
K. Chu,; Y. P. Liu,; Y. B. Li,; Y. L. Guo,; Y. Tian,; H. Zhang, Multi-functional Mo-doping in MnO2 nanoflowers toward efficient and robust electrocatalytic nitrogen fixation. Appl. Catal. B: Environ. 2020, 264, 118525.
Google Scholar
[18]
Z. S. Han,; C. Choi,; S. Hong,; T. S. Wu,; Y. L. Soo,; Y. Jung,; J. S. Qiu,; Z. Y. Sun, Activated TiO2 with tuned vacancy for efficient electrochemical nitrogen reduction. Appl. Catal. B: Environ. 2019, 257, 117896.
Google Scholar
[19]
S. Zhao,; H. X. Liu,; Y. Qiu,; S. Q. Liu,; J. X. Diao,; C. R. Chang,; R. Si,; X. H. Guo, An oxygen vacancy-rich two-dimensional Au/TiO2 hybrid for synergistically enhanced electrochemical N2 activation and reduction. J. Mater. Chem. A 2020, 8, 6586-6596.
Google Scholar
[20]
F. L. Lai,; J. R. Feng,; X. B. Ye,; W. Zong,; G. J. He,; C. Yang,; W. Wang,; Y. E. Miao,; B. C. Pan,; W. S. Yan, et al. Oxygen vacancy engineering in spinel-structured nanosheet wrapped hollow polyhedra for electrochemical nitrogen fixation under ambient conditions. J. Mater. Chem. A 2020, 8, 1652-1659.
Google Scholar
[21]
M. F. Shao,; R. K. Zhang,; Z. H. Li,; M. Wei,; D. G. Evans,; X. Duan, Layered double hydroxides toward electrochemical energy storage and conversion: Design, synthesis and applications. Chem. Commun. 2015, 51, 15880-15893.
Google Scholar
[22]
D. D. Jiang,; X. Q. Li,; Q. Jia, Design of two-dimensional layered double hydroxide nanosheets embedded with Fe3O4 for highly selective enrichment and isotope labeling of phosphopeptides. ACS Sustainable Chem. Eng. 2019, 7, 421-429.
Google Scholar
[23]
N. L. W. Septiani,; Y. V. Kaneti,; Y. N. Guo,; B. Yuliarto,; X. C. Jiang,; Y. Ide,; N. Nugraha,; H. K. Dipojono,; A. B. Yu,; Y. Sugahara, et al. Holey assembly of two-dimensional iron-doped nickel-cobalt layered double hydroxide nanosheets for energy conversion application. ChemSusChem 2020, 13, 1645-1655.
Google Scholar
[24]
D. J. Zhou,; Z. Cai,; Y. Jia,; X. Y. Xiong,; Q. X. Xie,; S. Y. Wang,; Y. Zhang,; W. Liu,; H. H. Duan,; X. M. Sun, Activating basal plane in NiFe layered double hydroxide by Mn2+ doping for efficient and durable oxygen evolution reaction. Nanoscale Horiz. 2018, 3, 532-537.
Google Scholar
[25]
D. Zhu,; L. H. Zhang,; R. E. Ruther,; R. J. Hamers, Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat. Mater. 2013, 12, 836-841.
Google Scholar
[26]
G. W. Watt,; J. D. Chrisp, Spectrophotometric method for determination of hydrazine. Anal. Chem. 1952, 24, 2006-2008.
Google Scholar
[27]
G. Kresse,; J. Hafner, Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys. Rev. B 1994, 49, 14251-14269.
Google Scholar
[28]
G. Kresse,; D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758-1775.
Google Scholar
[29]
G. Kresse,; J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.
Google Scholar
[30]
J. P. Perdew,; K. Burke,; M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865-3868.
Google Scholar
[31]
S. Grimme,; J. Antony,; S. Ehrlich,; H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Google Scholar
[32]
M. Cococcioni,; S. de Gironcoli, Linear response approach to the calculation of the effective interaction parameters in the LDA + U method. Phys. Rev. B 2005, 71, 035105.
Google Scholar
[33]
J. F. Zhang,; J. Y. Liu,; L. F. Xi,; Y. F. Yu,; N. Chen,; S. H. Sun,; W. C. Wang,; K. M. Lange,; B. Zhang, Single-atom Au/NiFe layered double hydroxide electrocatalyst: Probing the origin of activity for oxygen evolution reaction. J. Am. Chem. Soc. 2018, 140, 3876-3879.
Google Scholar
[34]
Y. Dong,; P. X. Zhang,; Y. L. Kou,; Z. Y. Yang,; Y. P. Li,; X. M. Sun, A first-principles study of oxygen formation over NiFe-layered double hydroxides surface. Catal. Lett. 2015, 145, 1541-1548.
Google Scholar
[35]
D. J. Chadi, Special points for Brillouin-zone integrations. Phys. Rev. B 1977, 16, 1746-1747.
Google Scholar
[36]
C. Choi,; S. Back,; N. Y. Kim,; J. Lim,; Y. H. Kim,; Y. Jung, Suppression of hydrogen evolution reaction in electrochemical N2 reduction using single-atom catalysts: A computational guideline. ACS Catal. 2018, 8, 7517-7525.
Google Scholar
[37]
X. H. Li,; T. S. Li,; Y. J. Ma,; Q. Wei,; W. B. Qiu,; H. R. Guo,; X. F. Shi,; P. Zhang,; A. M. Asiri,; L. Chen, et al. Boosted electrocatalytic N2 reduction to NH3 by defect-rich MoS2 nanoflower. Adv. Energy Mater. 2018, 8, 1801357.
Google Scholar
[38]
S. M. Yin,; W. G. Tu,; Y. Sheng,; Y. H. Du,; M. Kraft,; A. Borgna,; R. Xu, A highly efficient oxygen evolution catalyst consisting of interconnected nickel-iron-layered double hydroxide and carbon nanodomains. Adv. Mater. 2018, 30, 1705106.
Google Scholar
[39]
L. Yu,; H. Q. Zhou,; J. Y. Sun,; F. Qin,; F. Yu,; J. M. Bao,; Y. Yu,; S. Chen,; Z. F. Ren, Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting. Energy Environ. Sci. 2017, 10, 1820-1827.
Google Scholar
[40]
W. Wang,; Y. C. Liu,; J. Li,; J. Luo,; L. Fu,; S. L. Chen, NiFe LDH nanodots anchored on 3D macro/mesoporous carbon as a high-performance ORR/OER bifunctional electrocatalyst. J. Mater. Chem. A 2018, 6, 14299-14306.
Google Scholar
[41]
S. Sirisomboonchai,; S. S. Li,; A. Yoshida,; X. M. Li,; C. Samart,; A. Abudula,; G. Q. Guan, Fabrication of NiO Microflake@NiFe-LDH nanosheet heterostructure electrocatalysts for oxygen evolution reaction. ACS Sustainable Chem. Eng. 2019, 7, 2327-2334.
Google Scholar
[42]
J. F. Xie,; J. P. Xin,; R. X. Wang,; X. D. Zhang,; F. C. Lei,; H. C. Qu,; P. Hao,; G. W. Cui,; B. Tang,; Y. Xie, Sub-3 nm pores in two-dimensional nanomesh promoting the generation of electroactive phase for robust water oxidation. Nano Energy 2018, 53, 74-82.
Google Scholar
[43]
M. Asnavandi,; Y. C. Yin,; Y. B. Li,; C. H. Sun,; C. Zhao, Promoting oxygen evolution reactions through introduction of oxygen vacancies to benchmark NiFe-OOH catalysts. ACS Energy Lett. 2018, 3, 1515-1520.
Google Scholar
[44]
J. N. Wang,; G. R. Yang,; L. Wang,; W. Yan, Synthesis of one-dimensional NiFe2O4 nanostructures: Tunable morphology and high-performance anode materials for Li ion batteries. J. Mater. Chem. A 2016, 4, 8620-8629.
Google Scholar
[45]
S. L. Jiao,; Z. Y. Yao,; M. F. Li,; C. Mu,; H. W. Liang,; Y. J. Zeng,; H. W. Huang, Accelerating oxygen evolution electrocatalysis of two-dimensional NiFe layered double hydroxide nanosheets via space-confined amorphization. Nanoscale 2019, 11, 18894-18899.
Google Scholar
[46]
S. L. Jiao,; Z. Y. Yao,; F. Xue,; Y. F. Lu,; M. C. Liu,; H. Q. Deng,; X. F. Ma,; Z. X. Liu,; C. Ma,; H. W. Huang, et al. Defect-rich one-dimensional MoS2 hierarchical architecture for efficient hydrogen evolution: Coupling of multiple advantages into one catalyst. Appl. Catal. B: Environ. 2019, 258, 117964.
Google Scholar
[47]
S. Nayak,; K. M. Parida, Deciphering Z-scheme charge transfer dynamics in heterostructure NiFe-LDH/N-rGO/g-C3N4 nanocomposite for photocatalytic pollutant removal and water splitting reactions. Sci. Rep. 2019, 9, 2458.
Google Scholar
[48]
S. Anantharaj,; K. Karthick,; M. Venkatesh,; T. V. S. V. Simha,; A. S. Salunke,; L. Ma,; H. Liang,; S. Kundu, Enhancing electrocatalytic total water splitting at few layer Pt-NiFe layered double hydroxide interfaces. Nano Energy 2017, 39, 30-43.
Google Scholar
[49]
L. Q. Li,; C. Tang,; D. Z. Yao,; Y. Zheng,; S. Z. Qiao, Electrochemical nitrogen reduction: Identification and elimination of contamination in electrolyte. ACS Energy Lett. 2019, 4, 2111-2116.
Google Scholar
[50]
H. Y. Jin,; L. Q. Li,; X. Liu,; C. Tang,; W. J. Xu,; S. M. Chen,; L. Song,; Y. Zheng,; S. Z. Qiao, Nitrogen vacancies on 2D layered W2N3: A stable and efficient active site for nitrogen reduction reaction. Adv. Mater. 2019, 31, 1902709.
Google Scholar
[51]
Y. Cheng,; S. Y. Zhao,; B. Johannessen,; J. P. Veder,; M. Saunders,; M. R. Rowles,; M. Cheng,; C. Liu,; M. F. Chisholm,; R. De Marco, et al. Atomically dispersed transition metals on carbon nanotubes with ultrahigh loading for selective electrochemical carbon dioxide reduction. Adv. Mater. 2018, 30, 1706287.
Google Scholar
[52]
Y. Cheng,; J. P. Veder,; L. Thomsen,; S. Y. Zhao,; M. Saunders,; R. Demichelis,; C. Liu,; R. De Marco,; S. P. Jiang, Electrochemically substituted metal phthalocyanines, e-MPc (M = Co, Ni), as highly active and selective catalysts for CO2 reduction. J. Mater. Chem. A 2018, 6, 1370-1375.
Google Scholar
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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