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Nano Research 2023, 16(5): 6721-6727 https://doi.org/10.1007/s12274-023-5508-2
Research Article | Issue | Published: 27 February 2023

Hydrogen-assisted activation of N2 molecules on atomic steps of ZnSe nanorods

Show Author's Information Kun Du1,§,  Xiuyao Lang2,§,  Yuanyuan Yang1,  Chuanqi Cheng1,  Ning Lan1,  Kangwen Qiu3( ),  Jing Mao1,  Weichao Wang2,  Tao Ling1( )
Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Institute of New-Energy, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology College of Electronic Information and Optical Engineering, Nankai University, Tianjin 300071, China
College of Energy Engineering, Huanghuai University, Zhumadian 463000, China

§ Kun Du and Xiuyao Lang contributed equally to this work.

Keywords:
work function, ZnSe, atomic steps, electrocatalytic nitrogen reduction reaction
Topics:
Electrocatalysts
Cite this article:
Du K, Lang X, Yang Y, et al. Hydrogen-assisted activation of N2 molecules on atomic steps of ZnSe nanorods. Nano Research, 2023, 16(5): 6721-6727. https://doi.org/10.1007/s12274-023-5508-2
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Abstract Full text Electronic supplementary material About this article

Electrochemical reduction reaction of nitrogen (NRR) offers a promising pathway to produce ammonia (NH3) from renewable energy. However, the development of such process has been hindered by the chemical inertness of N2. It is recently proposed that hydrogen species formed on the surface of electrocatalysts can greatly enhance NRR. However, there is still a lack of atomic-level connection between the hydrogenation behavior of electrocatalysts and their NRR performance. Here, we report an atomistic understanding of the hydrogenation behavior of a highly twinned ZnSe (T-ZnSe) nanorod with a large density of surface atomic steps and the activation of N2 molecules adsorbed on its surface. Our theoretical calculations and in situ infrared spectroscopic characterizations suggest that the atomic steps are essential for the hydrogenation of T-ZnSe, which greatly reduces its work function and efficiently activates adsorbed N2 molecules. Moreover, the liquid-like and free water over T-ZnSe promotes its hydrogenation. As a result, T-ZnSe nanorods exhibit significantly enhanced Faradaic efficiency and NH3 production rate compared with the pristine ZnSe nanorod. This work paves a promising way for engineering electrocatalysts for green and sustainable NH3 production.


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Abstract
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Electronic supplementary material
About this article

Hydrogen-assisted activation of N2 molecules on atomic steps of ZnSe nanorods

Show Author's information Kun Du1,§, Xiuyao Lang2,§, Yuanyuan Yang1, Chuanqi Cheng1, Ning Lan1, Kangwen Qiu3( ), Jing Mao1, Weichao Wang2, Tao Ling1( )
Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Institute of New-Energy, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology College of Electronic Information and Optical Engineering, Nankai University, Tianjin 300071, China
College of Energy Engineering, Huanghuai University, Zhumadian 463000, China

§ Kun Du and Xiuyao Lang contributed equally to this work.

Abstract

Electrochemical reduction reaction of nitrogen (NRR) offers a promising pathway to produce ammonia (NH3) from renewable energy. However, the development of such process has been hindered by the chemical inertness of N2. It is recently proposed that hydrogen species formed on the surface of electrocatalysts can greatly enhance NRR. However, there is still a lack of atomic-level connection between the hydrogenation behavior of electrocatalysts and their NRR performance. Here, we report an atomistic understanding of the hydrogenation behavior of a highly twinned ZnSe (T-ZnSe) nanorod with a large density of surface atomic steps and the activation of N2 molecules adsorbed on its surface. Our theoretical calculations and in situ infrared spectroscopic characterizations suggest that the atomic steps are essential for the hydrogenation of T-ZnSe, which greatly reduces its work function and efficiently activates adsorbed N2 molecules. Moreover, the liquid-like and free water over T-ZnSe promotes its hydrogenation. As a result, T-ZnSe nanorods exhibit significantly enhanced Faradaic efficiency and NH3 production rate compared with the pristine ZnSe nanorod. This work paves a promising way for engineering electrocatalysts for green and sustainable NH3 production.

Keywords: work function, ZnSe, atomic steps, electrocatalytic nitrogen reduction reaction

References(37)

[1]

Galloway, J. N.; Townsend, A. R.; Erisman, J. W.; Bekunda, M.; Cai, Z. C.; Freney, J. R.; Martinelli, L. A.; Seitzinger, S. P.; Sutton M. A. Transformation of the nitrogen cycle: Recent trends, questions, and potential solutions. Science 2008, 320, 889–892.
DOI Google Scholar
[2]

Chen, J. G.; Crooks, R. M.; Seefeldt, L. C.; Bren, K. L.; Bullock, R. M.; Darensbourg, M. Y.; Holland, P. L.; Hoffman, B.; Janik, M. J.; Jones, A. K. et al. Beyond fossil fuel-driven nitrogen transformations. Science 2018, 360, eaar6611.
DOI Google Scholar
[3]

Wang, L.; Xia, M. K.; Wang, H.; Huang, K. F.; Qian, C. X.; Maravelias, C. T.; Ozin, G. A. Greening ammonia toward the solar ammonia refinery. Joule 2018, 2, 1055–1074.
DOI Google Scholar
[4]

Forrest, S. J. K.; Schluschaß, B.; Yuzik-Klimova, E. Y.; Schneider, S. Nitrogen fixation via splitting into nitrido complexes. Chem. Rev. 2021, 121, 6522–6587.
DOI Google Scholar
[5]

Service, R. F. Liquid sunshine. Science 2018, 361, 120–123.
DOI Google Scholar
[6]

Wan, Y. C.; Xu, J. C.; Lv, R. T. Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions. Mater. Today 2019, 27, 69–90.
DOI Google Scholar
[7]

Lv, C. D.; Yan, C. S.; Chen, G.; Ding, Y.; Sun, J. X.; Zhou, Y. S.; Yu, G. H. An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Angew. Chem., Int. Ed. 2018, 57, 6073–6076.
DOI Google Scholar
[8]

Geng, Z. G.; Liu, Y.; Kong, X. D.; Li, P.; Li, K.; Liu, Z. Y.; Du, J. J.; Shu, M.; Si, R.; Zeng, J. Achieving a record-high yield rate of 120.9 μg NH3·mgcat−1·h−1 for N2 electrochemical reduction over Ru single-atom catalysts. Adv. Mater. 2018, 30, 1803498.
DOI Google Scholar
[9]

Tang, C.; Qiao, S. Z. How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. Chem. Soc. Rev. 2019, 48, 3166–3180.
DOI Google Scholar
[10]

Zhang, L. L.; Ding, L. X.; Chen, G. F.; Yang, X. F.; Wang, H. H. Ammonia synthesis under ambient conditions: Selective electroreduction of dinitrogen to ammonia on black phosphorus nanosheets. Angew. Chem., Int. Ed. 2019, 58, 2612–2616.
DOI Google Scholar
[11]

Guo, C. X.; Ran, J. R.; Vasileff, A.; Qiao, S. Z. Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy Environ. Sci. 2018, 11, 45–56.
DOI Google Scholar
[12]

Qing, G. L. T.; Ghazfar, R.; Jackowski, S. T.; Habibzadeh, F.; Ashtiani, M. M.; Chen, C. P.; Smith III, M. R.; Hamann, T. W. Recent advances and challenges of electrocatalytic N2 reduction to ammonia. Chem. Rev. 2020, 120, 5437–5516.
DOI Google Scholar
[13]

Chen, G. F.; Cao, X. R.; Wu, S. Q.; Zeng, X. Y.; Ding, L. X.; Zhu, M.; Wang, H. H. Ammonia electrosynthesis with high selectivity under ambient conditions via a Li+ incorporation strategy. J. Am. Chem. Soc. 2017, 139, 9771–9774.
DOI Google Scholar
[14]

Ye, L.; Nayak-Luke, R.; Bañares-Alcántara, R.; Tsang, E. Reaction: “Green” ammonia production. Chem 2017, 3, 712–714.
DOI Google Scholar
[15]

Jewess, M.; Crabtree, R. H. Electrocatalytic nitrogen fixation for distributed fertilizer production? ACS Sustainable Chem. Eng. 2016, 4, 5855–5858.
DOI Google Scholar
[16]

Shipman, M. A.; Symes, M. D. Recent progress towards the electrosynthesis of ammonia from sustainable resources. Catal. Today 2017, 286, 57–68.
DOI Google Scholar
[17]

Zhang, L.; Ji, X. Q.; Ren, X.; Ma, Y. J.; Shi, X. F.; Tian, Z. Q.; Asiri, A. M.; Chen, L.; Tang, B.; Sun, X. P. Electrochemical ammonia synthesis via nitrogen reduction reaction on a MoS2 catalyst: Theoretical and experimental studies. Adv. Mater. 2018, 30, 1800191.
DOI Google Scholar
[18]

Wang, H.; Si, J. C.; Zhang, T. Y.; Li, Y.; Yang, B.; Li, Z.; Chen, J.; Wen, Z. H.; Yuan, C.; Lei, L. C. et al. Exfoliated metallic niobium disulfate nanosheets for enhanced electrochemical ammonia synthesis and Zn-N2 battery. Appl. Catal. B Environ. 2020, 270, 118892.
DOI Google Scholar
[19]

Suryanto, B. H. R.; Du, H. L.; Wang, D. B.; Chen, J.; Simonov, A. N.; MacFarlane, D. R. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nat. Catal. 2019, 2, 290–296.
DOI Google Scholar
[20]

Zhao, X.; Hu, G. Z.; Chen, G. F.; Zhang, H. B.; Zhang, S. S.; Wang, H. H. Comprehensive understanding of the thriving ambient electrochemical nitrogen reduction reaction. Adv. Mater. 2021, 33, 2007650.
DOI Google Scholar
[21]

Lin, S. S.; Zhang, X. H.; Chen, L. G.; Zhang, Q.; Ma, L. L.; Liu, J. G. A review on catalysts for electrocatalytic and photocatalytic reduction of N2 to ammonia. Green Chem. 2022, 24, 9003–9026.
DOI Google Scholar
[22]

Jia, H. P.; Quadrelli, E. A. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: Relevance of metal hydride bonds and dihydrogen. Chem. Soc. Rev. 2014, 43, 547–564.
DOI Google Scholar
[23]

Zhan, C. G.; Nichols, J. A.; Dixon, D. A. Ionization potential, electron affinity, electronegativity, hardness, and electron excitation energy: Molecular properties from density functional theory orbital energies. J. Phys. Chem. A 2003, 107, 4184–4195.
DOI Google Scholar
[24]

Islam, J.; Shareef, M.; Zabed, H. M.; Qi, X. H.; Chowdhury, F. I.; Das, J.; Uddin, J.; Kaneti, Y. V.; Khandaker, M. U.; Ullah, H. et al. Electrochemical nitrogen fixation in metal-N2 batteries: A paradigm for simultaneous NH3 synthesis and energy generation. Energy Storage Mater. 2023, 54, 98–119.
DOI Google Scholar
[25]

Ren, Y. W.; Yu, C.; Tan, X. Y.; Huang, H. L.; Wei, Q. B.; Qiu, J. S. Strategies to suppress hydrogen evolution for highly selective electrocatalytic nitrogen reduction: Challenges and perspectives. Energy Environ. Sci. 2021, 14, 1176–1193.
DOI Google Scholar
[26]

Wang, J.; Yu, L.; Hu, L.; Chen, G.; Xin, H. L.; Feng, X. F. Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential. Nat. Commun. 2018, 9, 1795.
DOI Google Scholar
[27]

Singh, A. R.; Rohr, B. A.; Schwalbe, J. A.; Cargnello, M.; Chan, K.; Jaramillo, T. F.; Chorkendorff, I.; Nørskov, J. K. Electrochemical ammonia synthesis—The selectivity challenge. ACS Catal. 2017, 7, 706–709.
DOI Google Scholar
[28]

Zhu, D.; Zhang, L. H.; Ruther, R. E.; Hamers, R. J. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat. Mater. 2013, 12, 836–841.
DOI Google Scholar
[29]

Liu, Y.; Wang, L. L.; Chen, L.; Wang, H. D.; Jadhav, A. R.; Yang, T.; Wang, Y. X.; Zhang, J. Q.; Kumar, A.; Lee, J. et al. Unveiling the protonation kinetics-dependent selectivity in nitrogen electroreduction: Achieving 75.05% selectivity. Angew. Chem., Int. Ed. 2022, 61, e202209555.
DOI Google Scholar
[30]

Cheng, H.; Ding, L. X.; Chen, G. F.; Zhang, L. L.; Xue, J.; Wang, H. H. Molybdenum carbide nanodots enable efficient electrocatalytic nitrogen fixation under ambient conditions. Adv. Mater. 2018, 30, 1803694.
DOI Google Scholar
[31]

Ling, T.; Jaroniec, M.; Qiao, S. Z. Recent progress in engineering the atomic and electronic structure of electrocatalysts via cation exchange reactions. Adv. Mater. 2020, 32, 2001866.
DOI Google Scholar
[32]

Sun, K. A.; Wu, X. Y.; Zhuang, Z. W.; Liu, L. Y.; Fang, J. J.; Zeng, L. Y.; Ma, J. G.; Liu, S. J.; Li, J. Z.; Dai, R. Y. et al. Interfacial water engineering boosts neutral water reduction. Nat. Commun. 2022, 13, 6260.
DOI Google Scholar
[33]

Wang, M. M.; Sun, K. A.; Mi, W. L.; Feng, C.; Guan, Z. K.; Liu, Y. Q.; Pan, Y. Interfacial water activation by single-atom Co–N3 sites coupled with encapsulated Co nanocrystals for accelerating electrocatalytic hydrogen evolution. ACS Catal. 2022, 12, 10771–10780.
DOI Google Scholar
[34]

Wang, Y. H.; Zheng, S. S.; Yang, W. M.; Zhou, R. Y.; He, Q. F.; Radjenovic, P.; Dong, J. C.; Li, S. N.; Zheng, J. X.; Yang, Z. L. et al. In situ Raman spectroscopy reveals the structure and dissociation of interfacial water. Nature 2021, 600, 81–85.
DOI Google Scholar
[35]

Gao, Y.; Yang, R.; Wang, C. H.; Liu, C. B.; Wu, Y. M.; Li, H. Z.; Zhang, B. Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes. Sci. Adv. 2022, 8, eabm9477.
DOI Google Scholar
[36]

Liu, H. L.; Han, J. L.; Yuan, J. L.; Liu, C. B.; Wang, D.; Liu, T.; Liu, M. J.; Luo, J. M.; Wang, A. J.; Crittenden, J. C. Deep dehalogenation of florfenicol using crystalline CoP nanosheet arrays on a Ti plate via direct cathodic reduction and atomic H. Environ. Sci. Technol. 2019, 53, 11932–11940.
DOI Google Scholar
[37]

Iriawan, H.; Andersen, S. Z.; Zhang, X. L.; Comer, B. M.; Barrio, J.; Chen, P.; Medford, A. J.; Stephens, I. E. L.; Chorkendorff, I.; Shao-Horn, Y. Methods for nitrogen activation by reduction and oxidation. Nat. Rev. Methods Primers 2021, 1, 56.
DOI Google Scholar
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Publication history
Copyright
Acknowledgements

Publication history

Received: 25 November 2022
Revised: 03 January 2023
Accepted: 15 January 2023
Published: 27 February 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 52071231 and 51722103) and the Natural Science Foundation of Tianjin city (No. 19JCJQJC61900). Calculations were performed on TianHe-1A at the National Supercomputer Center, Tianjin.

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