Efficient electrocatalytic conversion of N2 to NH3 using oxygen-rich vacancy lithium niobate cubes

doi:10.1016/j.cjche.2023.03.009

中国化学工程学报 ›› 2023, Vol. 62 ›› Issue (10): 132-138.DOI: 10.1016/j.cjche.2023.03.009

• Full Length Article • 上一篇下一篇

Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes

Shuhui Fan, Qi Wang, Yanan Hu, Qiang Zhao, Jinping Li, Guang Liu

Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

收稿日期:2023-01-29 修回日期:2023-02-23 出版日期:2023-10-28 发布日期:2023-12-23
通讯作者: Guang Liu,E-mail:liuguang@tyut.edu.cn
基金资助:
We are grateful for the financial support from the National Natural Science Foundation of China (22075196, 21878204), Key Research and Development Program of Shanxi Province (International Cooperation, 201903D421073), Research Project Supported by Shanxi Scholarship Council of China (2022-050).

Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes

Shuhui Fan, Qi Wang, Yanan Hu, Qiang Zhao, Jinping Li, Guang Liu

Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

Received:2023-01-29 Revised:2023-02-23 Online:2023-10-28 Published:2023-12-23
Contact: Guang Liu,E-mail:liuguang@tyut.edu.cn
Supported by:
We are grateful for the financial support from the National Natural Science Foundation of China (22075196, 21878204), Key Research and Development Program of Shanxi Province (International Cooperation, 201903D421073), Research Project Supported by Shanxi Scholarship Council of China (2022-050).

摘要/Abstract

摘要： Instead of the energy-intensive Haber-Bosch process, the researchers proposed a way to produce ammonia using water and nitrogen as feedstock, powered by electricity, without polluting the environment. Nevertheless, how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction (NRR) is still urgent and challenging. Herein, a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method. LiNbO₃ (lithium niobate, LN) cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process, which were used for electrocatalytic NRR under mild conditions. Compared with LN nanoparticles synthesized by solid phase reaction, LN cubes exhibit better NRR performance, with the highest ammonia yield rate (13.74 μg·h^-1·mg^-1) at the best potential of -0.45 V (vs. reversible hydrogen electrode, RHE) and the best Faradaic efficiency (85.43%) at -0.4 V. Moreover, LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current–time tests. Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst, which was conducive to the adsorption and activation of N₂ molecule and also increased the ECSA of electrocatalyst, thus providing more active sites for the NRR process.

关键词: Nitrogen reduction reaction, Ammonia yield rate, Oxygen vacancy, LiNbO₃ cubes, Electronic structure

Abstract: Instead of the energy-intensive Haber-Bosch process, the researchers proposed a way to produce ammonia using water and nitrogen as feedstock, powered by electricity, without polluting the environment. Nevertheless, how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction (NRR) is still urgent and challenging. Herein, a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method. LiNbO₃ (lithium niobate, LN) cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process, which were used for electrocatalytic NRR under mild conditions. Compared with LN nanoparticles synthesized by solid phase reaction, LN cubes exhibit better NRR performance, with the highest ammonia yield rate (13.74 μg·h^-1·mg^-1) at the best potential of -0.45 V (vs. reversible hydrogen electrode, RHE) and the best Faradaic efficiency (85.43%) at -0.4 V. Moreover, LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current–time tests. Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst, which was conducive to the adsorption and activation of N₂ molecule and also increased the ECSA of electrocatalyst, thus providing more active sites for the NRR process.

Key words: Nitrogen reduction reaction, Ammonia yield rate, Oxygen vacancy, LiNbO₃ cubes, Electronic structure

Shuhui Fan, Qi Wang, Yanan Hu, Qiang Zhao, Jinping Li, Guang Liu. Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes[J]. 中国化学工程学报, 2023, 62(10): 132-138.

Shuhui Fan, Qi Wang, Yanan Hu, Qiang Zhao, Jinping Li, Guang Liu. Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes[J]. Chinese Journal of Chemical Engineering, 2023, 62(10): 132-138.

参考文献

[1] X.L. Wang, L.M.Yang, Unveiling the underlying mechanism of nitrogen fixation by a new class of electrocatalysts two-dimensional TM@g-C₄N₃ monosheets, Appl. Surf. Sci. 576 (2022) 151839.
[2] C.C. Dong, F. Wei, J.D. Li, Q. Lu, X.J.Han, Uniform octahedral ZrO₂@C from carbonized UiO-66 for electrocatalytic nitrogen reduction, Mater. Today Energy 22 (2021) 100884.
[3] G.H. Wang, P. Shen, Y.J. Luo, X.T. Li, X.C. Li, K. Chu, A vacancy engineered MnO₂-x electrocatalyst promotes nitrate electroreduction to ammonia, Dalton Trans. 51 (24) (2022) 9206–9212.
[4] H. Zhang, B. Song, W.W. Zhang, Y.W. Cheng, Q.W. Chen, K. Lu, Activation of MoS₂ monolayer electrocatalysts via reduction and phase control in molten sodium for selective hydrogenation of nitrogen to ammonia, Chem. Sci. 13 (33) (2022) 9498–9506.
[5] Y.Q. Liu, L. Huang, Y.X. Fang, X.Y. Zhu, S.J. Dong, Achieving ultrahigh electrocatalytic NH₃ yield rate on Fe-doped Bi₂WO₆ electrocatalyst, Nano Res. 14 (8) (2021) 2711–2716.
[6] W. Mohammadi Aframehr, P.H.Pfromm, Activating dinitrogen for chemical looping ammonia Synthesis: Mn nitride layer growth modeling, Chem. Eng. Sci. 252 (2022) 117287.
[7] W. Al Maksoud, R.K. Rai, N. Morlanés, M. Harb, R. Ahmad, S. Ould-Chikh, D. Anjum, M.N. Hedhili, B.E. Al-Sabban, K. Albahily, L. Cavallo, J.M.Basset, Active and stable Fe-based catalyst, mechanism, and key role of alkali promoters in ammonia synthesis, J. Catal. 394 (2021) 353–365.
[8] K. Chen, Y.J. Luo, P. Shen, X.X. Liu, X.C. Li, X.T. Li, K. Chu, Boosted nitrate electroreduction to ammonia on Fe-doped SnS₂ nanosheet arrays rich in S-vacancies, Dalton Trans. 51 (27) (2022) 10343–10350.
[9] Mu, J.; Gao, X.-W.; Liu, Z.; Luo, W.-B.; Sun, Z.; Gu, Q.; Li, F., Boosting nitrogen electrocatalytic fixation by three-dimensional TiO₂-N nanowire arrays. Journal of Energy Chemistry 2022, 75, 293-300.
[10] Shaona, Chen, Boosting nitrogen reduction to ammonia on Fe-N₃S sites by introduction S into defect graphene, Mater. Today Energy 25 (2022) 100954.
[11] J. Teng, X. Qin, W.Y. Guo, X.L. Song, S.N. Xiao, Y.L. Min, Q.J. Xu, J.C.Fan, Boron nitride quantum dots coupled with cop nanosheet arrays grown on carbon cloth for efficient nitrogen reduction reaction, SSRN Electron. J. (2022) 440,135853.
[12] L.H. Ma, F.F. Xu, L.L. Zhang, Z.F. Nie, K. Xia, M.X. Guo, M.Z. Li, X. Ding, Breaking the linear correlations for enhanced electrochemical nitrogen reduction by carbon-encapsulated mixed-valence Fe₇(PO₄)₆, 能源化学(英文版) 31 (2022) (8)182–187, I0006.
[13] J.Y. Xu, X.L. Xu, Y. Du, D. Wu, H.M. Ma, X. Ren, Y.Y. Li, Q. Wei, Carbon-doped tin disulfide nanoflowers: A heteroatomic doping strategy for improving the electrocatalytic performance of nitrogen reduction to ammonia, New J. Chem. 46 (35) (2022) 16661–16665.
[14] Y.H. Cui, C.N. Sun, Y.B. Qu, T.Y. Dai, H.Y. Zhou, Z.L. Wang, Q. Jiang, The development of catalysts for electrochemical nitrogen reduction toward ammonia: Theoretical and experimental advances, Chem. Commun. 58 (74) (2022) 10290–10302.
[15] C.X. Guo, J.R. Ran, A. Vasileff, S.Z. Qiao, Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH₃) under ambient conditions, Energy Environ. Sci. 11 (1) (2018) 45–56.
[16] Y.J. Luo, Q.Q. Li, Y. Tian, Y.P. Liu, K. Chu, Amorphization engineered VSe_2-x nanosheets with abundant Se-vacancies for enhanced N₂ electroreduction, J. Mater. Chem. A 10 (4) (2022) 1742–1749.
[17] J. Liang, Q. Liu, A. Ali Alshehri, X.P.Sun, Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis, Nano Res. Energy 1 (2022) e9120010.
[18] S.L. Foster, S.I.P. Bakovic, R.D. Duda, S. Maheshwari, R.D. Milton, S.D. Minteer, M.J. Janik, J.N. Renner, L.F. Greenlee, Catalysts for nitrogen reduction to ammonia, Nat. Catal. 1 (7) (2018) 490–500.
[19] X.Z. Chen, N. Li, Z.Z. Kong, W.J. Ong, X.J. Zhao, Photocatalytic fixation of nitrogen to ammonia: State-of-the-art advancements and future prospects, Mater. Horiz. 5 (1) (2018) 9–27.
[20] Yuchi, Wan, Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions, Mater. Today 27 (2019) 69–90.
[21] Z.B. Du, J. Liang, S.X. Li, Z.Q. Xu, T.S. Li, Q. Liu, Y.L. Luo, F. Zhang, Y. Liu, Q.Q. Kong, X.F. Shi, B. Tang, A.M. Asiri, B.H. Li, X.P. Sun, Alkylthiol surface engineering: An effective strategy toward enhanced electrocatalytic N₂-to-NH₃ fixation by a CoP nanoarray, J. Mater. Chem. A 9 (24) (2021) 13861–13866.
[22] H.J. Chen, Z.Q. Xu, S.J. Sun, Y.S. Luo, Q. Liu, M.S. Hamdy, Z.S. Feng, X.P. Sun, Y.Wang, Plasma-etched Ti₂O₃ with oxygen vacancies for enhanced NH₃ electrosynthesis and Zn-N₂ batteries, Inorg. Chem. Front. 9 (18) (2022) 4608–4613.
[23] H.J. Chen, J. Liang, K. Dong, L.C. Yue, T.S. Li, Y.S. Luo, Z.S. Feng, N. Li, M.S. Hamdy, A. Ali Alshehri, Y. Wang, X.P. Sun, Q. Liu, Ambient electrochemical N₂-to-NH₃ conversion catalyzed by TiO₂ decorated juncus effusus-derived carbon microtubes, Inorg. Chem. Front. 9 (7) (2022) 1514–1519.
[24] C. Tang, S.Z. Qiao, How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully, Chem. Soc. Rev. 48 (12) (2019) 3166–3180.
[25] L. Shi, Y. Yin, H. Wu, R.A.K. Hirani, X.Y. Xu, J.Q. Zhang, N. Rafique, A.H. Asif, S. Zhang, H.Q.Sun, Controllable synthesis of a hollow Cr₂O₃ electrocatalyst for enhanced nitrogen reduction toward ammonia synthesis, Chin. J. Chem. Eng. 41 (2022) 358–365.
[26] Liu, Q.; Xu, T.; Luo, Y.; Kong, Q.; Li, T.; Lu, S.; Alshehri, A. A.; Alzahrani, K. A.; Sun, X., Recent advances in strategies for highly selective electrocatalytic N₂ reduction toward ambient NH₃ synthesis. Current Opinion in Electrochemistry 2021, 29, 100766.
[27] T. Xu, J. Liang, Y.Y. Wang, S.X. Li, Z.B. Du, T.S. Li, Q. Liu, Y.L. Luo, F. Zhang, X.F. Shi, B. Tang, Q.Q. Kong, A.M. Asiri, C. Yang, D.W. Ma, X.P. Sun, Enhancing electrocatalytic N₂-to-NH₃ fixation by suppressing hydrogen evolution with alkylthiols modified Fe₃P nanoarrays, Nano Res. 15 (2) (2022) 1039–1046.
[28] W.R. Liao, L. Qi, Y.L. Wang, J.Y. Qin, G.Y. Liu, S.J. Liang, H.Y. He, L.L.Jiang, Interfacial engineering promoting electrosynthesis of ammonia over Mo/phosphotungstic acid with high performance, Adv. Funct. Mater. 31 (22) (2021) 2009151.
[29] H. Li, L.Q. Wang, N. Li, J.M. Feng, F. Hou, S.H. Wang, J. Liang. Ion-exchange-induced Bi and K dual-doping of TiOx in molten salts for high-performance electrochemical nitrogen reduction, J. Energy Chem. 69 (2022) 26–34.
[30] J. Wang, H. Jang, G.K. Li, M.G. Kim, Z.X. Wu, X.E. Liu, J. Cho, Efficient electrocatalytic conversion of N₂ to NH₃ on NiWO₄ under ambient conditions, Nanoscale 12 (3) (2020) 1478–1483.
[31] F.H. Li, Q. Tang, A di-boron pair doped MoS₂ (B₂@MoS₂) single-layer shows superior catalytic performance for electrochemical nitrogen activation and reduction, Nanoscale 11 (40) (2019) 18769–18778.
[32] Q. Liu, X.X. Zhang, B. Zhang, Y.L. Luo, G.W. Cui, F.Y. Xie, X.P. Sun, Ambient N₂ fixation to NH₃ electrocatalyzed by a spinel Fe₃O₄ nanorod, Nanoscale 10 (30) (2018) 14386–14389.
[33] T.S. Li, J.J. Xia, H.H. Xian, Q.R. Chen, K. Xu, Y. Gu, Y.L. Luo, Q. Liu, H.R. Guo, E.Traversa, Fe(III) grafted MoO₃ nanorods for effective electrocatalytic fixation of atmospheric N₂ to NH₃, Int. J. Hydrog. Energy 47 (6) (2022) 3550–3555.
[34] Y.Z. Zhang, J. Hu, C.X. Zhang, A.T.F. Cheung, Y. Zhang, L.F. Liu, M.K.H. Leung, Mo₂C embedded on nitrogen-doped carbon toward electrocatalytic nitrogen reduction to ammonia under ambient conditions, Int. J. Hydrog. Energy 46 (24) (2021) 13011–13019.
[35] Y. Liu, Z.F. Pan, O.C. Esan, X.H. Liu, H.Z. Wang, L. An, Efficient electrocatalytic nitrogen reduction to ammonia with FeNi-Co/carbon mat electrodes, J. Alloys Compd. 927 (2022) 166973.
[36] Zemin, Feng, FeS₂/MoS₂@RGO hybrid materials derived from polyoxomolybdate-based metal-organic frameworks as high-performance electrocatalyst for ammonia synthesis under ambient conditions, Chem. Eng. J. 445 (2022) 136797.
[37] J.R. Han, Z.C. Liu, Y.J. Ma, G.W. Cui, F.Y. Xie, F.X. Wang, Y.P. Wu, S.Y. Gao, Y.H. Xu, X.P.Sun, Ambient N₂ fixation to NH₃ at ambient conditions: Using Nb₂O₅ nanofiber as a high-performance electrocatalyst, Nano Energy 52 (2018) 264–270.
[38] W.H. Kong, Z.C. Liu, J.R. Han, L. Xia, Y. Wang, Q. Liu, X.F. Shi, Y.P. Wu, Y.H. Xu, X.P. Sun, Ambient electrochemical N₂-to-NH₃ fixation enabled by Nb₂O₅ nanowire array, Inorg. Chem. Front. 6 (2) (2019) 423–427.
[39] L.S. Huang, J.W. Wu, P. Han, A.M. Al-Enizi, T.M. Almutairi, L.J. Zhang, G.F.Zheng, NbO₂ electrocatalyst toward 32% faradaic efficiency for N₂ fixation, Small Methods 3 (6) (2019) 1800386.
[40] T.X. Wu, M.M. Han, X.G. Zhu, G.Z. Wang, Y.X. Zhang, H.M. Zhang, H.J. Zhao, Experimental and theoretical understanding on electrochemical activation and inactivation processes of Nb₃O₇(OH) for ambient electrosynthesis of NH₃, J. Mater. Chem. A 7 (28) (2019) 16969–16978.
[41] J. Wang, G.K. Li, T. Wei, S.Z. Zhou, X.Q. Ji, X.E. Liu, Dopant-site lattice turbulence of Cu-substituted Nb₂O₅ for efficient nitrogen electroreduction, Nanoscale 13 (5) (2021) 3036–3041.
[42] W.H. Kong, R. Zhang, X.X. Zhang, L. Ji, G.S. Yu, T. Wang, Y.L. Luo, X.F. Shi, Y.H. Xu, X.P. Sun, WO₃ nanosheets rich in oxygen vacancies for enhanced electrocatalytic N₂ reduction to NH₃, Nanoscale 11 (41) (2019) 19274–19277.
[43] Z.C. Wang, X.K. Wu, J. Liu, D. Zhang, H. Zhao, X.Y. Zhang, Y.N. Qin, N.Z. Nie, D. Wang, J.P. Lai, L. Wang, Ordered vacancies on the body-centered cubic PdCu nanocatalysts, Nano Lett. 21 (22) (2021) 9580–9586.
[44] L. Xiao, S.L. Zhu, Y.Q. Liang, Z.Y. Li, S.L. Wu, S.Y. Luo, C.T. Chang, Z.D.Cui, Nanoporous nickel-molybdenum oxide with an oxygen vacancy for electrocatalytic nitrogen fixation under ambient conditions, ACS Appl. Mater. Interfaces 13 (26) (2021) 30722–30730.
[45] K. Chu, Y.J. Luo, P. Shen, X.C. Li, Q.Q. Li, Y.L.Guo, Unveiling the synergy of O-vacancy and heterostructure over MoO_{3- x} /MXene for N₂ electroreduction to NH₃, Adv. Energy Mater. 12 (3) (2022) 2103022.
[46] Y. Wang, X.Y. Zhou, Z. Chen, B. Cai, Z.Z. Ye, C.Y. Gao, J.Y. Huang, Synthesis of cubic LiNbO₃ nanoparticles and their application in vitro bioimaging, Appl. Phys. A 117 (4) (2014) 2121–2126.
[47] Z.L. Jian, X. Lu, Z. Fang, Y.S. Hu, J. Zhou, W. Chen, L.Q.Chen, LiNb₃O₈ as a novel anode material for lithium-ion batteries, Electrochem. Commun. 13 (10) (2011) 1127–1130.

Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes

Efficient electrocatalytic conversion of N₂ to NH₃ using oxygen-rich vacancy lithium niobate cubes

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