Crystal defect engineering of Bi₂Te₃ nanosheets by Ce doping for efficient electrocatalytic nitrogen reduction

Soloveichik, G. Electrochemical synthesis of ammonia as a potential alternative to the Haber–Bosch process. Nat. Catal. 2019, 2, 377–380.

Liang, J.; Liu, P. Y.; Li, Q. Y.; Li, T. S.; Yue, L. C.; Luo, Y. S.; Liu, Q.; Li, N.; Tang, B.; Alshehri, A. A. et al. Amorphous boron carbide on titanium dioxide nanobelt arrays for high-efficiency electrocatalytic NO reduction to NH₃. Angew. Chem., Int. Ed. 2022, 61, e202202087.

Deng, J.; Iñiguez, J. A.; Liu, C. Electrocatalytic nitrogen reduction at low temperature. Joule 2018, 2, 846–856.

Li, S. X.; Luo, Y. L.; Yue, L. C.; Li, T. S.; Wang, Y.; Liu, Q.; Cui, G. W.; Zhang, F.; Asiri, A. M.; Sun, X. P. An amorphous WC thin film enabled high-efficiency N₂ reduction electrocatalysis under ambient conditions. Chem. Commun. 2021, 57, 7806–7809.

Chen, X. Z.; Li, N.; Kong, Z. Z.; Ong, W. J.; Zhao, X. J. Photocatalytic fixation of nitrogen to ammonia: State-of-the-art advancements and future prospects. Mater. Horiz. 2018, 5, 9–27.

Wen, G. L.; Liang, J.; Liu, Q.; Li, T. S.; An, X.; Zhang, F.; Alshehri, A. A.; Alzahrani, K. A.; Luo, Y. L.; Kong, Q. Q. et al. Ambient ammonia production via electrocatalytic nitrite reduction catalyzed by a CoP nanoarray. Nano Res. 2022, 15, 972–977.

Cui, X. Y.; Tang, C.; Zhang, Q. A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Adv. Energy Mater. 2018, 8, 1800369.

Xue, X. L.; Chen, R. P.; Yan, C. Z.; Zhao, P. Y.; Hu, Y.; Zhang, W. J.; Yang, S. Y.; Jin, Z. Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: Advances, challenges and perspectives. Nano Res. 2019, 12, 1229–1249.

Ma, B. Y.; Zhao, H. T.; Li, T. S.; Liu, Q.; Luo, Y. S.; Li, C. B.; Lu, S. Y.; Asiri, A. M.; Ma, D. W.; Sun, X. P. Iron-group electrocatalysts for ambient nitrogen reduction reaction in aqueous media. Nano Res. 2021, 14, 555–569.

Mehta, P.; Barboun, P.; Herrera, F. A.; Kim, J.; Rumbach, P.; Go, D. B.; Hicks, J. C.; Schneider, W. F. Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis. Nat. Catal. 2018, 1, 269–275.

Cao, N.; Chen, Z.; Zang, K. T.; Xu, J.; Zhong, J.; Luo, J.; Xu, X.; Zheng, G. F. Doping strain induced Bi-Ti³⁺ pairs for efficient N₂ activation and electrocatalytic fixation. Nat. Commun. 2019, 10, 2877.

Liu, Q.; Xu, T.; Luo, Y. L.; Kong, Q. Q.; Li, T. S.; Lu, S. Y.; Alshehri, A. A.; Alzahrani, K. A.; Sun, X. P. Recent advances in strategies for highly selective electrocatalytic N₂ reduction toward ambient NH₃ synthesis. Curr. Opin. Electrochem. 2021, 29, 100766.

Xu, T.; Liang, J.; Wang, Y. Y.; Li, S. X.; Du, Z. B.; Li, T. S.; Liu, Q.; Luo, Y. L.; Zhang, F.; Shi, X. F. et al. Enhancing electrocatalytic N₂-to-NH₃ fixation by suppressing hydrogen evolution with alkylthiols modified Fe₃P nanoarrays. Nano Res. 2022, 15, 1039–1046.

Zhao, Y. X.; Zhao, Y. F.; Shi, R.; Wang, B.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Zhang, T. R. Tuning oxygen vacancies in ultrathin TiO₂ nanosheets to boost photocatalytic nitrogen fixation up to 700 nm. Adv. Mater. 2019, 31, 1806482.

Tao, H. C.; Choi, C.; Ding, L. X.; Jiang, Z.; Han, Z. S.; Jia, M. W.; Fan, Q.; Gao, Y. N.; Wang, H. H.; Robertson, A. W. et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem 2019, 5, 204–214.

Lv, C. D.; Qian, Y. M.; Yan, C. S.; Ding, Y.; Liu, Y. Y.; Chen, G.; Yu, G. H. Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions. Angew. Chem., Int. Ed. 2018, 57, 10246–10250.

Liu, C. W.; Li, Q. Y.; Wu, C. Z.; Zhang, J.; Jin, Y. G.; MacFarlane, D. R.; Sun, C. H. Single-boron catalysts for nitrogen reduction reaction. J. Am. Chem. Soc. 2019, 141, 2884–2888.

Ling, C. Y.; Niu, X. H.; Li, Q.; Du, A. J.; Wang, J. L. Metal-free single atom catalyst for N₂ fixation driven by visible light. J. Am. Chem. Soc. 2018, 140, 14161–14168.

Zhao, D. L.; Liang, J.; Li, J.; Zhang, L. C.; Dong, K.; Yue, L. C.; Luo, Y. S.; Ren, Y. C.; Liu, Q.; Hamdy, M. S. et al. A TiO_2−x nanobelt array with oxygen vacancies: An efficient electrocatalyst toward nitrite conversion to ammonia. Chem. Commun. 2022, 58, 3669–3672.

Tong, Y. Y.; Guo, H. P.; Liu, D. L.; Yan, X.; Su, P. P.; Liang, J.; Zhou, S.; Liu, J.; Lu, G. Q.; Dou, S. X. Vacancy engineering of iron-doped W₁₈O₄₉ nanoreactors for low-barrier electrochemical nitrogen reduction. Angew. Chem., Int. Ed. 2020, 59, 7356–7361.

Zhang, L. L.; Cong, M. Y.; Ding, X.; Jin, Y.; Xu, F. F.; Wang, Y.; Chen, L.; Zhang, L. X. A Janus Fe-SnO₂ catalyst that enables bifunctional electrochemical nitrogen fixation. Angew. Chem., Int. Ed. 2020, 59, 10888–10893.

Sun, T.; Zhang, G. Q.; Xu, D.; Lian, X.; Li, H. X.; Chen, W.; Su, C. L. Defect chemistry in 2D materials for electrocatalysis. Mater. Today Energy 2019, 12, 215–238.

Norris, D. J.; Efros, A. L.; Erwin, S. C. Doped nanocrystals. Science 2008, 319, 1776–1779.

Jo, W. J.; Jang, J. W.; Kong, K. J.; Kang, H. J.; Kim, J. Y.; Jun, H.; Parmar, K. P. S.; Lee, J. S. Phosphate doping into monoclinic BiVO₄ for enhanced photoelectrochemical water oxidation activity. Angew. Chem., Int. Ed. 2012, 51, 3147–3151.

Lei, F. C.; Zhang, L.; Sun, Y. F.; Liang, L.; Liu, K. T.; Xu, J. Q.; Zhang, Q.; Pan, B. C.; Luo, Y.; Xie, Y. Atomic-layer-confined doping for atomic-level insights into visible-light water splitting. Angew. Chem., Int. Ed. 2015, 54, 9266–9270.

Sun, D. D.; Zhang, G. J.; Li, D.; Liu, S. T.; Jia, X. L.; Zhou, J. S. A layered Bi₂Te₃ nanoplates/graphene composite with high gravimetric and volumetric performance for Na-ion storage. Sustainable Energy Fuels 2019, 3, 3163–3171.

Min, Y.; Park, G.; Kim, B.; Giri, A.; Zeng, J.; Roh, J. W.; Kim, S. I.; Lee, K. H.; Jeong, U. Synthesis of multishell nanoplates by consecutive epitaxial growth of Bi₂Se₃ and Bi₂Te₃ nanoplates and enhanced thermoelectric properties. ACS Nano 2015, 9, 6843–6853.

Zhang, N.; Zheng, F. F.; Huang, B. L.; Ji, Y. J.; Shao, Q.; Li, Y. Y.; Xiao, X. H.; Huang, X. Q. Exploring Bi₂Te₃ nanoplates as versatile catalysts for electrochemical reduction of small molecules. Adv. Mater. 2020, 32, 1906477.

Liu, M.; Yin, S. L.; Ren, T. L.; Xu, Y.; Wang, Z. Q.; Li, X. N.; Wang, L.; Wang, H. J. Two-dimensional heterojunction electrocatalyst: Au-Bi₂Te₃ nanosheets for electrochemical ammonia synthesis. ACS Appl. Mater. Interfaces 2021, 13, 47458–47464.

Wang, Q. T.; Cui, K.; Li, J.; Wu, Y. X.; Yang, Y. X.; Zhou, X. Z.; Ma, G. F.; Yang, Z. W.; Lei, Z. Q.; Ren, S. F. Iron ion irradiated Bi₂Te₃ nanosheets with defects and regulated hydrophilicity to enhance the hydrogen evolution reaction. Nanoscale 2020, 12, 16208–16214.

Qu, Q.; Liu, B.; Liang, J.; Li, H.; Wang, J. N.; Pan, D.; Sou, I. K. Expediting hydrogen evolution through topological surface states on Bi₂Te₃. ACS Catal. 2020, 10, 2656–2666.

Wu, T. W.; Zhu, X. J.; Xing, Z.; Mou, S. Y.; Li, C. B.; Qiao, Y. X.; Liu, Q.; Luo, Y. L.; Shi, X. F.; Zhang, Y. N. et al. Greatly improving electrochemical N₂ reduction over TiO₂ nanoparticles by iron doping. Angew. Chem., Int. Ed. 2019, 58, 18449–18453.

Xie, H. T.; Wang, H. B.; Geng, Q.; Xing, Z.; Wang, W.; Chen, J. Y.; Ji, L.; Chang, L.; Wang, Z. M.; Mao, J. Oxygen vacancies of Cr-doped CeO₂ nanorods that efficiently enhance the performance of electrocatalytic N₂ fixation to NH₃ under ambient conditions. Inorg. Chem. 2019, 58, 5423–5427.

Xu, B.; Xia, L.; Zhou, F. L.; Zhao, R. H.; Chen, H. Y.; Wang, T.; Zhou, Q.; Liu, Q.; Cui, G. W.; Xiong, X. L. et al. Enhancing electrocatalytic N₂ reduction to NH₃ by CeO₂ nanorod with oxygen vacancies. ACS Sustainable Chem. Eng. 2019, 7, 2889–2893.

Yang, X. T.; Ma, Y. F.; Liu, Y.; Wang, K. K.; Wang, Y. Q.; Liu, M.; Qiu, X. Q.; Li, W. Z.; Li, J. Defect-induced Ce-doped Bi₂WO₆ for efficient electrocatalytic N₂ reduction. ACS Appl. Mater. Interfaces 2021, 13, 19864–19872.

Xu, Y. B.; Ren, Z. M.; Ren, W. L.; Cao, G. H.; Deng, K.; Zhong, Y. B. Hydrothermal synthesis of single-crystalline Bi₂Te₃ nanoplates. Mater. Lett. 2008, 62, 4273–4276.

Musah, J. D.; Guo, C.; Novitskii, A.; Serhiienko, I.; Adesina, A. E.; Khovaylo, V.; Wu, C. M. L.; Zapien, J. A.; Roy, V. A. L. Ultralow thermal conductivity in dual-doped n-type Bi₂Te₃ material for enhanced thermoelectric properties. Adv. Electron. Mater. 2021, 7, 2000910.

Shahil, K. M. F.; Hossain, M. Z.; Teweldebrhan, D.; Balandin, A. A. Crystal symmetry breaking in few-quintuple Bi₂Te₃ films: Applications in nanometrology of topological insulators. Appl. Phys. Lett. 2010, 96, 153103.

Li, D.; Qin, X. Y.; Liu, Y. F.; Wang, N. N.; Song, C. J.; Sun, R. R. Improved thermoelectric properties for solution grown Bi₂Te_3−xSe_x nanoplatelet composites. RSC Adv. 2013, 3, 2632–2638.

Qi, X.; Ma, W. G.; Zhang, X.; Zhang, C. Raman characterization and transport properties of morphology-dependent two-dimensional Bi₂Te₃ nanofilms. Appl. Surf. Sci. 2018, 457, 41–48.

Liu, P. X.; Jing, P.; Xu, X.; Liu, B. C.; Zhang, J. Structural reconstruction of Ce-MOF with active sites for efficient electrocatalytic N₂ reduction. ACS Appl. Energy Mater. 2021, 4, 12128–12136.

Zhang, M.; Zhang, L.; Wang, H.; Bian, Z. Y. Hybrid electrocatalytic ozonation treatment of high-salinity organic wastewater using Ni-Ce/OMC particle electrodes. Sci. Total Environ. 2020, 724, 138170.

Dai, Z.; Qin, F.; Zhao, H. P.; Ding, J.; Liu, Y. L.; Chen, R. Crystal defect engineering of aurivillius Bi₂MoO₆ by Ce doping for increased reactive species production in photocatalysis. ACS Catal. 2016, 6, 3180–3192.

Liu, P.; Li, J. W.; Yan, J. Y.; Song, W. B. Defect-rich Fe-doped NiS/MoS₂ heterostructured ultrathin nanosheets for efficient overall water splitting. Phys. Chem. Chem. Phys. 2022, 24, 8344–8350.

Tao, L.; Duan, X. D.; Wang, C.; Duan, X. F.; Wang, S. Y. Plasma-engineered MoS₂ thin-film as an efficient electrocatalyst for hydrogen evolution reaction. Chem. Commun. 2015, 51, 7470–7473.

Huang, W. T.; Zhou, Q. W.; Su, S. Q.; Li, J.; Lu, X. B.; Gao, X. S.; Wang, X.; Jin, M. L.; Zhou, G. F.; Zhang, Z. et al. Ion beam defect engineering on ReS₂/Si photocathode with significantly enhanced hydrogen evolution reaction. Adv. Mater. Interfaces 2019, 6, 1801663.

Sun, Y. J.; Liang, Y. X.; Luo, M. C.; Lv, F.; Qin, Y. N.; Wang, L.; Xu, C.; Fu, E. G.; Guo, S. J. Defects and interfaces on PtPb nanoplates boost fuel cell electrocatalysis. Small 2018, 14, 1702259.

Geng, Z.; Liu, Y.; Kong, X.; Li, P.; Li, K.; Liu, Z.; Du, J.; Shu, M.; Si, R.; Zeng, J. Achieving a record-high yield rate of 120.9 μg ${}_{{\mathrm{N}\mathrm{H}}_3}$·mg_cat.⁻¹·h⁻¹ for N₂ electrochemical reduction over Ru single-atom catalysts. Adv. Mater. 2018, 30, 1803498.

Wang, J.; Huang, B. L.; Ji, Y. J.; Sun, M. Z.; Wu, T.; Yin, R. G.; Zhu, X.; Li, Y. Y.; Shao, Q.; Huang, X. Q. A general strategy to glassy M-Te (M = Ru, Rh, Ir) porous nanorods for efficient electrochemical N₂ fixation. Adv. Mater. 2020, 32, 1907112.

Chen, C.; Zhu, X. R.; Wen, X. J.; Zhou, Y. Y.; Zhou, L.; Li, H.; Tao, L.; Li, Q. L.; Du, S. Q.; Liu, T. T. et al. Coupling N₂ and CO₂ in H₂O to synthesize urea under ambient conditions. Nat. Chem. 2020, 12, 717–724.

Liu, Y. Q.; Huang, L.; Fang, Y. X.; Zhu, X. Y.; Nan, J. L.; Dong, S. J. Interfacial electron regulation of Rh atomic layer-decorated SnO₂ heterostructures for enhancing electrocatalytic nitrogen reduction. ACS Appl. Mater. Interfaces 2022, 14, 12304–12313.

Zhao, Z. Q.; Park, J.; Choi, C.; Hong, S.; Hui, X. C.; Zhang, H.; Benedict Lo, T. W.; Robertson, A. W.; Lv, Z. X.; Jung, Y. et al. Engineering vacancy and hydrophobicity of two-dimensional TaTe₂ for efficient and stable electrocatalytic N₂ reduction. Innovation 2022, 3, 100190.

Liu, Q.; Li, X. L.; He, Q.; Khalil, A.; Liu, D. B.; Xiang, T.; Wu, X. J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-MoS₂: Applications for visible-light-driven photocatalytic hydrogen evolution. Small 2015, 11, 5556–5564.

Wang, D. Z.; Zhang, X. Y.; Bao, S. Y.; Zhang, Z. T.; Fei, H.; Wu, Z. Z. Phase engineering of a multiphasic 1T/2H MoS₂ catalyst for highly efficient hydrogen evolution. J. Mater. Chem. A 2017, 5, 2681–2688.

Wang, J. Y.; Tang, J.; Guo, T.; Zhang, S. H.; Xia, W.; Tan, H. B.; Bando, Y.; Wang, X.; Yamauchi, Y. C₃N₄-digested 3D construction of hierarchical metallic phase MoS₂ nanostructures. J. Mater. Chem. A 2019, 7, 18388–18396.

Plecháček, T.; Navrátil, J.; Horák, J.; Lošt’ák, P. Defect structure of Pb-doped Bi₂Te₃ single crystals. Philos. Mag. 2004, 84, 2217–2228.

Kim, Y. H.; Kim, Y.; Kim, H. S.; Choi, S. M.; Kim, S. I.; Lee, K. H. Concentration-dependent excess Cu doping behavior and influence on thermoelectric properties in Bi₂Te₃. Int. J. Energy Res. 2022, 46, 3707–3713.

Zhao, Y. M.; Rabouw, F. T.; van Puffelen, T.; van Walree, C. A.; Gamelin, D. R.; de Mello Donegá, C.; Meijerink, A. Lanthanide-doped CaS and SrS luminescent nanocrystals: A single-source precursor approach for doping. J. Am. Chem. Soc. 2014, 136, 16533–16543.

Kiriya, D.; Tosun, M.; Zhao, P. D.; Kang, J. S.; Javey, A. Air-stable surface charge transfer doping of MoS₂ by benzyl viologen. J. Am. Chem. Soc. 2014, 136, 7853–7856.

Bi, J. H.; Ying, H.; Xu, H.; Zhao, X. Y.; Du, X. Y.; Hao, J. C.; Li, Z. H. Phosphorus vacancy-engineered Ce-doped CoP nanosheets for the electrocatalytic oxidation of 5-hydroxymethylfurfural. Chem. Commun. 2022, 58, 7817–7820.

Yan, G. Y.; Wu, T.; Xing, S. M.; Chen, F.; Zhao, B. W.; Gao, W. J. Ultrathin Ce-doped La₂O₃ nanofilm electrocatalysts for efficient oxygen evolution reactions. Nanotechnology 2022, 33, 245405.