BiOCl-Fe2O3@TiO2 Mesoporous Composite for Photoelectrochemical Synthesis of Ammonia

doi:10.6023/A21120562

Abstract

Nitrogen reduction reaction is an indispensable part of chemical production, and traditional Haber-Bosch process has the problems of high energy consumption and serious CO₂ emission. Solar-driven photoelectrochemical synthesis of ammonia has received much attention because it can be carried out under mild conditions. However, the yield of ammonia and conversion efficiency are too low to be practical due to the high dissociation energy of the triply bonded nitrogen molecule. The development of non-precious metal oxide catalysts for ammonia synthesis has the advantages of low commercial cost, high selectivity, and strong operability, which may provide the possibility for commercialization in green ammonia synthesis. In this work, we reported the synthesis of BiOCl-Fe₂O₃@TiO₂ mesoporous composite through a sol-gel method followed by in-situ decomposition approach. The obtained composites were systematically characterized and utilized for photoelectrochemical synthesis of ammonia. The results show that Fe₂O₃ is strongly coupled with TiO₂ to produce a metal oxide-semiconductor heterojunction, while BiOCl nanoparticles are uniformly distributed on the surfaces. Compared to pure TiO₂, the band gap of composite becomes remarkably narrowed. As a result, the visible light absorption is enhanced and the utilization of photogenerated carriers is increased. In addition, BiOCl-Fe₂O₃@TiO₂ composite has plenty of Ti³⁺ for improving the photoelectric migration efficiency. With the presence of BiOCl, the yield of ammonia is significantly increased. Compared with pure TiO₂, the ammonia yield of BiOCl-Fe₂O₃@TiO₂is increased by 7 times, and its ammonia production rate remains stable over 10 h test. Our work offers a new route for photoelectrocatalytic synthesis of green ammonia.

Key words: ammonia synthesis, photoelectrocatalyst, non-noble metal, valence band regulation, photogenerated carrier

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Xiawei Ying, Jianjun Fu, Min Zeng, Wen Liu, Tianyu Zhang, Peikang Shen, Xinyi Zhang. BiOCl-Fe₂O₃@TiO₂ Mesoporous Composite for Photoelectrochemical Synthesis of Ammonia[J]. Acta Chimica Sinica, 2022, 80(4): 503-509.

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Figure 1. (A) X-ray diffraction patterns of the catalyst BFT and FT; (B) N2 adsorption-desorption curve of catalyst BFT; (C) particle size distribution diagram corresponding to catalyst BFT; (D) TEM image of a macropore on the BFT; (E) and (F) HRTEM image of a macropore on the BFT; (G) HRTEM selected area and face scan energy spectrum of BFT

Figure 2. (A) XPS spectra of FT and BFT; (B) Ti 2p high-resolution spectra of FT and BFT; (C) Fe 2p high-resolution spectra of FT and BFT; (D) Bi 4f high-resolution spectra of BFT; (E) Cl 2p high-resolution spectra of BFT; (F) O 1s high-resolution spectra of FT and BFT

Figure 3. (A) UV-Vis absorption-concentration standard curve of 0.1 mol•L-1 Na2SO4 solution; (B) the polarization curve of the catalyst BFT under different conditions; (C) ammonia production rate of photoelectrocatalysis under different contents TiO2, FT and BFT (–0.45 V vs. RHE); (D) ammonia yield of BFT photocatalyst under different potentials

Figure 4. (A) The ammonia synthesis rate of the different contents under PC, PEC, EC and Ar; (B) current density curve of BFT in 10 h under different atmosphere conditions; (C) photocatalytic stability test of BFT at –0.45 V vs. RHE; (D) isotope experiment

Figure 5. (A) Schematic diagram of the PEC cell under 100 mW•cm-2 illumination in 0.1 mol•L-1 Na2SO4; (B) ultraviolet diffuse absorbance spectrum of TiO2 and BFT; (C) photoluminescence spectroscopy of TiO2, FT and BFT; (D) Mott-Schottky curves at 2 kHz of FT and BFT

References 34

[1]	Snyder, C. S.; Davidson, E. A.; Smith, P.; Venterea, R. T. Curr. Opin. Environ. Sustain. 2014, 9-10, 46. doi: 10.1016/j.cosust.2014.07.005
[2]	Kroeze, C.; de Vries, W.; Seitzinger, S. P. Curr. Opin. Environ. Sustain. 2014, 9-10, 105. doi: 10.1016/j.cosust.2014.09.009
[3]	Jonassen, K. R.; Hagen, L. H.; Vick, S. H. W.; Arntzen, M. Ø.; Eijsink, V. G. H.; Frostegård, Å.; Lycus, P.; Molstad, L.; Pope, P. B.; Bakken, L. R. ISME J. 2021, 16, 580. doi: 10.1038/s41396-021-01101-x
[4]	Qing, G.; Ghazfar, R.; Jackowski, S.; Habibzadeh, F.; Maleka Ashtiani, M.; Chen, C.; Smith, M.; Hamann, T. Chem. Rev. 2020, 120, 5437. doi: 10.1021/acs.chemrev.9b00659
[5]	Zhao, S.; Lu, X.; Wang, L.; Gale, J.; Amal, R. Adv. Mater. 2019, 31, 1805367. doi: 10.1002/adma.201805367
[6]	Erisman, J. W.; Sutton, M. A.; Galloway, J.; Klimont, Z.; Winiwarter, W. Nat. Geosci. 2008, 1, 636. doi: 10.1038/ngeo325
[7]	Suryanto, B. H. R.; Du, H.; Wang, D.; Chen, J.; Simonov, A. N.; Macfarlane, D. R. Nat. Catal. 2019, 2, 290. doi: 10.1038/s41929-019-0252-4
[8]	Liu, J.; Wei, Z.; Dou, Y.; Feng, Y.; Ma, J. Rare Met. 2020, 39, 874. doi: 10.1007/s12598-020-01451-z
[9]	Zhou, P.; Chao, Y.; Lv, F.; Lai, J.; Wang, K.; Guo, S. Sci. Bull. 2020, 65, 720. doi: 10.1016/j.scib.2019.12.025
[10]	Zhao, Y.; Zhao, Y.; Shi, R.; Wang, B.; Waterhouse, G. I. N.; Wu, L. Z.; Tung, C. H.; Zhang, T. Adv. Mater. 2019, 31, 1806482. doi: 10.1002/adma.201806482
[11]	Zhang, L.; Ji, X.; Ren, X.; Ma, Y.; Shi, X.; Tian, Z.; Asiri, A. M.; Chen, L.; Tang, B.; Sun, X. Adv. Mater. 2018, 30, 1800191. doi: 10.1002/adma.201800191
[12]	Yu, J.; Yang, Y.; Wei, M. Acta Chim Sinica. 2019, 77, 1129. (in Chinese) doi: 10.6023/A19070260
	(余俊, 杨宇森, 卫敏, 化学学报, 2019, 77, 1129.) doi: 10.6023/A19070260
[13]	Han, Q.; Wu, C.; Jiao, H.; Xu, R.; Wang, Y.; Xie, J.; Guo, Q.; Tang, J. Adv. Mater. 2021, 33, 2008180. doi: 10.1002/adma.202008180
[14]	Huang, H.; Shi, R.; Zhang, X.; Zhao, J.; Su, C.; Zhang, T. Angew. Chem. Int. Ed. 2021, 60, 22963. doi: 10.1002/anie.202110336
[15]	Liu, D.; Wang, J.; Bian, S.; Liu, Q.; Gao, Y.; Wang, X.; Chu, P. K.; Yu, X. Adv. Funct. Mater. 2020, 30, 2002731. doi: 10.1002/adfm.202002731
[16]	Xiong, K.; Chen, J.; Yang, N.; Jiang, S.; Li, L.; Wei, Z. Acta Chim. Sinica 2021, 79, 1138. (in Chinese) doi: 10.6023/A21040136
	(熊昆, 陈伽瑶, 杨娜, 蒋尚坤, 李莉, 魏子栋, 化学学报, 2021, 79, 1138.) doi: 10.6023/A21040136
[17]	Li, R.; Weng, Y.; Zhou, X.; Wang, X.; Mi, Y.; Chong, R.; Chong, R.; Han, H.; Li, C. Energy Environ. Sci. 2015, 8, 2377. doi: 10.1039/C5EE01398D
[18]	Yu, W.; Zhao, L.; Chen, F.; Zhang, H.; Guo, L. J. Phys. Chem. Lett. 2019, 10, 3024. doi: 10.1021/acs.jpclett.9b00863
[19]	Xu, F.; Meng, K.; Cheng, B.; Wang, S.; Xu, J.; Yu, J. Nat. Commun. 2020, 11, 4613. doi: 10.1038/s41467-020-18350-7
[20]	Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Chem. Rev. 2010, 110, 6503. doi: 10.1021/cr1001645
[21]	Yu, L.; Liu, J.; Xu, X.; Zhang, L.; Hu, R.; Liu, J.; Ouyang, L.; Yang, L.; Zhu, M. ACS Nano 2017, 11, 5120. doi: 10.1021/acsnano.7b02136
[22]	Pool, J. A.; Lobkovsky, E.; Chirik, P. J. Nature 2004, 427, 527. doi: 10.1038/nature02274
[23]	Xiong, H.; Wu, L.; Liu, Y.; Gao, T.; Li, K.; Long, Y.; Zhang, R.; Zhang, L.; Qiao, Z.; Huo, Q.; Ge, X.; Song, S.; Zhang, H. Adv. Energy Mater. 2021, 9, 1901634. doi: 10.1002/aenm.201901634
[24]	Zeng, M.; Zeng, X.; Peng, X.; Zhu, Z.; Liao, J.; Liu, K.; Wang, G.; Lin, S. Appl. Surf. Sci. 2016, 388, 352. doi: 10.1016/j.apsusc.2015.12.169
[25]	Mi, P. P.; Guo, M. G.; Dai, Y.; Zhang, X. Mod. Chem. Ind. 2021, 41, 138. (in Chinese)
	(米盼盼, 郭明钢, 代岩, 张旭, 现代化工, 2021, 41, 138.)
[26]	Cui, Z.; Song, H.; Ge, S.; He, W.; Liu, Y. Appl. Surf. Sci. 2019, 467-468, 505. doi: 10.1016/j.apsusc.2018.10.181
[27]	Zhang, W.; Dong, X.; Liang, Y.; Liu, R.; Sun, Y.; Dong, F. Rare Met. 2019, 38, 437. doi: 10.1007/s12598-019-01230-5
[28]	Xu, L.; Xie, Y.; Li, L.; Hu, Z.; Wang, Y.; Yu, J. C. Mater. Today Phys. 2021, 21, 100551.
[29]	Zhou, G.; Wang, F.; Shi, R. J. Catal. 2021, 398, 148. doi: 10.1016/j.jcat.2021.04.017
[30]	Yamashita, T.; Hayes, P. Appl. Surf. Sci. 2008, 254, 2441. doi: 10.1016/j.apsusc.2007.09.063
[31]	Zhao, Y.; Shi, R.; Bian, X.; Zhou, C.; Zhao, Y.; Zhang, S.; Wu, F.; Waterhouse, G. I. N.; Wu, L.; Tung, C.; Zhang, T. Adv. Sci. 2019, 6, 1802109. doi: 10.1002/advs.201802109
[32]	Liu, Q. X.; Ai, L. H.; Jiang, J. J. Mater. Chem. A 2018, 6, 4102. doi: 10.1039/C7TA09350K
[33]	Zhan, S.; Zhang, F. Acta Chim. Sinica 2021, 79, 146. (in Chinese) doi: 10.6023/A20090412
	(詹溯, 章福祥, 化学学报, 2021, 79, 146.) doi: 10.6023/A20090412
[34]	Kang, S.; Zhang, H.; Wang, G.; Zhang, Y.; Zhao, H.; Zhou, H.; Cai, W. Inorg. Chem. Front. 2019, 6, 1432. doi: 10.1039/C9QI00176J

基于BiOCl-Fe₂O₃@TiO₂介孔复合材料的光电化学合成氨性能研究

BiOCl-Fe₂O₃@TiO₂ Mesoporous Composite for Photoelectrochemical Synthesis of Ammonia

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[6]	Wang Ziqing, Chen Geng, Lin Jianxin, Wang Rong, Wei Kemei. Preparation of Ru/Ba-ZrO₂ Catalyst and Its Performance for Ammonia Synthesis [J]. Acta Chimica Sinica, 2013, 71(02): 205-212.
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[8]	. Proton Conduction in La0.9M0.1Ga0.8Mg0.2O3－α at Intermediate Temperature and Its Application to Synthesis of Ammonia at Atmospheric Pressure [J]. Acta Chimica Sinica, 2009, 67(7): 623-628.
[9]	LUO Xiao-Jun, WANG Rong, NI Jun, LIN Jian-Xin, WEI Ge-Mei. Effect of Precipitants on Structure and Catalytic Activity of Ru/CeO2 Catalysts for Ammonia Synthesis [J]. Acta Chimica Sinica, 2009, 67(22): 2573-2578.
[10]	FU Yao; CAO Wang-He*; TIAN Ying. Study on Transport Properties of Photo-generated Carriers in Nanocrystalline TiO₂ Film Electrode [J]. Acta Chimica Sinica, 2006, 64(17): 1761-1764.
[11]	LIN Jing-Dong, HUANG Gui-Yu, XU Zong-Xiang, LIAO Dai-Wei. Effects of Fluoride on Activities of Ru-based Ammonia Synthesis Catalysts [J]. Acta Chimica Sinica, 2004, 62(18): 1717-1720.
[12]	WANG WENXIANG;SUN SHUJUN. Studies on the reduction behavior of amonia synthesis catalysts containing rare earth oxides [J]. Acta Chimica Sinica, 1988, 46(2): 179-183.

基于BiOCl-Fe2O3@TiO2介孔复合材料的光电化学合成氨性能研究