基于BiOCl-Fe2O3@TiO2介孔复合材料的光电化学合成氨性能研究

doi:10.6023/A21120562

摘要/Abstract

传统合成氨工艺存在能耗高、污染严重的问题. 因此, 高效、低能耗绿色合成氨工艺的开发迫在眉睫. 光电化学以H₂O和N₂为原料, 可以在太阳光驱动下, 在常温常压条件下实现氨的合成, 因而受到广泛重视. 但总的来说, 效率和产率都达不到实际要求. 新型高效催化剂及工艺的开发是提高合成氨产率及效率的关键. 非贵金属催化剂具备成本低、来源广泛、可操作性强的优势, 有利于光电化学合成氨的产业化. 本实验采用溶胶凝胶结合原位热裂解的方法制备了分散性好、结构均匀的BiOCl-Fe₂O₃@TiO₂复合材料, 对其物相、微观结构、表面状态、光学性能、电学性能等方面进行了系统表征, 并探究了该材料在常温常压下光电化学合成氨的催化活性. 结果表明, 同纯介孔TiO₂相比_,BiOCl-Fe₂O₃@TiO₂的吸收带隙变窄, 可见光吸收能力增强, 光生载流子的利用率增加, 光电合成氨的产率提升了7倍, 且BiOCl-Fe₂O₃@TiO₂显示了优异的化学稳定性. 本研究工作为绿色合成氨催化材料及工艺设计提供了新思路.

关键词: 合成氨, 光电催化剂, 非贵金属, 价带调控, 光生载流子

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

引用此文

应霞薇, 浮建军, 曾敏, 刘文, 张天宇, 沈培康, 张信义. 基于BiOCl-Fe₂O₃@TiO₂介孔复合材料的光电化学合成氨性能研究[J]. 化学学报, 2022, 80(4): 503-509.

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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图/表 5

图1. (A) 催化剂BFT和FT的X射线衍射图; (B) 催化剂BFT的N2吸附-脱附曲线; (C) 催化剂BFT对应的粒径分布图; (D) BFT透射电镜图像; (E)和(F) 不同区域下BFT的高分辨率透射电镜图像; (G) BFT透射电镜选区及面扫能谱

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

图2. (A) FT和BFT催化剂的XPS谱; (B) TiO2和BFT的Ti 2p精细谱; (C) FT和BFT的Fe 2p精细谱; (D) BFT 的Bi 4f精细谱; (E) BFT的Cl 2p精细谱; (F) FT和BFT的O 1s精细谱

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

图3. (A) 0.1 mol•L-1 Na2SO4溶液紫外-可见光吸收-浓度标准曲线(插图: 550~700 nm紫外吸收光谱); (B) 催化剂BFT在不同条件下的极化曲线; (C) TiO2、FT和BFT组分条件下的光电催化氨产率(–0.45 V vs. RHE); (D) BFT在不同电位下光电催化的氨产率

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

图4. (A) 最佳实验下, 不同组分在光催化、光电催化、电催化、氩气条件下的合成氨速率; (B) 不同气氛条件下BFT 10 h时间内的电流密度曲线; (C) BFT在–0.45 V vs. RHE下的光电催化稳定性测试; (D) 同位素实验

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

图5. (A) 在0.1 mol•L-1 Na2SO4中, 光电催化电解池在100 mW•cm-2光照射下的示意图; (B) TiO2和BFT的紫外-可见光吸收光谱; (C) TiO2、FT和BFT的光致发光谱; (D) 2 kHz下FT和BFT的莫特-肖特基曲线

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

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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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