铁基金属有机凝胶衍生的三氧化二铁纳米片用于光芬顿降解罗丹明B

doi:10.6023/A22070304

摘要/Abstract

光催化剂在工业废水处理中发挥着重要作用. 本工作以室温下一步合成的片状铁基金属有机凝胶(Fe-based Metal-organic gel, Fe-MOG)为前驱体, 在不同温度下煅烧得到了片状(300-Fe₂O₃和400-Fe₂O₃)和球形(500-Fe₂O₃和600-Fe₂O₃)两种形貌的衍生三氧化二铁(Fe₂O₃). 通过一系列测试手段对衍生Fe₂O₃的晶体结构和光电性能进行了表征. 其中, 具有碳骨架结构的400-Fe₂O₃因其优良的电子传输性能和较高的光生电荷分离效率表现出优异的光催化活性, 可在中性条件下60 min内光降解97.5%的罗丹明B (Rh B), 并且在连续五次循环实验后其降解效率仍能达到85.3%. 本工作为开发和设计具有优异催化活性的半导体光催化剂提供了新的思路.

关键词: 金属有机凝胶, 三氧化二铁, 碳骨架, 光芬顿, 罗丹明B

Photocatalysts play an important role in industrial wastewater treatment. So far, the photocatalysts of photo- Fenton degradation of water pollutants include metal-organic frameworks, two-dimensional layered hydroxides, and transition metal oxides. Among them, transition metal oxides have become a research hotspot because of their easy availability of metal ions, stability and non-toxicity during degradation. In particular, ferric oxide (Fe₂O₃) has the advantages of wide visible light absorption range, good optical response and high thermodynamic stability, which is considered to be a promising semiconductor photocatalyst. Herein, in this work, Fe₂O₃ of two morphologies, flakes (namely 300-Fe₂O₃ and 400-Fe₂O₃) and spheres (namely 500-Fe₂O₃ and 600-Fe₂O₃) were obtained by calcinating sheet-like iron-based metal-organic gel (Fe-MOG) synthesized with Fe³⁺ and 1,10-phenanthroline-2,9-dicarboxylic acid in one step at room temperature, and were used for photo-Fenton degradation of rhodamine B (Rh B). The crystal structure and optoelectronic properties of the as-prepared Fe₂O₃ were characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy elemental mapping (EDS), the UV-Vis diffuse reflectance spectra (UV-Vis DRS) and electrochemical impedance spectroscopy (EIS). Among them, 400-Fe₂O₃ with carbon skeleton structure exhibited excellent electron transport performance and high photogenerated charge separation efficiency, endowing it with remarkable catalytic activity. In addition, the existence of oxygen vacancy in 400-Fe₂O₃ promoted the formation of Fe²⁺, which was the key factor to enhance the photo-Fenton activity. 400-Fe₂O₃ could photocatalytically degrade 97.5% Rh B within 60 min under neutral conditions, and the degradation efficiency was retained 85.3% after five consecutive cycles. Under visible light irradiation, a part of the photogenic electron (e^‒) generated by 400-Fe₂O₃ reacted with O₂ to generate superoxide anion radical (•O₂^‒), the other part of e^‒reduced Fe³⁺ to Fe²⁺ in situ. Subsequently, Fe²⁺ can catalyze the decomposition of H₂O₂ into hydroxyl radicals (•OH), and participated in the photodegradation of Rh B together with •O₂^‒. This work provides a new idea for the development and design of semiconductor photocatalysts with excellent catalytic activity.

Key words: metal-organic gel, ferric oxide, carbon skeleton, photo-Fenton, rhodamine B

引用此文

郭湾, 胡聪意, 甄淑君, 黄承志, 李原芳. 铁基金属有机凝胶衍生的三氧化二铁纳米片用于光芬顿降解罗丹明B[J]. 化学学报, 2022, 80(12): 1583-1591.

Wan Guo, Congyi Hu, Shujun Zhen, Chengzhi Huang, Yuanfang Li. Iron-based Metal-organic gel-derived Ferric oxide Nanosheets for Photo-Fenton Degradation of Rhodamine B[J]. Acta Chimica Sinica, 2022, 80(12): 1583-1591.

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图/表 7

图式1. (A) Fe-MOG和衍生Fe2O3的制备以及(B) Fe2O3用于光芬顿降解Rh B示意图

Scheme 1. Schematic representation of (A) the synthesis of Fe-MOG and derived Fe2O3 and (B) the mechanism of Fe2O3 based photo-Fenton system for Rh B degradation

图1. Fe-MOG的SEM图(A); 400-Fe2O3 的SEM图(B), TEM图(C, D), 高分辨TEM图(E)和EDS图(F)

Figure 1. (A) The SEM image of Fe-MOG; (B) The SEM image, (C, D) TEM images; (E) HRTEM and (F) EDS images of 400-Fe2O3

图2. Fe-MOG及衍生Fe2O3的PXRD谱图(A), FT-IR光谱(B), N2吸附-脱附等温线(C)和孔径分布曲线(D)

Figure 2. (A) The PXRD patterns, (B) the FT-IR spectra, (C) N2 adsorption-desorption isotherms and (D) pore size distributions of Fe-MOG and derived Fe2O3

图3. 400-Fe2O3的XPS谱图(A), Fe 2p (B), O 1s (C)和 C 1s (D)的高分辨XPS谱图

Figure 3. The XPS survey spectrum of 400-Fe2O3, the high-resolution XPS spectra of (B) Fe 2p, (C) O 1s and (D) C 1s in 400-Fe2O3

图4. 衍生Fe2O3的紫外-可见漫反射光谱(A)及其相应Tauc曲线(B), 瞬态光电流响应曲线(C)和电化学阻抗谱(D)

Figure 4. (A) UV-Vis diffuse reflection spectra, (B) Tauc plots, (C) transient photocurrent response curves and (D) electrochemical impedance spectroscopy of derived Fe2O3

图5. 黑暗和光照条件下不同催化体系中Rh B的降解效率(A); 不同时间段内衍生Fe2O3降解Rh B的效率(B)及相应的降解速率常数(kabs) (C); pH对400-Fe2O3降解Rh B效率的影响(D)及相应的降解速率常数(kabs) (E); 400-Fe2O3降解Rh B的循环实验(F). 实验条件: Rh B, 20.0 μmol?L?1; H2O2, 1.0 mmol?L?1; 400-Fe2O3, 0.05 mg?mL?1; pH, 7.0

Figure 5. Degradation efficiency of Rh B under the dark and light in different catalytic systems; (B) degradation efficiency in different time of Rh B by derived Fe2O3 and (C) the corresponding disappearance rate constant (kabs); (D) the kinetic curves comparison and (E) the corresponding disappearance rate constant (kabs) of Rh B degradation by 400-Fe2O3 at different pH values; (F) cyclic experiments of photo-Fenton degradation of Rh B by 400-Fe2O3. Reaction conditions: Rh B, 20.0 μmol?L?1; H2O2, 1.0 mmol?L?1; 400-Fe2O3, 0.05 mg?mL?1; pH, 7.0

图6. 400-Fe2O3的能带结构(A); 可见光照射下加入不同浓度的H2O2时的光电流变化(B); 400-Fe2O3降解Rh B的自由基捕获实验, 抑制剂浓度为1.0 mmol?L?1 (C); DMPO-?OH (D), DMPO-?O2? (E)和TEMPO-h+ (F)的ESR光谱

Figure 6. (A) The calculated band structure of 400-Fe2O3; (B) photocurrent changes upon the addition of different concentrations of H2O2 under visible light irradiation; (C) the free radical trapping experiments for degradation of Rh B by 400-Fe2O3, cinhibitors: 1.0 mmol?L?1; the ESR spectra of (D) DMPO-?OH, (E) DMPO-?O2?, and (F) TEMPO-h+ in the 400-Fe2O3 photo-Fenton systems

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