MIL-100(FeⅡ/FeⅢ)/ACF复合材料的制备及光催化脱色性能

doi:10.16085/j.issn.1000-6613.2023-1641

摘要/Abstract

摘要：

以七水合硫酸亚铁和无水硫酸铁为金属盐，均苯三甲酸为配体，活性碳纤维（ACF）为基材，在室温下采用原位生长法制备了MIL-100(Fe^Ⅱ/Fe^Ⅲ)/ACF复合材料。研究了复合材料的制备工艺和应用工艺对活性艳蓝KN-R光催化脱色效果的影响，并探讨了其光催化脱色的机理。结果表明：Fe²⁺与Fe³⁺的摩尔比为3∶1，原位生长20h条件下制备的复合材料，在1000W氙灯光照下处理120min，对加入0.32mL/L H₂O₂、pH为3.0、浓度为80mg/L的活性艳蓝KN-R染液的脱色率可达97.1%以上，而且在染液pH=3.0~6.2的范围内脱色率均在95.8%以上，重复使用5次后脱色率有所降低，但仍然可达85.5%。通过自由基捕获实验，发现在光催化体系中起主要作用的是羟基自由基（·OH）和光生空穴（h⁺）。采用扫描电子显微镜（SEM）、X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）对复合材料进行了表征，结果显示MIL-100(Fe^Ⅱ/Fe^Ⅲ)成功负载在ACF上，与MIL-100(Fe^Ⅱ)/ACF相比，MIL-100(Fe^Ⅱ/Fe^Ⅲ)/ACF的活性位点的结合能要高0.2~0.3eV。

关键词: MIL-100(Fe), 活性碳纤维, 染料降解, 自由基, 类芬顿反应

Abstract:

MIL-100 (Fe^Ⅱ/Fe^Ⅲ)/ACF composites were prepared by in-situ growth at room temperature using ferrous heptahydrate and anhydrous ferrous sulfate as metal salts, trimesic acid as ligand and active carbon fiber (ACF) as base material. The influence of the preparation and application processes of composites on the photocatalytic decolorization effect for reactive brilliant blue KN-R was studied and the mechanism of its photocatalytic decolorization was explored. The results showed that the decolorization rate of the composite, which was prepared by in-situ growth for 20h with the mole ratio of Fe²⁺ to Fe³⁺ of 3∶1 on 80mg/L reactive brilliant blue KN-R solution adding 0.32mL/L H₂O₂at pH 3.0 reached 97.1% under the condition of 1000W xenon light illumination and reacting for 120min. The decolorization rate was above 95.8% within the range of pH 3.0 to 6.2. After 5 times reuse, the decolorization rate was decreased but still could reach 85.5%. Through free radical capture experiments, it was found that hydroxyl radicals (·OH) and photo generated vacancies (h⁺) played the main role in the photocatalytic system. The composites were characterized by SEM, XRD, FTIR and XPS. The results indicated that MIL-100 (Fe^Ⅱ/Fe^Ⅲ) was successfully loaded on ACF. The active site binding energy of MIL-100 (Fe^Ⅱ/Fe^Ⅲ)/ACF was 0.2—0.3eV higher compared to MIL-100 (Fe^Ⅱ) / ACF.

Key words: MIL-100 (Fe), activated carbon fiber, dye degradation, free radical, Fenton-like reaction

中图分类号:

X703.1

季青豪, 范婷婷, 王春梅. MIL-100(Fe^Ⅱ/Fe^Ⅲ)/ACF复合材料的制备及光催化脱色性能[J]. 化工进展, 2024, 43(10): 5913-5921.

JI Qinghao, FAN Tingting, WANG Chunmei. Preparation and photocatalytic decolorization performance of MIL-100(Fe^Ⅱ/Fe^Ⅲ)/ACF composites[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5913-5921.

图/表 13

图1 Fe2+与Fe3+的摩尔比对脱色效果的影响

图2 原位生长时间对脱色效果的影响

图3 不同材料的SEM图（放大5000倍）

图4 ACF、MIL-100(FeⅡ)/ACF和MIL-100(FeⅡ/FeⅢ)/ACF的红外光谱图

图5 ACF、MIL-100(FeⅡ)/ACF和MIL-100(FeⅡ/FeⅢ)/ACF的XRD谱图

图6 MIL-100(FeⅡ/FeⅢ)/ACF和MIL-100(FeⅡ)/ACF的XPS谱图

表1 MIL-100(FeⅡ/FeⅢ)/ACF的元素分析

名称	峰位/eV	半峰宽/eV	面积/CPS·eV	占比/%
O 1s	531.29	3.09	411336.46	25.09
C 1s	284.80	2.61	480481.79	70.86
Fe 2p	711.10	3.26	282742.38	4.05

图7 黑暗条件下不同材料的脱色效果

图8 光照条件下不同材料的脱色效果

图9 H2O2用量对脱色效果的影响

图10 染液pH对脱色效果的影响

图11 重复使用的脱色效果

图12 添加不同捕捉剂的脱色效果

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