Preparation and photocatalytic decolorization performance of MIL-100(FeⅡ/FeⅢ)/ACF composites

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

Abstract

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

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

CLC Number:

X703.1

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.

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.

Figures/Tables 13

References 24

1	WANG Youzhao, PAN Yuan, ZHU Tong, et al. Enhanced performance and microbial community analysis of bioelectrochemical system integrated with bio-contact oxidation reactor for treatment of wastewater containing azo dye[J]. Science of the Total Environment, 2018, 634: 616-627.
2	靳君, 张聪璐. 多壁碳纳米管/壳聚糖复合材料对水中染料的吸附[J]. 工业水处理, 2022, 42(4): 100-105.
	JIN Jun, ZHANG Conglu. Adsorption of dyes in water by multiwall carbon nanotubes/chitosan composite[J]. Industrial Water Treatment, 2022, 42(4): 100-105.
3	孙孟威, 刘壮, 谢锐, 等. 镧离子插层MoS₂膜的制备及印染高盐水处理[J]. 化工进展, 2023, 42(1): 346-353.
	SUN Mengwei, LIU Zhuang, XIE Rui, et al. Preparation of lanthanum ion intercalated MoS₂ membrane for treating dyeing wastewater with high brine[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 346-353.
4	DJATOUBAI Essossimna, KHAN Muhammad Shuaib, Sajjad UL HAQ, et al. BiFeO₃ bandgap engineering by dopants and defects control for efficient photocatalytic water oxidation[J]. Applied Catalysis A: General, 2022, 643: 118737.
5	LI Haihong, WANG Yangtao, WANG Yang, et al. Bacterial degradation of anthraquinone dyes[J]. Journal of Zhejiang University-Science B, 2019, 20(6): 528-540.
6	ZHOU Feng, CAI Lei, YE Wenjie, et al. Efficient and controllable synthesis of 1-aminoanthraquinone via high-temperature ammonolysis using continuous-flow method[J]. Molecules, 2023, 28(11): 4314.
7	ZHOU Yuan, YANG Yaling, ZHAO Ruifang, et al. In situ generation of nano TiO₂ on activated carbon fiber with enhanced photocatalytic degradation performance[J]. Research on Chemical Intermediates, 2021, 47(9): 3769-3784.
8	WEI Haidi, SUN Encheng, ZHANG Shuai, et al. Adsorption/photocatalytic hierarchical nanomaterial g-C₃N₄/Bi₂WO₆/ACF composites to the dynamic degradation of toluene[J]. Journal of Materials Research, 2022, 37(2): 509-521.
9	LIU F, LIU Q, LIU Y, et al. Synthesis and photocatalytic activity of cubic cuprous oxide supported on activated carbon fibers[J]. Chemical Physics Letters, 2019, 718: 54-62.
10	REN Lipei, YU Yan, YANG Yuan, et al. Efficient removal of formaldehyde with ZIF-8 growth on TiO₂-coated activated carbon fiber felts prepared via atomic layer deposition[J]. Journal of Materials Science, 2019, 55: 3167-3180.
11	郭朋举, 何小波, 银凤翔. 电催化氮还原合成氨MOF基催化剂研究进展[J]. 化工进展, 2023, 42(4): 1797-1810.
	GUO Pengju, HE Xiaobo, YIN Fengxiang. Research progress in MOF-based catalysts for electrocatalytic nitrogen reduction to ammonia[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1797-1810.
12	李孟, 李炜, 张帅, 等. MOF及其复合材料吸附去除VOCs应用研究进展[J]. 化工进展, 2021, 40(1): 415-426.
	LI Meng, LI Wei, ZHANG Shuai, et al. Research progress on adsorption of VOCs by MOF and its composite[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 415-426.
13	蔡诗怡, 李津瑜, 吴丽霞, 等. 金属有机框架材料在锂硫电池的应用前沿进展[J]. 化工进展, 2021, 40(6): 3046-3057.
	CAI Shiyi, LI Jinyu, WU Lixia, et al. Progress of MOF materials applied in Li-S batteries[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3046-3057.
14	方龙龙, 郑文姬, 宁梦佳, 等. 功能化Zr-MOF强化混合基质膜CO₂分离[J]. 化工进展, 2022, 41(9): 4954-4962.
	FANG Longlong, ZHENG Wenji, NING Mengjia, et al. Enhanced CO₂ separation of mixed matrix membranes by functionalized Zr-MOF[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4954-4962.
15	ZHANG Chuang, LI Haichao, LI Chen, et al. Fe-loaded MOF-545(Fe): Peroxidase-like activity for dye degradation dyes and high adsorption for the removal of dyes from wastewater[J]. Molecules, 2019, 25(1): 168.
16	马宇晗. 铁基金属骨架MIL-53(Fe)的改性策略及其光芬顿降解水中盐酸四环素研究[D]. 长春: 吉林大学, 2021.
	MA Yuhan. Modification strategy of iron-based metal framework MIL-53(Fe) for photo-Fenton degradation of aqueous tetracycline hydrochloride[D]. Changchun: Jilin University, 2021.
17	WANG Fuxue, ZHANG Ziwei, WANG Fei, et al. Fe-Cu bimetal metal-organic framework for efficient decontamination via Fenton-like process: Synthesis, performance and mechanism[J]. Journal of Colloid and Interface Science, 2023, 649: 384-393.
18	王静, 娄娅娅, 王春梅. 铁基金属-有机框架材料/活性碳纤维复合材料的制备及其对染料的脱色[J]. 纺织学报, 2022, 43(8): 126-131.
	WANG Jing, LOU Yaya, WANG Chunmei. Preparation and decolorization of iron-based metal-organic framework/activated carbon fiber composites[J]. Journal of Textile Research, 2022, 43(8): 126-131.
19	王静, 娄娅娅, 王春梅. TiO₂/MIL-100(Fe)/锦纶复合材料的制备及其对有机染料的脱色[J]. 复合材料学报, 2022, 39(1): 232-241.
	WANG Jing, LOU Yaya, WANG Chunmei. Preparation of TiO₂/MIL-100(Fe)/nylon composite and its decolorization for organic dye[J]. Acta Materiae Compositae Sinica, 2022, 39(1): 232-241.
20	刘冬梅, 金彦, 马天凤, 等. 改性MIL-101(Fe)非均相芬顿反应降解罗丹明B[J]. 环境污染与防治, 2023, 45(5): 589-594, 601.
	LIU Dongmei, JIN Yan, MA Tianfeng, et al. Degradation of rhodamine B by modified MIL-101(Fe) heterogeneous Fenton reaction[J]. Environmental Pollution & Control, 2023, 45(5): 589-594, 601.
21	杜雅欣. 活性炭纤维复合光催化剂合成及性能研究[D]. 唐山: 华北理工大学, 2022.
	DU Yaxin. Study on synthesis and performance of activated carbon fiber composite photocatalyst[D]. Tangshan: North China University of Science and Technology, 2022.
22	GUO Lijun, LI Feifei, LIU Jianxin, et al. Improved visible light photocatalytic nitrogen fixation activity using a Fe^Ⅱ-rich MIL-101(Fe): Breaking the scaling relationship by photoinduced Fe^Ⅱ/Fe^Ⅲcycling[J]. Dalton Transactions, 2022, 51(34): 13085-13093.
23	YANG Taoyu, YU Deyou, WANG Dong, et al. Accelerating Fe(Ⅲ)/Fe(‍Ⅱ) cycle via Fe(‍Ⅱ) substitution for enhancing Fenton-like performance of Fe-MOFs[J]. Applied Catalysis B: Environmental, 2021, 286: 119859.
24	TAO Xumei, YUAN Xinjie, HUANG Liang. Effects of Fe(Ⅱ)/Fe(Ⅲ) of Fe-MOFs on catalytic performance in plasma/Fenton-like system[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 610: 125745.

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

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

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