铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究

doi:10.15541/jim20240486

无机材料学报 ›› 2025, Vol. 40 ›› Issue (7): 747-753.DOI: 10.15541/jim20240486 CSTR: 32189.14.jim20240486

所属专题：【能源环境】污染物催化去除(202512)；【能源环境】金属有机框架材料MOF(202512)

铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究

江宗玉¹(), 黄红花², 清江³, 王红宁¹(), 姚超¹, 陈若愚¹

1.常州大学江苏省精细石化工程重点实验室, 常州 213164
2.青岛海关技术中心, 青岛 266002
3.上海海关工业产品与原材料检验检测技术中心, 上海 200135

收稿日期:2024-11-15 修回日期:2025-02-19 出版日期:2025-07-20 网络出版日期:2025-02-25
通讯作者: 王红宁, 副教授. E-mail: hnwang@cczu.edu.cn
作者简介:江宗玉(2000-), 女, 硕士研究生. E-mail: 17855227241@163.com
基金资助:
青岛海关技术中心(266002);国家重点研发计划(2023YFC3306301)

Aluminum Ion Doped MIL-101(Cr): Preparation and VOCs Adsorption Performance

JIANG Zongyu¹(), HUANG Honghua², QING Jiang³, WANG Hongning¹(), YAO Chao¹, CHEN Ruoyu¹

1. Jiangsu Province Key Laboratory of Fine Petrochemical Engineering, Changzhou University, Changzhou 213164, China
2. Technology Center of Qingdao Customs, Qingdao 266002, China
3. Technical Center for Industrial Product and Raw Material Inspection and Testing, Shanghai Customs, Shanghai 200135, China

Received:2024-11-15 Revised:2025-02-19 Published:2025-07-20 Online:2025-02-25
Contact: WANG Hongning, associate professor. E-mail: hnwang@cczu.edu.cn
About author:JIANG Zongyu (2000-), female, Master candidate. E-mail: 17855227241@163.com
Supported by:
Technology Center of Qingdao Customs(266002);National Key Research and Development Program of China(2023YFC3306301)

摘要/Abstract

摘要：

挥发性有机化合物(VOCs)危害环境质量和人体健康。为了提高吸附剂对VOCs的吸附性能, 本研究基于金属有机框架(MOFs)中金属位点可以取代的策略, 采用一步溶剂热法在MIL-101(Cr)合成体系中掺杂丰富、廉价且环保的金属离子Al³⁺, 以增加MIL-101(Cr)表面的不饱和金属位点。通过调节Al³⁺掺杂量, 得到一系列Al-MIL-101(Cr)样品。通过不同手段表征Al-MIL-101(Cr)样品的形貌和结构, 并研究其对甲苯、正己烷、油气和对二甲苯的吸附性能。MIL-101(Cr)的甲苯、正己烷、油气和对二甲苯静态吸附容量分别为0.676、0.621、0.451和0.812 g·g^-1。随着Al³⁺掺杂量增多, Al-MIL-101(Cr)样品的吸附容量先增加后减小; 当Al³⁺掺杂量达到0.75 mmol时, Al-0.75- MIL-101(Cr)具有最大的吸附容量(0.911 g·g^-1甲苯, 0.755 g·g^-1正己烷, 0.713 g·g^-1油气, 0.875 g·g^-1对二甲苯)。通过单一组分甲苯穿透曲线评估Al-MIL-101(Cr)样品的动态吸附行为, 结果表明Al-MIL-101(Cr)具有良好的VOCs去除能力, 这与其较大的比表面积以及不饱和金属位点增多有关。

关键词: 金属有机框架, 挥发性有机化合物, 铝离子掺杂, 动态吸附, 稳定性

Abstract:

Volatile organic compounds (VOCs) pose significant risks to environmental quality and human health. To enhance adsorption performance of adsorbents for VOCs, further improvement of the unsaturated metal centers becomes a key factor based on the principle that metal ions can be replaced in metal organic frameworks (MOFs). Here, a one-step solvothermal synthesis system was utilized to dope abundant, cost-effective, and environment friendly Al³⁺ ions into MIL-101(Cr) for preparing Al-MIL-101(Cr). Morphologies and structures of MIL-101(Cr) and Al-MIL-101(Cr) samples, alongside the static adsorption performance for toluene, n-hexane, oil and p-xylene, were analyzed. Static adsorption capacities of toluene, n-hexane, oil, and p-xylene of MIL-101(Cr) were 0.676, 0.621, 0.451 and 0.812 g·g^-1, respectively. When Al³⁺ doping amount reached 0.75 mmol, Al-0.75-MIL-101(Cr) displayed maximum VOCs adsorption capacities (0.911 g·g^-1 for toluene, 0.755 g·g^-1 for n-hexane, 0.713 g·g^-1 for oil, and 0.875 g·g^-1 for p-xylene). The dynamic toluene adsorption behavior was assessed through single-component breakthrough curves. Both dynamic and static adsorption results demonstrate that Al-MIL-101(Cr) possesses excellent VOCs removal capabilities, which are attributed to the extensive specific surface area and augmented unsaturated metal sites.

Key words: metal organic framework, volatile organic compound, aluminum ion doping, dynamic adsorption, stability

中图分类号:

X511

江宗玉, 黄红花, 清江, 王红宁, 姚超, 陈若愚. 铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究[J]. 无机材料学报, 2025, 40(7): 747-753.

JIANG Zongyu, HUANG Honghua, QING Jiang, WANG Hongning, YAO Chao, CHEN Ruoyu. Aluminum Ion Doped MIL-101(Cr): Preparation and VOCs Adsorption Performance[J]. Journal of Inorganic Materials, 2025, 40(7): 747-753.

图/表 19

图1 MIL-101(Cr)和Al-MIL-101(Cr)的XRD图谱

Fig. 1 XRD patterns of MIL-101(Cr) and Al-MIL-101(Cr)

图2 MIL-101(Cr)和Al-MIL-101(Cr)的FT-IR光谱图

Fig. 2 FT-IR spectra of MIL-101(Cr) and Al-MIL-101(Cr)

图3 MIL-101(Cr) (a)、Al-0.25-MIL-101(Cr) (b)、Al-0.50- MIL-101(Cr) (c)、Al-0.75-MIL-101(Cr) (d)和Al-1.0-MIL- 101(Cr) (e)的SEM照片

Fig. 3 SEM images of MIL-101(Cr) (a), Al-0.25-MIL-101(Cr) (b), Al-0.50-MIL-101(Cr) (c), Al-0.75-MIL-101(Cr) (d), and Al-1.0-MIL-101(Cr) (e)

图4 MIL-101(Cr)和Al-MIL-101(Cr)的XPS全谱图

Fig. 4 XPS survey spectra of MIL-101(Cr) and Al-MIL-101(Cr)

图5 MIL-101(Cr)和Al-MIL-101(Cr)的氮气吸附-脱附等温线

Fig. 5 Nitrogen adsorption-desorption isotherms of MIL-101(Cr) and Al-MIL-101(Cr) Value of the vertical axis of Al-0.25-MIL-101(Cr) is shifted upwards by 80 units while that of Al-0.50-MIL-101(Cr) is shifted downwards by 80 units

表1 MIL-101(Cr)和Al-MIL-101(Cr)的结构参数

Table 1 Structural parameters of MIL-101(Cr) and Al-MIL-101(Cr)

图6 MIL-101(Cr) (a)、Al-0.25-MIL-101(Cr) (b)、Al-0.50-MIL-101(Cr) (c)、Al-0.75-MIL-101(Cr) (d) 和Al-1.0-MIL-101(Cr) (e)的静态吸附容量

Fig. 6 Static adsorption capacities of MIL-101(Cr) (a), Al-0.25-MIL-101(Cr) (b), Al-0.50-MIL-101(Cr) (c), Al-0.75-MIL-101(Cr) (d), and Al-1.0-MIL-101(Cr) (e)

图7 MIL-101(Cr)和Al-MIL-101(Cr)的动态甲苯吸附穿透曲线

Fig. 7 Dynamic toluene adsorption breakthrough curves of MIL-101(Cr) and Al-MIL-101(Cr)

表2 MIL-101(Cr)和Al-MIL-101(Cr)的动态甲苯吸附参数

Table 2 Dynamic toluene adsorption parameters of MIL-101 (Cr) and Al-MIL-101(Cr)

图8 Al-0.75-MIL-101(Cr)的甲苯吸附穿透拟合曲线

Fig. 8 Toluene adsorption breakthrough fitting curves of Al-0.75-MIL-101(Cr) Colorful figure is available on website

图9 Al-0.75-MIL-101(Cr)在不同温度下的动态甲苯吸附穿透曲线

Fig. 9 Breakthrough curves of dynamic toluene adsorption of Al-0.75-MIL-101(Cr) at different temperatures

图S1 Al-0.75-MIL-101(Cr)的Al2P XPS谱图

Fig. S1 Al2p XPS spectrum of Al-0.75-MIL-101(Cr)

图S2 Al-MIL-101(Cr)样品的孔径分布曲线

Fig. S2 Pore size distribution curves of Al-MIL-101(Cr)

图S3 MIL-101(Cr) (a)、Al-0.25-MIL-101(Cr) (b)、Al-0.50-MIL-101(Cr) (c)、Al-0.75-MIL-101(Cr) (d)和Al-1.0-MIL-101(Cr) (e)对甲苯、正己烷、油气和对二甲苯的解吸效率图

Fig. S3 Desorption efficiency diagrams of toluene, n-hexane, oil and p-xylene of MIL-101(Cr) (a), Al-0.25-MIL-101(Cr) (b), Al-0.50-MIL-101(Cr) (c), Al-0.75-MIL-101(Cr) (d), andAl-1.0-MIL-101(Cr) (e)

图S4 MIL-101(Cr)和Al-MIL-101(Cr)的正己烷、甲苯以及油气的静态吸附容量与SBET(a)和Vt(b)的关系图

Fig. S4 Relationships between static adsorption capacities of MIL-101(Cr) and Al-MIL-101(Cr) for n-hexane, toluene, and oil and SBET (a) and Vt (b) A: MIL-101(Cr); B: Al-0.25-MIL-101(Cr); C: Al-0.50-MIL-101(Cr); D: Al-0.75-MIL-101(Cr); E: Al-1.0-MIL-101(Cr)

图S5 Al-0.75-MIL-101(Cr)的5次动态甲苯吸附穿透曲线

Fig. S5 Five times dynamic toluene adsorption breakthrough curves of Al-0.75-MIL-101(Cr)

表S1 Al-0.75-MIL-101(Cr)的5次动态甲苯吸附参数比较

Table S1 Comparison of 5 times dynamic toluene adsorption parameters of Al-0.75-MIL-101(Cr)

表S2 Al-0.75-MIL-101(Cr)的5次动态甲苯吸附Yoon-Nelson模型的拟合参数

Table S2 Yoon-Nelson model fitting parameters of 5 times dynamic toluene adsorption for Al-0.75-MIL-101(Cr)

表S3 Al-0.75-MIL-101(Cr)在不同温度下的动态甲苯吸附参数比较

Table S3 Comparison of dynamic toluene adsorption parameters of Al-0.75-MIL-101(Cr) at different temperatures

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铝离子掺杂MIL-101(Cr)的制备及其VOCs吸附性能研究

Aluminum Ion Doped MIL-101(Cr): Preparation and VOCs Adsorption Performance

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