HCDs@MIL-100(Fe)吸附剂的制备及其苯吸附性能研究

doi:10.6023/A22020074

摘要/Abstract

苯是一种典型的挥发性有机物, 对环境和人体都有较大的危害. 金属有机骨架(MOFs)在吸附挥发性有机物的方面有良好的应用潜力, 但水的存在会降低MOFs的吸附能力. 本工作采用疏水性碳点(HCDs)与MIL-100(Fe)原位合成制备HCDs@MIL-100(Fe)-Cx复合材料, 提高苯的吸附性能. 结果表明, 疏水性碳点通过担载或嵌入的方式与MIL-100(Fe)复合, 复合后的材料比表面积显著增加且具备了多级孔; 协同吸附作用显著提高了材料对苯的吸附量、苯/水竞争吸附选择性以及疏水性, 在25 ℃下, 相对压力为0.9时, HCDs@MIL-100(Fe)-C1对苯的吸附容量是MIL-100(Fe)的2.9倍; HCDs@MIL-100(Fe)-C1对苯/水的竞争吸附选择性最高可达3.4, 而MIL-100(Fe)最高仅达2.4; 复合材料低浓度苯的捕获能力得到增强, HCDs@MIL-100(Fe)-C1的动态穿透时间是MIL-100(Fe)的1.4倍; 且具有良好的循环稳定性.

关键词: 金属有机骨架, 吸附, 疏水性, 碳点, 原位复合

Benzene is a typical volatile organic compound with high photochemical reaction activity, which can seriously harm the environment and human health. Adsorption is an effective method to remove volatile organic compounds (VOCs), and the core of the adsorption method is the development of adsorbents. The high specific surface area and pore volume of metal-organic frameworks (MOFs) make them useful in the field of VOCs adsorption. However, the presence of water lead to a decrease in the adsorption capacity of MOFs. In this work, hydrophobic carbon dots (HCDs)@MIL-100(Fe)-Cx composites were prepared by in situ synthesis of hydrophobic carbon dots with MIL-100(Fe) to improve their benzene adsorption performance. The composite adsorbents were characterized by powder X-ray diffraction (PXRD), N₂ adsorption-desorption, thermal gravimetric (TG), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and transmission electron microscope (TEM), the static adsorption capacity of HCDs@MIL-100(Fe)-Cx for benzene and water was determined by gravimetric vapor adsorption analyzer, the dynamic adsorption performance of benzene was investigated by measuring the breakthrough curve of the fixed bed. The results showed that the HCDs were compounded with MIL-100(Fe) by loading or embedding, and the specific surface area of the compounded materials increased significantly and possessed hierarchical pores. The synergistic adsorption of HCDs and MIL-100(Fe) greatly enhanced the adsorption capacity of benzene and the competitive adsorption selectivity of benzene/water. At 25 ℃, when the relative pressure was 0.9, the benzene adsorption capacity of HCDs@MIL-100(Fe)-C1 was 2.9 times that of MIL-100(Fe). When the relative pressure was 0.1, the adsorption capacity of HCDs@MIL-100(Fe)-C1 for benzene was increased by 175.66 mg/g compared with MIL-100(Fe), while the adsorption capacity for water was only increased by 16.87 mg/g, and the competitive adsorption selectivity of HCDs@MIL-100(Fe)-C1 was up to 3.4, while the highest for MIL-100(Fe) was only 2.4. Water contact angle experiments confirmed that HCDs improved the hydrophobicity of MIL-100(Fe). The ability of the composite to capture low concentration of benzene was enhanced; the dynamic breakthrough time of HCDs@MIL-100(Fe)-C1 was 1.4 times that of MIL-100(Fe), and it has perfect cyclic stability. Therefore, HCDs@MIL-100(Fe)-Cx has reference significance for the preparation of adsorbents with high VOCs adsorption performance.

Key words: metal-organic frameworks (MOFs), adsorption, hydrophobicity, carbon dots, in situ composite

引用此文

刘芳, 潘婷婷, 任秀蓉, 鲍卫仁, 王建成, 胡江亮. HCDs@MIL-100(Fe)吸附剂的制备及其苯吸附性能研究[J]. 化学学报, 2022, 80(7): 879-887.

Fang Liu, Tingting Pan, Xiurong Ren, Weiren Bao, Jiancheng Wang, Jiangliang Hu. Research on Preparation and Benzene Adsorption Performance of HCDs@MIL-100(Fe) Adsorbents[J]. Acta Chimica Sinica, 2022, 80(7): 879-887.

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图/表 15

图1. HCDs@MIL-100(Fe)-Cx的PXRD图谱

Figure 1. PXRD patterns of HCDs@MIL-100(Fe)-Cx

图2. (a) MIL-100(Fe)的SEM谱图; (b) HCDs@MIL-100(Fe)-C1的SEM谱图; (c) HCDs@MIL-100(Fe)-C2的SEM谱图; (d) HCDs@MIL- 100(Fe)-C3的SEM谱图

Figure 2. SEM images of (a) MIL-100(Fe), (b) HCDs@MIL- 100(Fe)-C1, (c) HCDs@MIL-100(Fe)-C2 and (d) HCDs@MIL- 100(Fe)-C3

图3. (a) HCDs@MIL-100(Fe)-C1的TEM图像; (b) HCDs@MIL- 100(Fe)-C2的TEM图像; (c) HCDs@MIL-100(Fe)-C3的TEM图像

Figure 3. TEM images of (a) HCDs@MIL-100(Fe)-C1, (b) HCDs@MIL-100(Fe)-C2 and (c) HCDs@MIL-100(Fe)-C3

图4. HCDs@MIL-100(Fe)-Cx的(a) 77 K下氮气吸脱附等温线、 (b) DFT微孔孔径分布、(c) BJH介孔孔径分布

Figure 4. (a) N2 adsorption and desorption isotherms of the HCDs@MIL-100(Fe)-Cx at 77 K, (b) micropore size distributions of the HCDs@MIL-100(Fe)-Cx by using DFT model and (c) mesopore size distributions of the HCDs@MIL-100(Fe)-Cx by using BJH model

Sample	A_BET/(m²•g^–1)	Pore volume/(cm³•g^–1)
Sample	A_BET/(m²•g^–1)	V_total	V_meso	V_micro
HCDs	3.70	0.0053	0.0050	0.0003
MIL-100(Fe)	786.21	0.46	0.24	0.22
HCDs@MIL-100(Fe)-C1	1546.97	1.33	0.98	0.35
HCDs@MIL-100(Fe)-C2	1458.87	1.29	0.96	0.33
HCDs@MIL-100(Fe)-C3	1406.97	1.15	0.83	0.32

表1. HCDs@MIL-100(Fe)-Cx的比表面积和孔容

Table 1. Specific surface area and pore volume of HCDs@MIL- 100(Fe)-Cx

图5. HCDs和MIL-100(Fe)的作用示意图 (a)骨架嫁接或缺陷位产生; (b)表面担载; (c)孔道填充

Figure 5. Action diagram of HCDs and MIL-100(Fe) (a) frameworks grafting or composition of defect sites; (b) surface loading; (c) filling of pores

图6. HCDs@MIL-100(Fe)-Cx的红外谱图 (A) MIL-100(Fe), (B) HCDs@MIL-100(Fe)-C1, (C) HCDs@MIL-100(Fe)- C2, (D) HCDs@MIL-100(Fe)-C3, (E) HCDs

Figure 6. FTIR spectra of HCDs@MIL-100(Fe)-Cx (A) MIL-100(Fe), (B) HCDs@MIL-100(Fe)-C1, (C) HCDs@MIL-100(Fe)- C2, (D) HCDs@MIL-100(Fe)-C3, (E) HCDs

图7. HCDs@MIL-100(Fe)-Cx的苯-TPD

Figure 7. Benzene-TPD curve of HCDs@MIL-100(Fe)-Cx

图8. (a) MIL-100(Fe)的水接触角; (b) HCDs@MIL-100(Fe)-C1的水接触角; (c) HCDs@MIL-100(Fe)-C2的水接触角; (d) HCDs@MIL- 100(Fe)-C3的水接触角; (e) HCDs的水接触角

Figure 8. Water contact angle of (a) MIL-100(Fe), (b) HCDs@MIL- 100(Fe)-C1, (c) HCDs@MIL-100(Fe)-C2, (d) HCDs@MIL-100(Fe)-C3, (e) HCDs

图9. 25 ℃下 (a) HCDs@MIL-100(Fe)-Cx对苯的吸附等温线、(b) HCDs@MIL-100(Fe)-Cx对水的吸附等温线、(c) IAST模型预测HCDs@MIL-100(Fe)-Cx对苯/水的竞争吸附选择性

Figure 9. Adsorption isotherms of (a) HCDs@MIL-100(Fe)-Cx on benzene, (b) HCDs@MIL-100(Fe)-Cx on water and (c) IAST model prediction of HCDs@MIL-100(Fe)-Cx on benzene/water competitive adsorption selectivity at 25 ℃

吸附剂	吸附量/(mg•g^–1)
	p/p₀=0.1		p/p₀=0.9
	苯	水	苯	水
HCDs	0.31	2.47	461.57	22.97
MIL-100(Fe)	226.06	62.38	356.10	307.79
HCDs@MIL-100(Fe)-C1	401.71	79.25	1029.23	549.57
HCDs@MIL-100(Fe)-C2	375.81	84.78	942.77	569.52
HCDs@MIL-100(Fe)-C3	372.54	83.62	850.58	505.13

表2. HCDs@MIL-100(Fe)-Cx不同相对压力下苯和水的吸附量

Table 2. Adsorption capacity of HCDs@MIL-100(Fe)-Cx for benzene and water under different relative pressures

图10. HCDs@MIL-100(Fe)-Cx上苯的吸附热和吸附量的函数关系

Figure 10. The isosteric heat of benzene adsorption on the HCDs@MIL-100(Fe)-Cx as a function of the amounts adsorbed of benzene

图11. (a) 25 ℃下HCDs@MIL-100(Fe)-Cx的动态穿透曲线; (b) 25 ℃下HCDs@MIL-100(Fe)-Cx的Yoon-Nelson模型拟合曲线 (A) MIL-100(Fe), (B) HCDs@MIL-100(Fe)-C1, (C) HCDs@MIL-100(Fe)- C2, (D) HCDs@MIL-100(Fe)-C3

Figure 11. (a) Benzene breakthrough curves of HCDs@MIL-100(Fe)- Cx at 25 ℃ and (b) Yoon and Nelson model fitted curves of HCDs@MIL-100(Fe)-Cx at 25 ℃ (A) MIL-100(Fe), (B) HCDs@MIL-100(Fe)-C1, (C) HCDs@MIL-100(Fe)- C2, (D) HCDs@MIL-100(Fe)-C3

吸附剂	k/min^–1
MIL-100(Fe)	0.0861
HCDs@MIL-100(Fe)-C1	0.1583
HCDs@MIL-100(Fe)-C2	0.2869
HCDs@MIL-100(Fe)-C3	0.2342

表3. 苯在HCDs@MIL-100(Fe)-Cx上Yoon-Nelson模型拟合得到的速率常数

Table 3. The rate constant of benzene on HCDs@MIL-100(Fe)-Cx obtained by Yoon and Nelson model

图12. 25 ℃下HCDs@MIL-100(Fe)-Cx对苯的循环稳定性

Figure 12. Cyclic stability of benzene on HCDs@MIL-100(Fe)-Cx at 25 ℃

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