Research on Preparation and Benzene Adsorption Performance of HCDs@MIL-100(Fe) Adsorbents

doi:10.6023/A22020074

Abstract

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

Cite this article

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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Fig. & Tab. 15

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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HCDs@MIL-100(Fe)吸附剂的制备及其苯吸附性能研究