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

doi:10.15541/jim20240486

Abstract

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

CLC Number:

X511

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.

Figures/Tables 19

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

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

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)

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

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

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

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)

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

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

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

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

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

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

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)

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)

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

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

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

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

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