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, based on the principle that metal ions can be replaced in metal organic framework (MOFs), improving unsaturated metal centers, a one-step solvothermal method was utilized to dope abundant, cost-effective, and environmentally friendly Al³⁺ ions into MIL-101(Cr) synthesis system for preparing Al-MIL-101(Cr). Various techniques were employed to analyze the morphology and structure of MIL-101(Cr) and Al-MIL-101(Cr) samples, alongside an investigation into the static toluene, hexane, oil and p-xylene adsorption performance. The static toluene, hexane, gasoline and p-xylene adsorption capacities of MIL-101 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) demonstrated maximum VOCs adsorption capacities (0.991 g·g^-1 for toluene, 0.755 g·g^-1 for hexane, 0.713 g·g^-1 for oil, and 0.875 g·g^-1for p-xylene). The dynamic toluene adsorption behavior was assessed through single-component breakthrough curves. Both dynamic and static adsorption results confirmed that Al-MIL-101(Cr) possess excellent VOCs removal capabilities, which 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, DOI: 10.15541/jim20240486.

References

[1] YE Q Q, CHEN Y Y, LI Y Z,et al. Management of typical VOCs in air with adsorbents: status and challenges. Dalton Transactions, 2023, 52(35): 12169.
[2] FETISOV V, GONOPOLSKY A M, DAVARDOOST H,et al. Regulation and impact of VOC and CO₂ emissions on low-carbon energy systems resilient to climate change: a case study on an environmental issue in the oil and gas industry. Energy Science & Engineering, 2023, 11(4): 1516.
[3] HE T, KONG X J, BIAN Z X,et al. Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks. Nature Materials, 2022, 21(6): 689.
[4] GAN G Q, FAN S Y, LI X Y,et al. Adsorption and membrane separation for removal and recovery of volatile organic compounds. Journal of Environmental Sciences, 2023, 123: 96.
[5] WANG H C, GUO H, ZHAO Y X,et al. Thermodynamic analysis of a petroleum volatile organic compounds (VOCs) condensation recovery system combined with mixed-refrigerant refrigeration. International Journal of Refrigeration, 2020, 116: 23.
[6] WU X M, ZHANG Q G, SOYEKWO F,et al. Pervaporation removal of volatile organic compounds from aqueous solutions using the highly permeable PIM-1 membrane. AIChE Journal, 2016, 62(3): 842.
[7] YANG Y, ZHAO S H, CUI L F,et al. Recent advancement and future challenges of photothermal catalysis for VOCs elimination: from catalyst design to applications. Green Energy & Environment, 2023, 8(3): 654.
[8] QIAN X F, YUE D T, TIAN Z Y,et al. Carbon quantum dots decorated Bi₂WO₆ nanocomposite with enhanced photocatalytic oxidation activity for VOCs. Applied Catalysis B: Environmental, 2016, 193: 16.
[9] QIN L B, XU Z, LIU L,et al. In-situ biodegradation of volatile organic compounds in landfill by sewage sludge modified waste-char. Waste Management, 2020, 105: 317.
[10] SUGIMOTO I, NAGAOKA T, SEYAMA M,et al. Classification and characterization of atmospheric VOCs based on sorption/desorption behaviors of plasma polymer films. Sensors and Actuators B: Chemical, 2007, 124(1): 53.
[11] YANG K, XUE F, SUN Q,et al. Adsorption of volatile organic compounds by metal-organic frameworks MOF-177. Journal of Environmental Chemical Engineering, 2013, 1(4): 713.
[12] WANG Y, XIE J, WU Y C,et al. A magnetic metal-organic framework as a new sorbent for solid-phase extraction of copper(II), and its determination by electrothermal AAS. Microchimica Acta, 2014, 181(9): 949.
[13] XIE L H, LIU X M, HE T,et al. Metal-organic frameworks for the capture of trace aromatic volatile organic compounds. Chem, 2018, 4(8): 1911.
[14] YE Z C, YAO J C, ZHENG W,et al. The preparation and adsorption performance of Co-doped MIL-101(Cr) for low-concentration C3F8. Chemical Engineering Science, 2023, 282: 119302.
[15] LLEWELLYN P L, BOURRELLY S, SERRE C,et al. High uptakes of CO₂ and CH₄ in mesoporous metal-organic frameworks MIL-100 and MIL-101. Langmuir, 2008, 24(14): 7245.
[16] CAO J W, LI Y X, MA X B,et al. Constructing binuclear sites to modulate the charge distribution of MIL-101 for enhanced toluene adsorption performance: experimental and theoretical studies. Separation and Purification Technology, 2025, 354: 129400.
[17] SHAO P, KUANG X Y, DING L P,et al. Can CO₂ molecule adsorb effectively on Al-doped boron nitride single walled nanotube? Applied Surface Science, 2013, 285: 350.
[18] XIA X N, XU Y Z, CHEN Y,et al. Fabrication of MIL-101(Cr/Al) with flower-like morphology and its catalytic performance. Applied Catalysis A: General, 2018, 559: 138.
[19] JAVANBAKHT V, RAFIEE Z.Fibrous polyester sponge modified with carboxymethyl cellulose and zeolitic imidazolate frameworks for methylene blue dye removal in batch and continuous adsorption processes. Journal of Molecular Structure, 2022, 1249: 131552.
[20] AWADALLAH-F A, ELKHATAT A M, AL-MUHTASEB S A. Impact of synthesis conditions on meso- and macropore structures of resorcinol-formaldehyde xerogels. Journal of Materials Science, 2011, 46(24): 7760.
[21] WICKENHEISSER M, HERBST A, TANNERT R,et al. Hierarchical MOF-xerogel monolith composites from embedding MIL-100(Fe, Cr) and MIL-101(Cr) in resorcinol-formaldehyde xerogels for water adsorption applications. Microporous and Mesoporous Materials, 2015, 215: 143.
[22] FENG L J, LI J L, OU Y Y,et al. Study on the Pb(II) adsorption mechanism on acid-modified ceramsite made from sewage sludge and industrial solid wastes. International Journal of Applied Ceramic Technology, 2024, 21(5): 3389.
[23] TIWARI S, SALEEM M, MISHRA A,et al. Structural, optical, and dielectric studies on Sr-doped biferroic YCrO₃. Journal of Superconductivity and Novel Magnetism, 2019, 32(8): 2521.
[24] WANG Y Q, FU X, PAN T T,et al. Stable effect on MIL-101(Cr) with Cu²+ for the toluene adsorption. Journal of Solid State Chemistry, 2022, 316: 123633.
[25] ZHENG Y, CHU F C, ZHANG B,et al. Ultrahigh adsorption capacities of carbon tetrachloride on MIL-101 and MIL-101/graphene oxide composites. Microporous and Mesoporous Materials, 2018, 263: 71.
[26] ZHANG F F, SHANG H, WANG L,et al. Substituent-induced electron-transfer strategy for selective adsorption of N₂ in MIL-101(Cr)-X metal-organic frameworks. ACS Applied Materials & Interfaces, 2022, 14(1): 2146.
[27] CAO E P, ZHENG Y H, ZHANG H,et al. In-situ regenerable Cu/Zeolite adsorbent with excellent H₂S adsorption capacity for blast furnace gas. Separation and Purification Technology, 2024, 336: 126305.
[28] WANG H Y, WANG B D, LI J H,et al. Adsorption equilibrium and thermodynamics of acetaldehyde/acetone on activated carbon. Separation and Purification Technology, 2019, 209: 535.
[29] KONGGIDINATA M I, CHAO B, LIAN Q Y,et al. Equilibrium, kinetic and thermodynamic studies for adsorption of BTEX onto ordered mesoporous carbon (OMC). Journal of Hazardous Materials, 2017, 336: 249.