MIL-101 (Cr)

Application: 1) Gas (such as carbon dioxide) and pollutant adsorption

• Catalog: OFC869288095
• CAS: 869288-09-5
• Category: Fluorinated Metal-organic Frameworks (MOFs)

• Unit Molecular Formula: C24H12O15FCr3
• Unit Molecular Weight: 715.33
• Coordination Metal: Cr
• Linkers: Terephthalic acid
• Particle Size: 500-800 nm
• Appearance: Grey green powder
• Storage: 1) Keep sealed in dry and cool condition; 2) It is recommended to activate for 10 hours at 110 degree in vacuum before gas-adsorption test.
• Stability: 1) MIL-101(Cr) is stable in air and acqeous solutions (PH 1-12); 2)Thermal stability, thermal decomposition temperature above 300 ° C
• Pore Size: Aperture: 1.2-1.6 nm;; Pore size: 2.9-3.4 nm
• Pore Volume: 2.0-2.4 cm3/g
• Surface Area: BET Specific surface: 2800-3200 m2/g

• Coordination Metal: Cr
• Linkers: Terephthalic acid

Case Study

MIL-101(Cr) as a Carrier for the Synthesis of New Imprinted Polymer (MIL-101@MIP)

Zhao K, et al. Journal of Environmental Chemical Engineering, 2024, 12(5), 113569.

In this case, a novel surface-imprinted polymer (MIL-101@MIP) was successfully synthesized using the metal-organic framework MIL-101(Cr), which features a large specific surface area, to achieve rapid and selective removal of bisphenol S (BPS) from environmental samples.
Materials
0.25 mmol of BPS, 1.0 mmol of 2-acrylamide-2-methylpropanesulfonic acid, 0.15 g of MIL-101(Cr), 50 mL of ultrapure water, 5.0 mmol of N,N'-methylenebisacrylamide, 10 mg of azobisisobutyronitrile
Preparation of MIL-101@MIP as follow:
Pre-polymerization:
1. Disperse the BPS, 2-acrylamide-2-methylpropanesulfonic acid, and MIL-101(Cr) into the ultrapure water.
2. Pre-polymerize the mixture at 30°C for 4 hours.
Polymerization:
1. Dissolve the N,N'-methylenebisacrylamide and azobisisobutyronitrile in the pre-polymerized mixture.
2. Mix evenly using ultrasound.
3. Bubble nitrogen continuously for 15 minutes to ensure an oxygen-free environment.
4. React the mixture at 60°C for 24 hours.
Extraction and Purification: Extract the obtained MIL-101@MIP using Soxhlet extraction to remove the template BPS until no BPS is detected using HPLC at 258 nm. Dry the washed products in a vacuum oven at 60°C for 12 hours.

MIL-101(Cr) for the Synthesis of ODA-modified m-MIL-101(Cr)

Yasmin Saadavi Y, et al. Chemical Engineering Research and Design, 2024, 208, 446-455.

The case successfully developed a method to synthesize Octadecylamine (ODA)-modified m-MIL-101(Cr) particles and incorporated them into PU sponges using PDMS as an adhesive. The resulting m-MIL-101(Cr)@PU sponges exhibited enhanced hydrophobicity and reusability, making them effective for oil and organic solvent removal applications. This work demonstrates the potential of m-MIL-101(Cr) for practical environmental applications, overcoming the limitations of traditional MIL-101(Cr) powders.
Functionalization of MIL-101(Cr)
0.3 g (1.1 mmol) of octadecylamine was added to 30 mL of dry toluene. After adding 0.5 g of MIL-101(Cr), the reaction mixture was sonicated for 10 min and stirred for 24 h at 120 °C under N₂ atmosphere. Finally, the functionalized MIL-101(Cr) nanoparticles, m-MIL-101(Cr), were centrifuged, washed with toluene three times, and dried at 80 °C for 12 h.
Fabrication of m-MIL-101(Cr)@PU Sponge Composites
Small pieces (1x1x1 cm³) of PU sponge were washed with ethanol and acetone. The cleaned PU sponges were dried in an oven at 50°C for 3 hours.
0.1 g of PDMS was dissolved in 15 mL of chloroform. 0.1 g of m-MIL-101(Cr) powder was dispersed in the PDMS solution using sonication for 10 minutes.
The PU sponge pieces were then immersed in the MIL-101(Cr)/PDMS or m-MIL-101(Cr)/PDMS mixture and stirred for 1 hour. Finally, the m-MIL-101(Cr) coated PU sponges were separated and dried at 60°C for 24 hours. The synthesized m-MIL-101(Cr)@PU sponges were thoroughly characterized to confirm the successful modification and incorporation of the particles.

MIL-101(Cr) as a Carrier for the Synthesis of MIL-101(Cr)/Fc-COOH

Lu J, et al. Separation and Purification Technology, 2024, 346, 127442.

MIL-101(Cr) is known for its large specific surface area, excellent water stability, and chemical stability, making it an ideal material for wastewater treatment. However, its limited light absorption capacity restricts its applications. To enhance its optical properties while maintaining its structural integrity, ferrocene carboxylic acid (Fc-COOH) was loaded onto MIL-101(Cr) through post-synthesis modification. The resulting composite, MIL-101(Cr)/Fc-COOH (1:2) (abbreviated as CFCC-2), demonstrated exceptional performance, achieving a 96% removal rate of tetracycline in just 30 minutes.
Synthesis of CFCC-2:
MIL-101(Cr) and a specified amount of Fc-COOH were ultrasonically dissolved in 20 mL of ethanol (EtOH) for 30 minutes. The resulting solution was then transferred to a polytetrafluoroethylene-lined autoclave and maintained at 100 °C for 12 hours. Finally, the product was washed three times with EtOH and dried at 80 °C. The mass ratio of MIL-101(Cr) to Fc-COOH was 1:2.

MIL-101(Cr) for the Synthesis of Amine-modified MIL-101(Cr) via Post-synthetic Modification

Yang K, et al. Solid State Sciences, 2024, 153, 107572.

Both MIL-101(Cr) and Cu-BTC are three-dimensional structural materials with the advantages of large specific surface area, large pore volume and high stability. In this case, using MIL-101(Cr) and Cu-BTC as substrates, amine-modified MOFs were prepared by rationally introducing amine groups into the MOF pores through the dual-solvent method, thus synergistically enhancing CO2 absorption with Cu-BTC.
Synthesis of Cu-BTC:
First, 2.077 g of Cu(NO₃)₂·3H₂O was dissolved in 15 mL of deionized water and stirred for 15 min at room temperature to obtain solution A. Then, 1.000 g of H₃BTC was weighed and dissolved in a mixture of anhydrous ethanol and DMF in the ratio of 1:1 for 10 min, and stirred for 10 min to obtain solution B. The solutions A and B were mixed and stirred for 30 min and then transferred to a 100 ml reactor and reacted at 80°C for 24 hours. The blue precipitate was then washed with DMF and anhydrous ethanol and the washed solid was separated by centrifugation. Finally, the solid was placed in a vacuum oven and dried at 393 K for 12 h to obtain a blue powder.
Synthesis of amino modified MIL-101(Cr) and Cu-BTC:
Weighed 0.5 g each of prepared MIL-101(Cr) and Cu-BTC, activated in a vacuum oven at 120°C for 12 h. Dissolved in a beaker containing 30 ml of anhydrous ethanol, respectively, and added a certain volume of EDA, DETA, and TETA, and stirred for 10 min, and then the mixtures were transferred to 100 ml of the reactor, and reacted at 100°C for 12 h,. It was cooled to room temperature, centrifuged to separate the products and washed several times with ethanol, and the modified MIL-101(Cr) and Cu-BTC were noted as n-DETA/EDA/TETA-MIL-101 and n-DETA/EDA/TETA-Cu-BTC, respectively.

MIL-101(Cr) for the Preparation of DABCO-based Bicationic Ionic Liquid-grafted MIL-101(Cr) via Bottom-up method

Feng N, et al. Separation and Purification Technology, 2024, 128851.

In this case, a bottom-up strategy was designed to prepare MIL-101(Cr) grafted with a DABCO-based dicationic ionic liquid for use in CO₂ cycloaddition reactions.
Synthesis of [TNH₂]Cl Ionic Liquid
Dissolve 5 mmol of triethylenediamine (DABCO) and 5 mmol of 2-chloroethylamine hydrochloride in 6 mL of ethanol. Stir the solution at 30 °C for 12 hours under a nitrogen atmosphere. Remove the solvent by rotary evaporation after the reaction. Wash the mixture with ethyl acetate and ethanol. Dissolve the white powder in deionized water and adjust the pH to 8 using KOH. Wash with methanol and dry under vacuum at 60 °C to obtain the [TNH₂]Cl ionic liquid.
Synthesis of Cl[TNH₂]Cl@MIL-101(Cr)
Mix 1 g of MIL-101(Cr), 7.8 mmol of AlCl₃·6H₂O, and 3.7 mmol of methoxyacetyl chloride in 70 mL of nitromethane. React at 100 °C for 5 hours. Centrifuge to remove the solvent and wash the obtained powder with deionized water. Heat-treat the powder in 100 °C water for 24 hours. Wash the powder and treat it in tetrahydrofuran at 67 °C for 3 hours. Wash the green powder sequentially with tetrahydrofuran and ethanol, then dry at 80 °C for 24 hours to obtain Cl@MIL-101(Cr). Add 300 mg of Cl@MIL-101(Cr) to 5.4 mmol of DABCO dissolved in 30 mL of ethanol. React at 60 °C under a nitrogen atmosphere for 48 hours. Centrifuge, wash with ethanol, and dry the green powder at 80 °C under vacuum conditions for 24 hours to obtain Cl[T]@MIL-101(Cr). Disperse 300 mg of Cl[T]@MIL-101(Cr) and 5.4 mmol of 2-chloroethylamine hydrochloride in 30 mL of ethanol. React at 80 °C for 48 hours under a nitrogen atmosphere. Centrifuge and wash the powder with ethanol to remove unreacted components. Vacuum-dry the powder at 80 °C for 12 hours and disperse it in ethanol. Add KOH solution dropwise to adjust the pH to 8. Stir for 5 hours, centrifuge, and wash several times with ethanol and deionized water. Vacuum-dry the green powder at 80 °C for 24 hours to obtain the final product, Cl[TNH₂]Cl@MIL-101(Cr).

MIL-101(Cr) for the Synthesis of Lanthanum-modified MIL-101(Cr) Porous Adsorbent via Co-precipitation Method

Qiu C, et al. Materials Today Communications, 2024, 40, 109613.

In this case, a lanthanum-modified MIL-101(Cr) porous adsorbent, referred to as nLa-MIL-101(Cr), was successfully synthesized using a post-synthesis modification method.
Materials
MIL-101(Cr)
n-hexane
Lanthanum nitrate hexahydrate (La(NO3)3·6H2O)
Ethanol (C2H6O)
Sodium hydroxide (NaOH)
Preparation Method
Lanthanum was introduced into MIL-101(Cr) by coprecipitation. Specifically, 0.025, 0.05, and 0.075 mmol of La(NO₃)₃·6H₂O were mixed with 25 mL of n-hexane and dissolved using ultrasonic treatment for 15 minutes. The solution concentrations were 0.01, 0.03, and 0.05 mol/L, respectively. Then, 250 mg of MIL-101(Cr) was added to the solution and stirred for 1 hour to ensure complete deposition. After vacuum drying at 60 °C for 12 hours, powders treated with solutions of different lanthanum concentrations were obtained.
Next, 25 mL of freshly prepared NaOH solution (pH=10) was added dropwise to the sample and stirred vigorously for 6 hours. To obtain pure samples, they were washed with deionized water and ethanol several times until the pH reached neutral. Finally, the sample was vacuum dried at 85 °C overnight. The resulting powders were labeled as nLa-MIL-101(Cr), where n represents 1, 3, and 5, based on the concentration of the lanthanum solution.