Calix[4]arene@MIL-101 as host@MOF for cage-in-cage pore space partitioning for enhanced CO2 separation and catalysis

Highly stable para-sulfonated calix[4]arene (SCA), a bowl-shaped macrocycle possessing intrinsic porosity, was incorporated into the spherical voids of the micro–mesoporous MIL-101(Cr) metal–organic framework by adsorptive loading from a solution. The pore-space partitioning in the MOF by polar func...

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Bibliographic Details
Published in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2025-01, Vol.13 (5), p.3894-3902
Main Authors: Saied Shafiei Navid, Rahman Hosseinzadeh, Oestreich, Robert, Abdpour, Soheil, Thi Hai Yen Beglau, Janiak, Christoph
Format: Article
Language:English
Subjects:
Adsorptivity
Aqueous solutions
Cages
Carbon dioxide
Carboxylic acids
Catalysis
Catalytic activity
Catalytic converters
Chromium
Esterification
Leaching
Metal-organic frameworks
Partitioning
Porosity
Sulfuric acid
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Summary:Highly stable para-sulfonated calix[4]arene (SCA), a bowl-shaped macrocycle possessing intrinsic porosity, was incorporated into the spherical voids of the micro–mesoporous MIL-101(Cr) metal–organic framework by adsorptive loading from a solution. The pore-space partitioning in the MOF by polar functionalized macrocyclic molecules, which can also act as hosts, led to the host@MOF composite SCA@MIL-101 which demonstrated a high affinity to CO2 without the involvement of alkaline amino functionalities. The SCA@MIL-101-w materials with w = 5, 10 and 30 wt% SCA showed high stability (including in aqueous medium, at least under non-basic conditions), and slow leaching kinetics due to the near match of the SCA size and the pore entrances of the MOF. Despite the lower surface area and pore volume for w = 30 wt% SCA in MIL-101 (SBET = 1073 m2 g−1 and Vpore = 0.52 cm3 g−1) vs. MIL-101 (2660 m2 g−1 and 1.0 cm3 g−1), the pore-space partitioning approach allows the improvement of the CO2 uptake capacity to 103 cm3 g−1 for SCA@MIL-101-30 over MIL-101 with 66 cm3 g−1 (273 K and 1 bar). This also increases the CO2/N2 selectivity, such that SCA@MIL-101-30 has a selectivity of 11 vs. 4 for MIL-101 for a 15 : 85 v : v CO2/N2 mixture at 293 K and 1 bar. Additionally, the SCA@MIL-101-30 composite showed good catalytic activity in the esterification of carboxylic acids, giving quantitative conversion on par with H2SO4 under the chosen conditions.
ISSN:2050-7488
2050-7496
DOI:10.1039/d4ta07357f