CO2 fixation reaction over pyrimidinium-based dicationic ionic liquid in MIL-101(Cr)

被引：0

作者：

Nataj, Seyedeh Molood Masoom ^{[1
]}

Kaliaguine, Serge ^{[1
]}

Fontaine, Frederic-Georges ^{[2
]}

机构：

[1] Univ Laval, Chem Engn Dept, Quebec City, PQ G1V 0A6, Canada

[2] Univ Laval, Chem Dept, Quebec City, PQ G1V 0A6, Canada

来源：

APPLIED CATALYSIS A-GENERAL | 2025年 / 697卷

基金：

加拿大自然科学与工程研究理事会;

关键词：

Metal-organic frameworks; MIL-101(Cr); CO2; utilization; Cyclic carbonate; METAL-ORGANIC FRAMEWORKS; CARBON-DIOXIDE; CYCLIC CARBONATES; CHEMICAL FIXATION; HETEROGENEOUS CATALYSTS; EFFICIENT CONVERSION; HIGHLY EFFICIENT; ADSORPTION; EPOXIDES; CYCLOADDITION;

D O I：

10.1016/j.apcata.2025.120186

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Modified metal-organic frameworks (MOFs) encapsulating new ionic N-heterocyclic-based functional groups, prepared via a ship-in-a-bottle approach, introduce a novel catalytic system for COQ conversion with epoxides. The MIL-101(Cr) framework was functionalized with novel ionic liquids (ILs) such as 1,5-bis(2-aminopyrimidinium)pentane bromide (2AMP-DBrP) and 1,5-bis(2-aminopyrimidinium)ethyl ether bromide (2AMP-DBrEE), resulting in cationic pyrimidinium-containing Cr-MOFs with free bromide ions, namely MIL101-2AMP-DBrP and MIL101-2AMP-DBrEE. Although the surface area (2456 and 2408 m2/g) and pore volume (1.44 and 1.41 cm3/g) of these encapsulated materials were reduced compared to pristine MIL-101(Cr) (3425 m2/g and 1.78 cm3/g), the COQ adsorption capacity at low pressure was notably increased (3.51 and 4.05 mmol g-1 of COQ). These modified MOFs demonstrated exceptional catalytic performance and stability in COQ fixation with various epoxides, achieving a high turnover frequency (TOF) of 82.5 h-1 under mild conditions (0.1 MPa, 90 degrees C) without the need for co-catalysts or solvents, which are essential criteria for commercial viability. Moreover, in situ FTIR analysis suggests that the enhanced performance is due to COQ activation via carbamic acid formation facilitated by primary amino groups and epoxide activation through hydrogen bonding. This dual activation mechanism is critical for achieving high catalytic efficiency under mild conditions and underscores the innovative and significant advancements presented in this work compared to existing IL-MOFs.

引用

页数：14

共 82 条

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