Halogen-Decorated Metal–Organic Frameworks for Efficient and Selective CO 2 Capture, Separation, and Chemical Fixation with Epoxides under Mild Conditions

作者：Anirban Karmakar, Andreia A. C. D. Santos, Noemi Pagliaricci, João Pires, Mary Batista, Elisabete C. B. A. Alegria, Ana Martín-Calvo, Juan José Gutiérrez‐Sevillano, Sofı́a Calero, M. Fátima C. Guedes da Silva, Riccardo Pettinari, Armando J. L. Pombeiro · 发表于：ACS Applied Materials & Interfaces · 年份：2024 · DOI：10.1021/acsami.4c02560 · 被引用次数：14 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Carbon Dioxide Capture Technologies、Carbon dioxide utilization in catalysis

In the present work, three novel halogen-appended cadmium(II) metal–organic frameworks [Cd 2 (L1) 2 (4,4′-Bipy) 2 ] n ·4 n (DMF) ( 1 ), [Cd 2 (L2) 2 (4,4′-Bipy) 2 ] n ·3 n (DMF) ( 2 ), and [Cd(L3)(4,4′-Bipy)] n ·2 n (DMF) ( 3 ) [where L1 = 5-{(4-bromobenzyl)amino}isophthalate; L2 = 5-{(4-chlorobenzyl)amino}isophthalate; L3 = 5-{(4-fluorobenzyl)amino}isophthalate; 4,4′-Bipy = 4,4′-bipyridine; and DMF = N, N ′-dimethylformamide] have been synthesized under solvothermal conditions and characterized by various analytical techniques. The single-crystal X-ray diffraction analysis demonstrated that all the MOFs feature a similar type of three-dimensional structure having a binuclear [Cd 2 (COO) 4 (N) 4 ] secondary building block unit. Moreover, MOFs 1 and 2 contain one-dimensional channels along the b -axis, whereas MOF 3 possesses a 1D channel along the a -axis. In these MOFs, the pores are decorated with multifunctional groups, i.e., halogen and amine. The gas adsorption analysis of these MOFs demonstrate that they display high uptake of CO 2 (up to 5.34 mmol/g) over N 2 and CH 4 . The isosteric heat of adsorption ( Q st ) value for CO 2 at zero loadings is in the range of 18–26 kJ mol –1 . In order to understand the mechanism behind the better adsorption of CO 2 by our MOFs, we have also performed configurational bias Monte Carlo simulation studies, which confirm that the interaction between our MOFs and CO 2 is stronger compared to those with N 2 and CH 4 . Various noncovalent i...