Computational Design of Functionalized Imidazolate Linkers of Zeolitic Imidazolate Frameworks for Enhanced CO2 Adsorption,The Journal of Physical Chemistry C

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Computational Design of Functionalized Imidazolate Linkers of Zeolitic Imidazolate Frameworks for Enhanced CO2 Adsorption
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2015-10-01 00:00:00 , DOI: 10.1021/acs.jpcc.5b08043
M. Althaf Hussain ₁ , Yarasi Soujanya ₁ , G. Narahari Sastry ₁

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Zeolitic imidazolate frameworks (ZIFs) represent the class of metal–organic frameworks (MOFs) that possess high porosity, large surface area, exceptional thermal, and chemical stability. Because of these properties, ZIFs are being employed extensively in gas separation and selective CO₂ adsorption. We have chosen the structural modification approach to enhance the CO₂ binding ability of various imidazolate (Im) linkers of ZIFs by systematically varying the substituents at 2, 4, and 5 positions of Im ring with CH₃, Cl, CN, OH, NH₂, and NO₂ functional groups. Density functional theory (DFT) calculations have been employed to identify and quantify the CO₂ binding ability of various adsorption sites present in 137 Im linkers. The study demonstrates that the Im linkers with asymmetrical substitution, viz. NO₂/OH, CN/OH, and Cl/OH combinations are highly promising linkers of ZIFs for efficient CO₂ adsorption. The QTAIM analysis characterizes these interactions as noncovalent interactions which are stabilized by weak hydrogen bond and van der Waals (vdWs) interactions. Localized molecular orbital energy decomposition analysis (LMO-EDA) performed on substituted Im···CO₂ complexes reveals that CO₂ binding is governed by a combination of H-bonding, electrostatic, and dispersion interactions. The findings of the study will serve as guide-in principles to synthesize new adsorbents with enhanced and selective CO₂ adsorption.

中文翻译：

沸石咪唑酸酯骨架的功能化咪唑酸酯连接基用于增强CO ₂吸附的计算设计

沸石咪唑酸盐骨架（ZIF）代表一类金属-有机骨架（MOF），具有高孔隙率，大表面积，出色的热稳定性和化学稳定性。由于这些特性，ZIF被广泛用于气体分离和选择性CO ₂吸附。我们选择了结构修饰方法来通过系统地改变CH ₃，Cl，CN，OH，NH的Im环的2、4和5位上的取代基来增强ZIF的各种咪唑酯（Im）接头的CO ₂结合能力。₂和NO ₂官能团。密度泛函理论（DFT）计算已用于识别和量化CO ₂137 Im接头中存在的各种吸附位点的结合能力。研究表明，具有不对称取代的Im接头，即。NO ₂ / OH，CN / OH和Cl / OH组合是ZIF高效连接CO _2的极有希望的连接基。QTAIM分析将这些相互作用表征为非共价相互作用，通过弱氢键和范德华力（vdWs）相互作用得以稳定。对取代的Im···CO ₂配合物进行的局部分子轨道能量分解分析（LMO-EDA）显示，CO ₂结合是由H键，静电和分散相互作用共同决定的。该研究的结果将作为指导原则，以合成具有增强的和选择性的CO ₂吸附能力的新吸附剂。

更新日期：2015-10-01

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