Raptis Dionysios, Livas Charalampos, Stavroglou George, Giappa Rafaela Maria, Tylianakis Emmanuel, Stergiannakos Taxiarchis, Froudakis George E
Department of Chemistry, University of Crete, Voutes Campus, GR-71003 Heraklion, Crete, Greece.
Department of Materials Science and Technology, University of Crete, Voutes Campus, GR-71003 Heraklion, Crete, Greece.
Molecules. 2022 May 26;27(11):3448. doi: 10.3390/molecules27113448.
The interaction strength of nitrogen dioxide (NO) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal-organic frameworks (MOFs) in order to enhance their uptake of NO molecules. Among the functional groups considered, the highest interaction energy with NO (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSOH) at the RI-DSD-BLYP/def2-TZVPP level of theory-an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO interactions (-OSOH, -POH, -OPOH) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO uptake performance not only in MOFs but also in various other porous materials.
通过进行密度泛函理论（DFT）计算，研究了二氧化氮（NO）与一组43个功能化苯分子的相互作用强度。所研究的官能团经过精心挑选，作为对现有金属有机框架（MOF）有机连接体的潜在修饰，以增强它们对NO分子的吸附能力。在考虑的官能团中，在RI-DSD-BLYP/def2-TZVPP理论水平下，发现苯基硫酸氢酯（-OSOH）与NO的相互作用能最高（5.4千卡/摩尔）——该相互作用几乎是非功能化苯相应结合能（2.0千卡/摩尔）的三倍。选择与NO相互作用最强的基团（-OSOH、-POH、-OPOH）对IRMOF-8的连接体进行功能化，并通过巨正则蒙特卡罗（GCMC）模拟研究它们在环境温度下、宽压力范围内对NO的吸附能力趋势。预测的等温线表明，通过在框架中引入强结合官能团，NO的吸附能力显著增强，这使它们不仅在MOF中，而且在各种其他多孔材料中，都有望成为改善NO吸附性能的修饰候选物。
