Dahmani R, Grubišić S, Djordjević I, Ben Yaghlane S, Boughdiri S, Chambaud G, Hochlaf M
Université Gustave Eiffel, COSYS/LISIS, 5 Bd Descartes, 77454 Champs sur Marne, France.
University of Belgrade - Institute of Chemistry, Technology and Metallurgy, Department of Chemistry, Njegoševa 12, 11000 Belgrade, Republic of Serbia.
J Chem Phys. 2021 Jan 14;154(2):024303. doi: 10.1063/5.0037594.
In search for future good adsorbents for CO capture, a nitrogen-rich triazole-type Metal-Organic Framework (MOF) is proposed based on the rational design and theoretical molecular simulations. The structure of the proposed MOF, named Zinc Triazolate based Framework (ZTF), is obtained by replacing the amine-organic linker of MAF-66 by a triazole, and its structural parameters are deduced. We used grand-canonical Monte Carlo (GCMC) simulations based on generic classical force fields to correctly predict the adsorption isotherms of CO and HO. For water adsorption in MAF-66 and ZTF, simulations revealed that the strong hydrogen bonding interactions of water with the N atoms of triazole rings of the frameworks are the main driving forces for the high adsorption uptake of water. We also show that the proposed ZTF porous material exhibits exceptional high CO uptake capacity at low pressure, better than MAF-66. Moreover, the nature of the interactions between CO and the MAF-66 and ZTF surface cavities was examined at the microscopic level. Computations show that the interactions occur at two different sites, consisting of Lewis acid-Lewis base interactions and hydrogen bonding, together with obvious electrostatic interactions. In addition, we investigated the influence of the presence of HO molecules on the CO adsorption on the ZTF MOF. GCMC simulations reveal that the addition of HO molecules leads to an enhancement of the CO adsorption at very low pressures but a reduction of this CO adsorption at higher pressures.
为了寻找未来用于捕获二氧化碳的优良吸附剂，基于合理设计和理论分子模拟，提出了一种富氮三唑型金属有机框架材料（MOF）。所提出的名为基于三唑锌的框架材料（ZTF）的MOF结构，是通过用三唑取代MAF-66中的胺类有机连接体而得到的，并推导了其结构参数。我们基于通用经典力场进行了巨正则蒙特卡罗（GCMC）模拟，以正确预测二氧化碳和水的吸附等温线。对于MAF-66和ZTF中的水吸附，模拟结果表明，水与框架三唑环上的氮原子之间强烈的氢键相互作用是水高吸附量的主要驱动力。我们还表明，所提出的ZTF多孔材料在低压下表现出异常高的二氧化碳吸附容量，优于MAF-66。此外，在微观层面研究了二氧化碳与MAF-66和ZTF表面空腔之间相互作用的性质。计算结果表明，相互作用发生在两个不同的位点，包括路易斯酸-路易斯碱相互作用和氢键，以及明显的静电相互作用。此外，我们研究了水分子的存在对ZTF MOF上二氧化碳吸附的影响。GCMC模拟表明，添加水分子在极低压力下会导致二氧化碳吸附增强，但在较高压力下会导致二氧化碳吸附减少。
