Boulmène Reda, Prakash Muthuramalingam, Hochlaf Majdi
Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 Bd Descartes, 77454 Marne- La-Vallée, France.
Phys Chem Chem Phys. 2016 Nov 2;18(43):29709-29720. doi: 10.1039/c6cp04650a.
Ab initio and DFT studies on CO interacting with different tautomers and isomers of triazole (TZ) are carried out to understand the adsorption mechanism and their mutual preferential sites. We used post Hartree-Fock methods (MP2, CCSD(T), and CCSD(T)-F12) and various DFTs (PBE, PBE0, M05-2X, and M11) with and without considering the dispersion correction for comparison. We determined hence the equilibrium structures, vibrational frequencies and binding energies of TZ-CO clusters and mapped their potential energy surfaces along the intermonomer coordinates. We find that the most stable TZ-CO clusters, some of them are already known, are not relevant for CO capture in porous materials. In addition, we show that the bonding between TZ and CO is due to various kinds of noncovalent interactions such as π-stacking, acid-base pair electron donor-electron acceptor (EDA) interactions along with N-HO and C-HO H-bonds with CO. Our analysis reveals the existence of site selectivity effects when CO binds to TZ. These effects are related to the magnitude of the interaction potentials, in the order EDA (+N-HO) > EDA (+C-HO) > CN[double bond, length as m-dash]N > π-stacking > σ type N-HO > C-HO H-bonds. This is the first report on the importance of competition between EDA, π-stacking and σ-bonds for CO capture and catalytic applications. Findings from this work may be used to give insights into the site specific CO capture ability of porous materials such as metal organic frameworks (MOFs), zeolitic imidazolate frameworks (ZIFs) or functionalized polymers. Finally, we show that IR spectroscopy of CO within the pores is neither a specific nor an efficient marker in probe-molecule experiments.
开展了关于一氧化碳（CO）与三唑（TZ）的不同互变异构体和异构体相互作用的从头算和密度泛函理论（DFT）研究，以了解吸附机制及其相互的优先吸附位点。我们使用了后哈特里 - 福克方法（MP2、CCSD(T) 和 CCSD(T)-F12）以及各种DFT方法（PBE、PBE0、M05-2X 和 M11），并比较了考虑和不考虑色散校正的情况。由此我们确定了TZ-CO团簇的平衡结构、振动频率和结合能，并沿着单体间坐标绘制了它们的势能面。我们发现，最稳定的TZ-CO团簇（其中一些已为人所知）与多孔材料中CO的捕获无关。此外，我们表明TZ与CO之间的键合是由于多种非共价相互作用，如π-堆积、酸碱对电子供体 - 电子受体（EDA）相互作用以及与CO形成的N-HO和C-HO氢键。我们的分析揭示了CO与TZ结合时存在位点选择性效应。这些效应与相互作用势的大小有关，顺序为EDA（+N-HO）> EDA（+C-HO）> C≡N > π-堆积 > σ型N-HO > C-HO氢键。这是关于EDA、π-堆积和σ键之间竞争对CO捕获和催化应用重要性的首次报道。这项工作的发现可用于深入了解多孔材料（如金属有机框架（MOF）、沸石咪唑酯框架（ZIF）或功能化聚合物）的位点特异性CO捕获能力。最后，我们表明在探针分子实验中，孔内CO的红外光谱既不是特异性的也不是有效的标记物。
