Porous Metal-Organic Polyhedra: Morphology, Porosity, and Guest Binding.
Porous Metal-Organic Polyhedra: Morphology, Porosity, and Guest Binding.
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多孔金属有机多面体：形态，孔隙率和宾客结合。
DOI：
10.1021/acs.inorgchem.0c01935
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发表时间：
2020-11-02
影响因子：
4.6
通讯作者：
Schröder M
中科院分区：
文献类型：
--
作者：
Argent SP;da Silva I;Greenaway A;Savage M;Humby J;Davies AJ;Nowell H;Lewis W;Manuel P;Tang CC;Blake AJ;George MW;Markevich AV;Besley E;Yang S;Champness NR;Schröder M
设计可以选择性吸附CO2或CH 4的多孔材料是一个重要的环境和工业目标，这需要了解原子尺度上所涉及的主客体相互作用。很少观察到在去溶剂化时显示永久孔隙度的金属有机多面体（MOPs）。我们报告了一个家庭的MOPs（Cu-1a，Cu-1b，Cu-2），这是从填充笼之间的空腔，而不是从多面体内获得其永久孔隙度。因此，对于Cu-1a，笼外的空隙率总计为56%，笼内仅为2%。这些MOP结构的相对稳定性是合理的，考虑到他们的弱非定向包装使用Hirshfeld表面分析的相互作用。Cu-1a的特殊稳定性使得能够使用原位X射线和中子衍射结合DFT计算对CO2和CH 4的吸附进行详细的结构研究。吸附CO2和CH 4在Cu-1a中的主要结合位点是由苯环表面限定的开放金属位点和口袋。更重要的是，Cu-1a水合样品的结构分析揭示了吸附的CO2分子和Cu（II）结合的水分子之间的强氢键，揭示了先前的经验和理论观察，即含有开放金属位点的金属有机框架（MOF）材料的部分水合增加了它们对CO2的吸收。MOP-气体结合的晶体学研究的结果已经合理化，使用DFT计算，产生个人的结合能为各种孔隙环境的Cu-1a。我们报告了一个家庭的金属有机多面体（MOP），这是从填充笼之间的空腔，而不是从多面体内部获得永久的多孔性。这些MOP结构的相对稳定性是合理的，考虑到他们的弱非定向包装使用Hirshfeld表面分析的相互作用。详细的结构调查的吸附CO2和CH 4的报告使用原位X射线和中子衍射，再加上DFT计算。
Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a. We report a family of metal−organic polyhedra (MOP), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analysis. A detailed structural investigation into the adsorption of CO2 and CH4 is reported using in situ X-ray and neutron diffraction, coupled with DFT calculations.
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影响因子：
15
作者：
Furukawa, Hiroyasu;Kim, Jaheon;Yaghi, Omar M.
通讯作者：
Yaghi, Omar M.
DOI：
10.1073/pnas.1504586112
发表时间：
2015-11-17
影响因子：
11.1
作者：
Baek, Seung Bin;Moon, Dohyun;Kim, Kwang S.
通讯作者：
Kim, Kwang S.
影响因子：
8.4
作者：
Duong, Thien D.;Sapchenko, Sergey A.;Schroeder, Martin
通讯作者：
Schroeder, Martin
影响因子：
15
作者：
Gosselin, Eric J.;Decker, Gerald E.;Bloch, Eric D.
通讯作者：
Bloch, Eric D.
影响因子：
2.8
作者：
COOPER, AI;POLIAKOFF, M
通讯作者：
POLIAKOFF, M