MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal network of 18-membered rings and μ3-oxo-centered trinuclear units
MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal network of 18-membered rings and μ3-oxo-centered trinuclear units
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DOI：
10.1021/ja0621086
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发表时间：
2006-08-09
影响因子：
15
通讯作者：
Latroche, Michel
中科院分区：
文献类型：
--
作者：
Loiseau, Thierry;Lecroq, Ludovic;Latroche, Michel
合成了一种新的均苯三甲酸铝Al_（12）O（OH）（18）（H_2O）（3）（Al-2（OH）（4））[btc]（6）（.）在温和的水热条件下（210 ℃，24 h），以1，3，5-苯三甲酸（均苯三甲酸或H3 btc）为原料，合成了24 H（2）O，命名为MIL-96。从1，3，5-苯三甲酸三甲酯（Me（3）btc）、HF和TEOS的混合物中生长允许单晶XRD分析的六方晶体。MIL-96结构显示出三维（3D）框架，包含孤立的三核mu（3）-氧代桥接铝簇和无限链的AlO 4（OH）（2）和AlO 2（OH）（4）八面体，形成基于18元环的蜂窝晶格。这两种类型的铝基团通过均苯三甲酸酯物质彼此连接，其诱导铝八面体的波纹链，通过μ（2）-羟基键与特定的-cis-cis-trans-序列连接。MIL-96的3D框架揭示了三种类型的笼。其中两个位于特殊位置0 0 0和2/3 1/3 1/4处，其孔隙体积分别估计为417和635埃（3），并包裹着自由水分子。第三种具有较小的孔体积，并且含有无序的铝八面体物种（Al（OH）（6））。固态NMR表征与晶体结构以及元素和热分析一致。用Al-27 3QMAS技术分辨了铝的四个晶位。该产物在室温下能够吸附二氧化碳和甲烷（4.4mmol（.）g（-1）的CO2和1.95 mmol（.）g（-1），对于CH 4，在10巴下）和氢气，在77 K下（在3巴下为1.91重量%）。
A new aluminum trimesate Al12O(OH)(18)(H2O)(3)(Al-2(OH)(4))[btc](6)(.)24H(2)O, denominated MIL-96, was synthesized under mild hydrothermal conditions ( 210 C, 24 h) in the presence of 1,3,5-benzenetricarboxylic acid ( trimesic acid or H 3 btc) in water. Hexagonal crystals, allowing a single-crystal XRD analysis, are grown from a mixture of trimethyl 1,3,5-benzenetricarboxylate (Me(3)btc), HF, and TEOS. The MIL-96 structure exhibits a three-dimensional (3D) framework containing isolated trinuclear mu(3)-oxo-bridged aluminum clusters and infinite chains of AlO4(OH)(2) and AlO2(OH)(4) octahedra forming a honeycomb lattice based on 18-membered rings. The two types of aluminum groups are connected to each other through the trimesate species, which induce corrugated chains of aluminum octahedra, linked via mu(2)-hydroxo bonds with the specific -cis-cis-trans- sequence. The 3D framework of MIL-96 reveals three types of cages. Two of them, centered at the special positions 0 0 0 and 2/3 1/3 1/4, have estimated pore volumes of 417 and 635 angstrom(3), respectively, and encapsulate free water molecules. The third one has a smaller pore volume and contains disordered aluminum octahedral species (Al(OH)(6)). The solid-state NMR characterization is consistent with crystal structure and elemental and thermal analyses. The four aluminum crystallographic sites are resolved by means of Al-27 3QMAS technique. This product is able to sorb both carbon dioxide and methane at room temperature (4.4 mmol(.)g(-1) for CO2 and 1.95 mmol(.)g(-1) for CH4 at 10 bar) and hydrogen at 77 K (1.91 wt % under 3 bar).