Functional Materials Design, Discovery & Development (FMD3), Advanced Membranes & Porous Materials Center, Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.
Department of Chemistry, University of Crete , Voutes 71003 Heraklion, Greece.
J Am Chem Soc. 2016 Oct 5;138(39):12767-12770. doi: 10.1021/jacs.6b08176. Epub 2016 Sep 24.
The ability to direct the assembly of hexagonal building units offers great prospective to construct the awaited and looked-for hypothetical polybenzene (pbz) or "cubic graphite" structure, described 70 years ago. Here, we demonstrate the successful use of reticular chemistry as an appropriate strategy for the design and deliberate construction of a zirconium-based metal-organic framework (MOF) with the intricate pbz underlying net topology. The judicious selection of the perquisite hexagonal building units, six connected organic and inorganic building blocks, allowed the formation of the pbz-MOF-1, the first example of a Zr(IV)-based MOF with pbz topology. Prominently, pbz-MOF-1 is highly porous, with associated pore size and pore volume of 13 Å and 0.99 cm g, respectively, and offers high gravimetric and volumetric methane storage capacities (0.23 g g and 210.4 cm (STP) cm at 80 bar). Notably, the pbz-MOF-1 pore system permits the attainment of one of the highest CH adsorbed phase density enhancements at high pressures (0.15 and 0.21 g cm at 35 and 65 bar, respectively) as compared to benchmark microporous MOFs.
将六方结构单元进行定向组装，为构建人们期待已久的假设性聚苯（pbz）或“立方石墨”结构提供了巨大的可能性，这种结构早在 70 年前就已被描述。在这里，我们成功地展示了使用网状化学作为一种合适的策略，用于设计和精心构建具有复杂 pbz 潜在网络拓扑结构的基于锆的金属有机骨架（MOF）。明智地选择必要的六方结构单元，即六个连接的有机和无机建筑砌块，使得 pbz-MOF-1 的形成成为可能，这是首例具有 pbz 拓扑结构的基于 Zr（IV）的 MOF。值得注意的是，pbz-MOF-1 具有高度多孔性，其相关孔径和孔体积分别为 13Å 和 0.99cm³/g，并且提供了高重量和体积甲烷储存容量（在 80 巴时分别为 0.23g/g 和 210.4cm³(STP)）。值得注意的是，与基准微孔 MOF 相比，pbz-MOF-1 的孔系统可以实现高压下 CH 吸附相密度增强之一（在 35 和 65 巴时分别为 0.15 和 0.21g/cm³）。
