Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
J Am Chem Soc. 2009 Oct 28;131(42):15120-1. doi: 10.1021/ja9072707.
The first crystalline beryllium-based metal-organic framework has been synthesized and found to exhibit an exceptional surface area useful for hydrogen storage. Reaction of 1,3,5-benzenetribenzoic acid (H(3)BTB) and beryllium nitrate in a mixture of DMSO, DMF, and water at 130 degrees C for 10 days affords the solvated form of Be(12)(OH)(12)(1,3,5-benzenetribenzoate)(4) (1). Its highly porous framework structure consists of unprecedented saddle-shaped Be(12)(OH)(12) rings connected through tritopic BTB(3-) ligands to generate a 3,12 net. Compound 1 exhibits a BET surface area of 4030 m(2)/g, the highest value yet reported for any main group metal-organic framework or covalent organic framework. At 77 K, the H(2) adsorption data for 1 indicate a fully reversible uptake of 1.6 wt % at 1 bar, with an initial isosteric heat of adsorption of -5.5 kJ/mol. At pressures up to 100 bar, the data show the compound to serve as an exceptional hydrogen storage material, reaching a total uptake of 9.2 wt % and 44 g/L at 77 K and of 2.3 wt % and 11 g/L at 298 K. It is expected that reaction conditions similar to those reported here may enable the synthesis of a broad new family of beryllium-based frameworks with extremely high surface areas.
首个结晶的铍基金属有机骨架已被合成，并被发现具有用于储氢的特殊表面积。在 130°C 下，将 1,3,5-苯三甲酸（H(3)BTB）和硝酸铍在 DMSO、DMF 和水的混合物中反应 10 天，可得到 Be(12)(OH)(12)(1,3,5-苯三甲酸)(4)（1）的溶剂化物。其高度多孔的骨架结构由前所未有的鞍形Be(12)(OH)(12)环组成，这些环通过三齿 BTB(3-)配体连接，生成一个 3,12 网络。化合物 1 具有 4030 m(2)/g 的 BET 表面积，这是迄今为止报道的任何主族金属有机骨架或共价有机骨架的最高值。在 77 K 下，1 的 H(2)吸附数据表明，在 1 巴时可完全可逆地吸收 1.6wt%的氢气，初始等吸附热为-5.5 kJ/mol。在高达 100 巴的压力下，数据表明该化合物是一种出色的储氢材料，在 77 K 时总吸收量达到 9.2wt%和 44 g/L，在 298 K 时达到 2.3wt%和 11 g/L。预计，类似于这里报道的反应条件可能会促使具有极高表面积的新型铍基框架家族的广泛合成。
