Design and synthesis of an exceptionally stable and highly porous metal-organic framework
Design and synthesis of an exceptionally stable and highly porous metal-organic framework
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DOI：
10.1038/46248
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发表时间：
1999-11-18
期刊：
影响因子：
64.8
通讯作者：
Yaghi, OM
中科院分区：
文献类型：
--
作者：
Li, H;Eddaoudi, M;Yaghi, OM
开放的金属-有机骨架被广泛认为是在催化、分离、气体储存和分子识别中有应用前景的材料（1-15）。与常规使用的微孔无机材料如沸石相比，这些有机结构具有通过控制孔的结构和功能化进行更灵活的合理设计的潜力。到目前为止，这些开放的框架不能支持永久的多孔性和避免在不存在客体分子如溶剂的情况下塌陷，这阻碍了该领域的进一步进展（14，15）。在这里，我们报告了金属有机框架的合成，该框架保持结晶，如X射线单晶分析所证明的，并且当完全去溶剂化和加热至300摄氏度时稳定。这种合成是通过借用金属羧酸盐簇化学的想法来实现的，其中有机二羧酸盐连接体用于当用单羧酸盐封端时产生超四面体簇的反应中。添加的连接剂的刚性和发散特性允许将除尘剂接合成三维框架，从而产生比大多数多孔结晶沸石具有更高表观表面积和孔体积的结构。这种简单和潜在的通用设计策略目前正在追求新相和复合材料的合成，并用于气体存储应用。
Open metal-organic frameworks are widely regarded as promising materials for applications(1-15) in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field(14,15). Here we report the synthesis of a metal-organic framework which remains crystalline, as evidenced by Xray single-crystal analyses, and stable when fully desolvated and when heated up to 300 degrees C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the dusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.