Structure-directing Role of Graphene in the Synthesis of Metal-Organic Framework Nanowire

 Abstract: Graphene can be decorated with functional groups on either side of its basal plane, giving rise to bifunctional nanoscale building block that can undergo face-to-face assembly. We demonstrate that benzoic acid-functionalized graphene (BFG) can act as structure directing template in influencing the crystal growth of metal-organic framework (MOF). BFG is also incorporated into MOF as framework linker. Due to the high density of carboxylic groups on benzoic acid-functionalized graphene, an unusual MOF nanowire which grows in the [220] direction was synthesized. The diameter of the nanowire correlates closely to the lateral dimensions of the BFG. The intercalation of graphene in MOF imparts new electrical properties such as photoelectric transport in the otherwise insulating MOF. The results point to the possibility of using functionalized graphene to synthesize a wide range of structural motifs in MOF with adjustable metrics and properties.

   

现行的纳米研究，很多涉及怎样用一个模板来生长低维纳米材料。我们最近的工作显示，二维石墨烯也可以做为一个分子模板，来诱导金属有机骨架材料的生长，我们首次用bottom-up+graphene structure-directing的方法合成了MOF-5的纳米线。其基本机理如下图所示：

 

有趣的是，官能化的石墨烯是插层于纳米线中，拉曼mapping提供了关键的证据：

TEM和衍射花样的结果显示，该纳米线是沿着【220】方向生长的，因此，从生长机理上看，官能化的石墨烯诱导了完全不同于石墨烯氧化物的生长，其区别如下图所示：

 

 

该文已于近期发表于JACS(J. AM. CHEM. SOC. 2010, 132, 14487–14495)。

发表之后的感慨是：好不容易。因为此前已经有三篇graphene+MOF的文章分别发表于Adv Mater， Adv Funct Materi和J Mater Chem，要突破重围找到我们的originality实属不易。就像我们老板说，发这个paper，就像为了挽救一个出生不久先天不足的婴儿，提出一百种挽救措施，做N多实验（尽管结果有平平，只好拼工作量）很费劲才让其活过来。所以，从一开始，最好就优生优育，从一个全新的idea和concept开始，而不是简单的follow别人看有没有结果的改进或性能的提高。

 JACS_132-14487

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