Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface
Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface
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DOI：
10.1021/jacs.6b12776
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发表时间：
2017-03-01
影响因子：
15
通讯作者：
Nishihara, Hiroshi
中科院分区：
文献类型：
--
作者：
Matsuoka, Ryota;Sakamoto, Ryota;Nishihara, Hiroshi
合成的二维聚合物，或自下而上的纳米片，是具有平面周期性的超薄聚合物骨架。它们可以使用原子、离子或分子成分以直接、自下而上的方式合成。然而，很少有基于碳碳键形成的研究，这意味着对这些根本重要的化学键有一个潜在的新的研究领域。在这里，我们描述了全碳，pi-共轭的石墨二炔纳米片的自下而上的合成。液/液界面协议包括在室温下将六乙基苯的二氯甲烷溶液分层在含有铜催化剂的水层上。多层石墨二炔(厚度，24 nm；结构域大小，>；25，µm)通过连续的炔烃-炔烃同系偶联反应在界面上出现。气/液界面合成法更为成功。在室温下，将极少量的六乙基苯以二氯甲烷和甲苯的混合物洒在水相表面，得到了单晶石墨二烯纳米片，其具有规则的六方结构域，较低的氧化程度，以及均匀的厚度(3.0 nm)和横向尺寸(1.5微米)。
Synthetic two-dimensional polymers, or bottom-up nano sheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon,pi-conjugated graphdiyne nanosheets.A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25,mu m) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 mu m).