Reductive coordination replication of V2O5 sacrificial macrostructures into vanadium-based porous coordination polymers
Reductive coordination replication of V2O5 sacrificial macrostructures into vanadium-based porous coordination polymers
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DOI：
10.1039/c4ce01501k
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发表时间：
2015-01-01
期刊：
影响因子：
3.1
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
--
作者：
Reboul, Julien;Yoshida, Kenji;Kitagawa, Susumu
钒基多孔配位聚合物（或金属-有机骨架）具有多孔性和电子性，这使得这些新材料在分子分离、传感和多相催化等方面具有广泛的应用前景。将它们整合到充分利用其固有特性的系统中需要多种方法，允许将PCP晶体组装成定义明确的薄膜，图案，纤维或形成异质结构。在这篇论文中，[V（OH）ndc]（n）（ndc = 1，4-naphthalenedicarboxylate）PCP晶体的多晶宏观结构和异质结构的合成通过溶解-重结晶过程，所谓的配位复制，其中预成形的V2 O 5牺牲相被替换为共生PCP晶体在H（2）ndc作为有机连接剂的存在下，在还原环境下。在此过程中，V2 O 5既作为金属源又作为模板，为所得的介观多晶结构提供形状。作为还原剂的抗坏血酸既促进牺牲V2 O 5相的溶解，又提供构建[V（OH）ndc]（n）骨架所需的V-III物质。应用该方法成功地合成了二维图案。
Vanadium-based porous coordination polymers (or metal-organic frameworks) possess both porous and electronic properties, which make these new materials appealing for applications in molecular separation, sensing and heterogeneous catalysis. Their integration into systems that fully exploit their intrinsic properties requires versatile methods allowing assembly of the PCP crystals into well-defined films, patterns, fibers or the formation of heterostructures. In this contribution, polycrystalline macrostructures and heterostructures made of [V(OH)ndc](n) (ndc = 1,4-naphthalenedicarboxylate) PCP crystals were synthesized through a dissolution-recrystallization process, so-called coordination replication, where a pre-shaped V2O5 sacrificial phase was replaced by well-intergrown PCP crystals in the presence of H(2)ndc as an organic linker and under a reductive environment. In this process, V2O5 acts both as the metal source and as the template that provides the shape to the resulting mesoscopic polycrystalline architecture. Ascorbic acid, acting as the reducing agent, both promotes the dissolution of the sacrificial V2O5 phase and provides the V-III species required for the construction of the [V(OH)ndc](n) framework. Two-dimensional patterns were successfully synthesized by applying this procedure.