Multifunctional Materials & Composites (MMC) Laboratory, Department of Engineering Science, University of Oxford, Parks Road, Oxford OX1 3PJ, United Kingdom.
ACS Appl Mater Interfaces. 2021 Feb 17;13(6):7801-7811. doi: 10.1021/acsami.0c22307. Epub 2021 Feb 3.
Metal-organic frameworks (MOFs) stand as one of the most promising materials for the development of advanced technologies owing to their unique combination of properties. The conventional synthesis of MOFs involves a direct reaction of the organic linkers and metal salts; however, their postsynthetic modification is a sophisticated route to produce new materials or to confer novel properties that cannot be attained through the traditional methods. This work describes the postsynthetic MOF-to-MOF transformation of a nonluminescent MOF (Zn-based Oxford University-1 material [Zn-BDC, where BDC = 1,4-benzene dicarboxylate] (OX-1)) into a highly luminescent framework (Ag-based Oxford University-2 material [Ag-BDC] (OX-2)) by a simple immersion of the former in a silver salt solution. The conversion mechanism exploits the uncoordinated oxygen atoms of terephthalate linkers found in OX-1, instead of the unsaturated metal sites commonly employed, making the reaction much faster. The materials derived from the OX-1 to OX-2 transformation are highly luminescent and exhibit a selective response to acetone, turning them into a promising candidate for manufacturing fluorometric sensors for the diagnosis and monitoring of diabetes mellitus. Our methodology can be extended to other metals such as lead (Pb). The fabrication of a polymer mixed-matrix membrane containing OX-1 is used as a proof-of-concept for capturing Pb ions (as pollutants) from water. This research instigates the exploration of alternative methodologies to confer MOFs with special aptitudes for photochemical sensing or for environmental applications such as water purification.
金属-有机骨架(MOFs)因其独特的性质组合而成为开发先进技术最有前途的材料之一。MOFs 的传统合成涉及有机连接体和金属盐的直接反应;然而,它们的后合成修饰是一种复杂的途径,可以生产新材料或赋予传统方法无法获得的新性质。这项工作描述了一种非发光 MOF(基于锌的牛津大学-1 材料[Zn-BDC,其中 BDC=1,4-苯二甲酸酯](OX-1))通过简单浸入银盐溶液中转化为高度发光的框架(基于银的牛津大学-2 材料[Ag-BDC](OX-2))的后合成 MOF-to-MOF 转化。转化机制利用了 OX-1 中发现的对苯二甲酸酯配体的未配位氧原子,而不是通常使用的不饱和金属位,从而使反应速度更快。从 OX-1 到 OX-2 的转化所得到的材料具有高度的发光性,并对丙酮表现出选择性响应,使它们成为制造用于诊断和监测糖尿病的荧光传感器的有前途的候选材料。我们的方法可以扩展到其他金属,如铅(Pb)。包含 OX-1 的聚合物混合基质膜的制造用作从水中捕获 Pb 离子(作为污染物)的概念验证。这项研究引发了对赋予 MOFs 特殊光化学传感能力或用于环境应用(如净水)的替代方法的探索。