钛
多孔性
金属有机骨架
纳米技术
介孔材料
材料科学
星团(航天器)
金属
连接器
计算机科学
催化作用
化学
冶金
有机化学
吸附
操作系统
复合材料
程序设计语言
作者
Carlos Martí‐Gastaldo,Eloy Pablo Gómez-Oliveira,Javier Castells‐Gil,Clara Chinchilla-Garzón,Andrés Uscategui-Linares,Josep Albero,Neyvis Almora‐Barrios,Sergio Tatay,Natalia M. Padial
标识
DOI:10.26434/chemrxiv-2024-s7vqn
摘要
The increasing use of Metal-Organic Frameworks (MOFs) in separation, catalysis or storage is linked to the targeted modifi-cation of their composition or porosity metrics. While modification of pore shape and size necessarily implies the assembly of alternative nets, compositional changes often rely on post-synthetic modification adapted to the functionalisation or exchange of the organic linker, or the modification of the inorganic cluster by metal exchange methods. We describe an alternative methodology that enables the integration of both types of modification, structural and compositional, in titanium MOFs by metal exchange reaction of the heterometallic cluster Ti2Ca2. A systematic analysis of this reactivity with MUV-10 is used to understand which experimental variables are crucial to enable replacement of calcium only, or to integrate metal exchange with structural transformation. The isoreticular expanded framework MUV-30, is next used to template the formation of MUV-301, a titanium framework not accessible by direct synthesis that displays the largest mesoporous cages reported to date. Given that the interest of Ti MOFs in photoredox applications often meets the limitations imposed by the challenges of titanium solution chemistry to design concrete candidates, this soft strategy based on pre-assembled frameworks will help integrating specific combinations of metals into highly porous architectures.
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