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Changing the perception of defects as irregularities or imperfections in crystalline frameworks into correlated domains amenable to chemical control and targeted design might offer unprecedented opportunities for the design of porous materials with superior performance or distinctive behavior in catalysis, separation, storage, or guest recognition. From a chemical standpoint though, the establishment of synthetic routes adapted to the systematic control of chemical composition for guiding the generation and growth of correlated disorder is arguably crucial to consider defect engineering a practicable route towards adjusting framework function. By using UiO-66 as experimental platform, we integrate systematic experimental design with high-throughput synthetic and characterization routines for efficient exploration of the framework chemical space and analysis of the corresponding defective materials. Periodic disorder arising from controlled generation and growth of missing cluster vacancies can be chemically controlled by the relative concentration of linker and modulator, which has been used to isolate a crystallographically pure “disordered” reo phase for the first time. Cs-corrected scanning transmission electron microscopy with sub-unit-cell resolution is also used to proof the coexistence of correlated domains of missing linker and cluster vacancies, whose relative sizes are fixed by the linker concentration. The impact of this relative distribution of correlated disorder in the porosity and catalytic activity of the material reveals that, contrarily to the common belief of “the more defects the better”, surpassing a certain defectivity threshold can have a detrimental effect often unaccounted for.

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Synthetic control of correlated disorder in UiO-66 frameworks

Sergio Tatay / University of Valencia
Sonia Martínez-Giménez / University of Valencia
Ana Rubio-Gaspar / University of Valencia
Javier Castells-Gil / University of Valencia
Zhuoya Dong /ShanghaiTech University
Alvaro Mayoral / ShanghaiTech University 
Neyvis Almora-Barrios / University of Valencia
Natalia M. Padial / Universidad de Valencia, ICMol
Carlos Martí-Gastaldo / University of Valencia

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