Sequential Sol‐Gel Self‐Assembly and Nonclassical Gel‐Crystal Transformation of the Metal‐Organic Framework Gel

Abstract Metal‐organic framework (MOF) gel, an emerging subtype of MOF structure, is unique in formation and function; however, its evolutionary process remains elusive. Here, the evolution of a model gel‐based MOF, UiO‐66(Zr) gel, is explored by demonstrating its sequential sol‐gel self‐assembly and nonclassical gel‐crystal transformation. The control of the sol‐gel process enables the observation and characterization of structures in each assembly stage (phase‐separation, polycondensation, and hindered‐crystallization) and facilitates the preparation of hierarchical materials with giant mesopores. The gelation mechanism is tentatively attributed to the formation of zirconium oligomers. By further utilizing the pre‐synthesized gel, the nonclassical gel‐crystal transformation is achieved by the modulation in an unconventional manner, which sheds light on crystal intermediates and distinct crystallization motions (“growth and splitting” and “aggregation and fusion”). The overall sol‐gel and gel‐crystal evolutions of UiO‐66(Zr) enrich self‐assembly and crystallization domains, inspire the design of functional structures, and demand more in‐depth research on the intermediates in the future.