Hierarchical Engineering of Single-Crystalline Mesoporous Metal–Organic Frameworks with Hollow Structures

Although the superiority of hierarchical structure has driven extensive demand for applications, establishing hierarchy in a long-range-ordered single crystal remains a formidable challenge due to the inherent competition and contradiction between single crystallinity and controllable hierarchical structure. Herein, we demonstrate a growth and dissociation kinetics cooperative strategy for synthesizing a family of hollow single-crystalline mesoporous metal-organic frameworks (meso-MOFs) with hierarchical structures. The approach employs a dual-template method, integrating both hard and soft templates. By adjusting the HCl/CH₃COOH ratio, the reaction system's pH can be tuned to regulate the dissociation kinetics of the acid-sensitive seeds serving as hard templates for the formation of hollow structure, while simultaneously modifying the concentration of the dual acids to control the growth kinetics of meso-MOF shells. The competition between maintaining a single crystallinity and achieving a well-defined hierarchical structure can be effectively balanced. Driven by the two interfacial kinetics, we successfully obtained the octahedral meso-MOF nanoparticles that not only exhibit a well-defined hollow structure with precisely controllable hollow size (∼81-1120 nm) and tunable wall thickness (∼28.6-61.3 nm) but also retain their single-crystal integrity. Specifically, the dissociation kinetics of seeds governed the formation of hollow structures, while the growth kinetics of single-crystalline meso-MOF shells ensured uniform coverage and structural integrity. Based on this strategy, we further developed a series of novel hollow meso-MOFs with hierarchical nanostructures, including hollow open-capsule meso-MOFs, 2D hollow meso-MOFs, hollow interlayer-structured meso-MOFs, macro-meso-micro trimodal porous MOFs, and so on.