Versatile Structural Engineering of Metal-Organic Frameworks Enabling Switchable Catalytic Selectivity

The structure engineering of metal-organic frameworks (MOFs) forms the cornerstone of their applications. Nonetheless, realizing the simultaneous versatile structure engineering of MOFs remains a significant challenge. Herein, a dynamically mediated synthesis strategy to simultaneously engineer the crystal structure, defect structure, and nanostructure of MOFs is proposed. These include amorphous Zr-ODB nanoparticles, crystalline Zr-ODB-hz (ODB = 4,4 '-oxalyldibenzoate, hz = hydrazine) nanosheets, and defective d-Zr-ODB-hz nanosheets. Aberration-corrected scanning transmission electron microscopy combined with low-dose high-angle annular dark-field imaging technique vividly portrays these engineered structures. Concurrently, the introduced hydrazine moieties confer self-reduction properties to the respective MOF structures, allowing the in situ installation of catalytic Pd nanoparticles. Remarkably, in the hydrogenation of vanillin-like biomass derivatives, Pd/Zr-ODB-hz yields partially hydrogenated alcohols as the primary products, whereas Pd/d-Zr-ODB-hz exclusively produces fully hydrogenated alkanes. Density functional theory calculations, coupled with experimental evidence, uncover the catalytic selectivity switch triggered by the change in structure type. The proposed strategy of versatile structure engineering of MOFs introduces an innovative pathway for the development of high-performance MOF-based catalysts for various reactions. A dynamically mediated synthesis strategy achieves versatile structure engineering of crystalline Zr-ODB-hz nanosheets and defective crystalline d-Zr-ODB-hz nanosheets. The Pd/Zr-ODB-hz catalyst gives partially hydrogenated alcohols as the main products for the catalytic conversion of vanillin. In contrast, the defective Pd/d-Zr-ODB-hz catalyst shows switchable product selectivity and gives further hydrogenolysized alkanes as the only product.image