Crystal-Engineered Ce-MOF-Derived Catalysts: Defects and Interfaces as Drivers of Catalysis

Abstract

Cerium (Ce)-based materials are highly attractive platforms for catalyst design because their reversible Ce 3+ /Ce 4+ redox chemistry, oxygen-vacancy (O v ) formation, and strong Ce-O interactions enable dynamic control of oxygen mobility and interfacial reactivity. In recent years, Ce-based metal-organic frameworks (Ce-MOFs) have emerged as versatile precursors and model systems for extending these features into crystallographic defined coordination environments. Through careful control of cluster connectivity, linker chemistry, defect density, and heterometal incorporation, crystal engineering provides a route to program the local structure of Ce-MOFs and to translate these features into MOF-derived oxide catalysts. This highlight review summarizes recent progress in understanding how crystal engineering governs defect formation, Ce 3+ /Ce 4+ equilibria, O v topology, and metal-ceria (CeO 2 ) interfaces in both Ce-MOFs and their derived oxides. First, the defect chemistry of CeO 2 is outlined as the oxidelevel foundation for vacancy formation, redox flexibility, and oxygen transport. The structural diversity and redox behaviour of Ce-MOFs are then discussed, with emphasis on Ce(III)-and Ce(IV)-based architectures, ligand-to-metal charge transfer (LMCT), and mixed-valence behaviour. Building on this basis, key crystal engineering strategies in Ce-MOFs are highlighted, including modulator-controlled defect generation, topology control, heterometal interface engineering, and electronic tuning through linker design. Finally, the review examines how MOF-to-oxide transformation preserves or restructures programmed features to generate defect-rich CeO₂ lattices, engineered metal-CeO 2 interfaces, and multimetal oxide systems with enhanced catalytic performance. By linking molecular-scale framework design to oxidephase functionality, this review establishes crystal engineering as a unifying strategy for the rational development of next-generation Ce-based catalytic materials.