Beyond the Cube: Morphology Engineering of Prussian Blue Analogues

ABSTRACT Prussian blue (PB) and its analogues (PBAs) are a class of coordination compounds that have attracted increasing attention in recent years owing to their open frameworks, tunable compositions, and reversible redox characteristics. Their functional performances are strongly influenced by their morphological features. Therefore, a systematic discussion of PB/PBAs morphologies is essential for the rational design and practical application of PB/PBAs. In this review, we comprehensively summarize the diverse morphologies of PB/PBAs, classifying reported PB/PBAs into two main categories: cubic structures (including solid cubes, hollow cubes, core–shell morphology, and more complex hollow or stepped cubes) and noncubic structures (such as spherical, rod, prismatic, polyhedral, and heterostructure forms). The correlations between morphology and performance are then systematically analyzed. Furthermore, PB/PBAs‐derived materials with specific morphologies (including metal oxides, metal sulfides, metal phosphides, and metal carbides) are discussed with respect to their performance enhancement in specific applications. Finally, the challenges and future perspectives are outlined, highlighting the need for more precise and controllable preparation of multiscale structures, a deeper understanding of morphology‐structure‐performance relationships, and cross‐scale optimization from microscopic structures to electrode and device levels.