Correlating structure-activity-stability relationship of high-valent 3d-metal-based MOFs and MOF-derived materials for electrochemical energy conversion and storage

The energy crises and environmental pollution are the current main challenges for society. In this regard, efficient electrochemical energy conversion and storage technologies could be a promising solution to overcome these challenges. In the past few years, metal-organic frameworks (MOFs) and their derived materials have emerged as potential candidates for energy conversion and storage owing to their finely tuned structural and electronic properties, 3D morphology, large surface area, abundant active sites, good stability, and improved mass transport and diffusion. Among the thousands of MOFs reported in the literature, most are prepared using divalent 3d-metals (i.e., Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) with a combination of various organic linkers. In contrast, MOFs based on high-valent 3d metals, such as Ti, V, Cr, and Mn are less studied but have shown promise in energy conversion and storage. The high-valent 3d-metal-based MOFs offer easier synthesis, facile charge, and mass transport, tunable electronic properties, and high synergistic effects. Although many reviews have been published in recent years, none have focused on high-valent 3d-metal-based MOFs and their usage in energy conversion and storage. The current review summarizes the applications of MOFs made from high-valent 3d metals (Ti, V, Cr, and Mn) and their derived materials. This review focuses on the structure, porosity, and stability of high-valent 3d-metal-based MOFs and MOF-derived materials with their application in energy conversion and storage. Taking into account pioneering reports, this review offers a deeper comprehension and insight into the characteristics and uses of high-valent 3d-metal-based MOFs and MOF-derived materials. The recent progress, challenges related to the field, and the structure-activity-stability correlation have been established with plausible prospects.