Mechanistic Principles for Engineering Hierarchical Porous Metal–Organic Frameworks

Metal-organic frameworks (MOFs) have generated tremendous research interest in the past two decades, due to their high surface areas, tailorable active sites, and tunable structures. Hierarchical porous MOFs (HP-MOFs) with two or more pore systems are particularly attractive, benefiting from improved active site accessibility and enhanced mass diffusivity in applications involving bulk molecules. This review outlines the mechanistic principles used for the rational design of HP-MOFs, current techniques used to measure their hierarchical porosities, as well as their emerging applications. We then critically summarize the current challenges in this field and provide a contemporary perspective on the technological innovations that would address current synthetic challenges in the field of HP-MOFs. The aim of this review is to provide an in-depth understanding of the formation mechanisms, materials chemistry, and structural and chemical properties of HP-MOFs while exploring ways to enhance the performance of current MOF materials in a range of fields.