Influence of Water Content on Speciation and Phase Formation in Zr–Porphyrin‐Based MOFs

Abstract Controlled synthesis of phase‐pure metal–organic frameworks (MOFs) is essential for their application in technological areas such as catalysis or gas sorption. Yet, knowledge of their phase formation and growth remain rather limited, particularly with respect to species such as water whose vital role in MOF synthesis is often neglected. As a consequence, synthetic protocols often lack reproducibility when multiple MOFs can form from the same metal source and linker, and phase mixtures are obtained with little or no control over their composition. In this work, the role of water in the formation of the Zr–porphyrin MOF disordered PCN‐224 (dPCN‐224) is investigated. Through X‐ray total scattering and scanning electron microscopy, it is observed that dPCN‐224 forms via a metal–organic intermediate that consists of Zr₆O₄(OH)₄ clusters linked by tetrakis(4‐carboxy‐phenyl)porphyrin molecules. Importantly, water is not only essential to the formation of Zr₆O₄(OH)₄ clusters, but it also plays a primary role in dictating the formation kinetics of dPCN‐224. This multidisciplinary approach to studying the speciation of dPCN‐224 provides a blueprint for how Zr‐MOF synthesis protocols can be assessed and their reproducibility increased, and highlights the importance of understanding the role of water as a decisive component in Zr‐MOF formation.