Two‐Periodic MoS2‐Type Metal–Organic Frameworks with Intrinsic Intralayer Porosity for High‐Capacity Water Sorption

Abstract 2D metal–organic frameworks (2D‐MOFs) are an important class of functional porous materials. However, the low porosity and surface area of 2D‐MOFs have greatly limited their functionalities and applications. Herein, the rational synthesis of a class of mos ‐MOFs with molybdenum disulfide ( mos ) net based on the assembly of trinuclear metal clusters and 3‐connected tripodal organic ligands is reported. The non‐crystallographic (3,6)‐connected mos net, different from the 3‐connected hcb net of graphene, offers abundant intralayer voids courtesy of the split of one node into two. Indeed, mos ‐MOFs exhibit high apparent Brunauer‐Emmett‐Teller surface areas, significantly superior to those of other 2D‐MOF analogs. Markedly, hydrolytically stable Cr‐ mos ‐MOF‐1 displays an impressive water vapor uptake of 0.75 g g −1 at 298 K and P / P 0 = 0.9, among the highest in 2D‐MOFs. The combined water adsorption and X‐ray diffraction study reveal the water adsorption mechanisms, suggesting the importance of intralayer porosities of mos ‐MOFs for high‐performance water capture. This study paves the way for a reliable approach to synthesizing 2D‐MOFs with high porosity and surface areas for diverse applications.