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

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/P₀ = 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.