Lamellar membranes, especially assembled by microporous framework nanosheets, have excited interest for fast molecular permeation. However, the underlying molecular dissolution behaviors on membrane surface, especially at pore entrances, remain unclear. Here, hierarchical metal-organic framework (MOF) lamellar membranes with 7 nm-thick surface layer and 553 nm-thick support layer are prepared. Hydrophilic (–NH2) or hydrophobic (–CH3) groups are decorated at pore entrances on surface layer to manipulate wettability, while –CH3 groups on support layer provide comparable, low-resistance paths. We demonstrate that molecular dissolution behaviors are determined by molecule-molecule and molecule-pore interactions, derived from intrinsic parameters of molecule and membrane. Importantly, two dissolution model equations are established: for hydrophobic membrane surface, dissolution activation energy (ES) obeys ES=Kmln[(γL-γC)μd2], while turns to ES=Kaln[(γL-γC)δeμd2] for hydrophilic one. Particularly, hydrophilic pore entrances exert strong interaction with polar molecules, thus compensating the energy consumed by molecule rearrangement, giving fast permeation (> 270 L m-2 h-1 bar-1).

Two-dimensional (2D) lamellar membranes are promising for efficient molecule transfer, while the underlying molecule transfer mechanism is rarely elucidated. Herein, heterostructured nanosheets are prepared by self-assembling small-sized hydrophilic cyanuric acid melamine (CMN) and hydrophobic g-C3N4 nanosheets. The resultant lamellar membranes show comparable affinity to both polar and nonpolar solvents, allowing them to dissolve on membrane surface and diffuse through membrane channels. Permeance results demonstrate that the transfer of polar solvents is controlled by dissolution and diffusion processes, while that of nonpolar solvents is governed by dissolution process. And the corresponding equations are established. Importantly, polar solvents are induced to form ordered arrangement in hydrophilic nanodomains and then maintain this state in hydrophobic nanodomains, affording low-resistance transfer thus high permeance: 1025 L m-2 h-1 bar-1 for acetonitrile. In contrast, nonpolar solvents with disordered arrangement acquire lower permeance than that of polar ones, but with comparable diffusion ability in these membranes.