Nonuniformity of Transport Coefficients in Ultrathin Nanoscale Membranes and Nanomaterials

The quest to reduce transport resistance in separations using nanomaterials has led to considerable interest in nanoscale adsorbents and ultrathin membranes. It is now established that interfacial resistance limits the performance of such nanosized materials; however, the origin of this resistance is uncertain. While it is associated with surface pore blockages and distortions in some materials, its existence even in ideal materials is largely putative. Here, we report equilibrium molecular dynamics (EMD) simulations with ideal zeolite-based nanosheets, indicating the transport resistance to be entirely distributed within the solid, without contribution from an interfacial effect. We demonstrate the presence of an internal entry region over which fluid decorrelation occurs, and in which the local transport coefficient inside the crystal is nonuniform and position-dependent, increasing to the uniform value in the bulk material at larger distances. Our EMD-based diffusivity profiles within the nanomaterial enable us to unequivocally determine the entry length, and reveal an internal excess resistance, frequently assumed to be an interfacial resistance, due to significant reduction of the internal transport coefficient in the entrance and exit regions. A decrease in the entry length with loading in PON zeolite nanosheets is seen. We demonstrate a reduction in external resistance in the external bulk chambers used in simulations, triggered by the interplay of incomplete decorrelation in the nanosheet and periodic boundary conditions imposed on the system comprising the nanosheet and surrounding bulk reservoirs when the nanosheet thickness is less than the entry length. Our analysis of the transport dynamics within the nanosheet demonstrates that, at least for ideal systems, decomposition of the inhomogeneous diffusivity-based internal resistance into an interfacial and a uniform transport coefficient-based internal contribution is not appropriate for finite-sized systems. Our results will enable the improved design of nanoscale membranes and materials for applications in separation and other processes.