Multidimensional Building Blocks for Molecular Sieve Membranes.

Chemical separations aiming for high-purity commodities are critical to modern society. Compared to distillation, chemical absorption, and adsorption, membrane separation is attractive for its energy efficiency, ease of operation, and compact footprint. Molecular sieve membranes (MSMs) are broadly defined as membranes that are constructed from intrinsically and artificially porous materials. On the basis of our recent studies, this Account will first summarize the evolution of MSMs from the viewpoint of dimensionality of building blocks, which fundamentally determines the stacking architectures, intercrystalline gaps, and mass transfer channels of MSMs. Intergrowth of three-dimensional (3D) crystals as primary building blocks gives rise to classical MSMs. However, the poor connection between crystals inherent to those membranes results in intercrystalline gaps that are catastrophic for separation selectivity. We adopted a variety of strategies to close the crystal boundary gaps, including microwave synthesis, electrochemical-ionothermal synthesis, and modular integration. These efforts make us better understand the structure-performance relationship in membranes and create solutions for industrial processes. Excitingly, we first scaled-up the microwave synthesis of a Linde type A (LTA) zeolite membrane and built the world's largest ethanol dehydration membrane unit with an annual capacity of 100,000 tons. MSMs can also be made of two-dimensional (2D) nanosheets as primary building blocks. Those strike a balance between permeation rate and selectivity because the nanometer thickness ensures the minimization of the mass-transfer resistance of the membrane and the layer-by-layer stacking mode can significantly reduce the intercrystalline gaps. By publishing our first report on metal-organic framework (MOF) nanosheet membranes in Science, we committed to establishing top-down and bottom-up methods for assembly of laminae. Once the stacking, orientation, and connection between the layers are meticulously controlled, nanosheet building blocks with diversity open the door for ultrapermeable and selective MSMs. We recently proposed a supramolecule array membrane (SAM) with zero-dimensional (0D) molecules as primary building blocks, which has great potential to absolutely eliminate intercrystalline gaps in membranes. In contrast to the classical transport through nanopores of membranes, selective transport through the intermolecular spacing of supramolecules is creatively realized within the SAM, which marks a new breakthrough in ultraprecise sieving of molecules with tiny differences in size and revolutionizes MSMs in regard to stacking modes, intercrystalline gaps, and transport channels. MSMs have proven to be successful in diverse applications and have triggered wide interest. A unique perspective on the dimensionality evolution of building blocks will accelerate the progress of MSMs. The synergy of multidimensional MSMs will be a positive response to fundamental bottlenecks and industrial questions of membranes and will unlock the potential of membranes to displace the existing separation technologies in the future.