Development of Macroscopic Nanoporous Graphene Membranes for Gas Separation

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Separating components of a gas from a mixture is a critical step in several important industrial processes including natural gas purification, hydrogen production, carbon dioxide sequestration, and oxy-combustion. For such applications, gas separation membranes are attractive because they offer relatively low energy costs but can be limited by low flow rates and low selectivities. Nanoporous graphene membranes have the potential to exceed the permeance and selectivity limits of existing gas separation membranes. This is made possible by the atomic thickness of the material, which can support sub-nanometer pores that enable molecular sieving while presenting low resistance to permeate flow. The feasibility of gas separation by graphene nanopores has been demonstrated experimentally on micron-scale areas of graphene. However, scaling up to macroscopic sizes presents significant challenges, including graphene imperfections and control of the selective nanopore size distribution across large areas. The overall objective of this thesis research is to develop macroscopic graphene membranes for gas separation. Investigation reveals that the inherent permeance of large areas of graphene results from the presence of micron-scale tears and nanometer-scale intrinsic defects. Stacking multiple graphene layers is shown to reduce leakage exponentially. A model is developed for the inherent permeance of multi-layer graphene and shown to accurately explain measured flow rates. Applying this model to membranes with created selective pores, it is predicted that by proper choice of the support membrane beneath graphene or adequate leakage sealing, it should be possible to construct a selectively permeable graphene membrane despite the presence of defects. Interfacial polymerization and atomic layer deposition steps during membrane fabrication are shown to effectively seal micron-scale tears and nanometer-scale defects in graphene. The support membrane is designed to isolate intrinsic defects and reduce leakage through tears. Methods of creating a high density of selectively permeable nanopores are explored. Knudsen selectivity is achieved using macroscopic three-layer graphene membranes on polymer supports by high density ion bombardment. Separation ratios exceeding the Knudsen effusion limit are achieved with single-layer graphene on optimized supports by low density ion bombardment followed by oxygen plasma etching, providing evidence of molecular sieving based gas separation through centimeter-scale graphene membranes.