Direct Chemical Vapor Deposition Synthesis of Porous Single‐Layer Graphene Membranes with High Gas Permeances and Selectivities

Abstract Single‐layer graphene containing molecular‐sized in‐plane pores is regarded as a promising membrane material for high‐performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching‐based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade‐off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. In this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single‐layer graphene membranes with the highest H₂/CH₄ separation performances recorded to date (H₂ permeance > 4000 GPU and H₂/CH₄ selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non‐covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single‐layer graphene exploits its tremendous potential as high‐performance gas‐sieving membranes.