▎ 摘　　要

Two-dimensional materials are the essential building blocks of breakthrough membrane technologies due to minimal permeation barriers across atomically thin pores. Tunable pore size fabrication combined with independently controlled pore number density is necessary for outstanding performance but remains a challenge. There is a great need for parallel, upscalable methods that can control pore size from sub-nm to >5 nm, a pore size range required for membranes with effective molecular separation. Here we report a dry, facile, and scalable process introducing atomic defects by design, followed by selective etching of graphene edge atoms able to controllably expand the nanopore dimensions from sub-nm to 5 nm. The attainable average pore sizes at 10(15) m(-2) pore density promise applicability to various separation applications. We investigate the gas permeation and separation mechanisms, finding that these membranes display molecular sieving (H-2/CH4 separation factor = 9.3; H-2 permeance = 3370 gas permeation units (GPU)) and reveal the presence of interweaved transport phenomena of pore chemistry, surface flow, and gas molecule momentum transfer. We observe the smooth transition from molecular sieving to effusion at unprecedented permeance (H-2/CH4 separation factor = 3.7; H-2 permeance = 10(7) GPU). Our scalable graphene membrane fabrication approach in combination with sub-5 nm pores opens a new route employing 2D membranes to study gas transport and effectively paving the way to industrial applications.