Tuning the Transport Properties of Gases in Porous Graphene Membranes with Controlled Pore Size and Thickness

Abstract Porous graphene membranes have emerged as promising alternatives for gas‐separation applications due to their atomic thickness enabling ultrahigh permeance, but they suffer from low gas selectivity. Whereas decreasing the pore size below 3 nm is expected to increase the gas selectivity due to molecular sieving, it is rather challenging to generate a large number of uniform small pores on the graphene surface. Here, a pore‐narrowing approach via gold deposition onto porous graphene surface is introduced to tune the pore size and thickness of the membrane to achieve a large number of small pores. Through the systematic approach, the ideal combination is determined as pore size below 3 nm, obtained at the thickness of 100 nm, to attain high selectivity and high permeance. The resulting membrane shows a H₂/CO₂ separation factor of 31.3 at H₂ permeance of 2.23 × 10⁵ GPU (1 GPU = 3.35 × 10⁻¹⁰ mol s⁻¹ m⁻² Pa⁻¹), which is the highest value reported to date in the 10⁵ GPU permeance range. This result is explained by comparing the predicted binding energies of gas molecules with the Au surface, −5.3 versus −21 kJ mol⁻¹ for H₂ and CO₂, respectively, increased surface–gas interactions and molecular‐sieving effect with decreasing pore size.