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.