Gas transport mechanisms through molecularly thin membranes

TL;DR

This study investigates gas transport through atomically thin carbon nanomembranes, revealing that adsorption governs permeation and explaining nonlinear water vapor permeation with a focus on activation energy and entropy effects.

Contribution

It provides the first comprehensive analysis of gas permeation mechanisms in molecularly thin CNMs, highlighting adsorption's key role and the influence of activation energy and entropy.

Findings

Permeation is governed by adsorption and activation energy.

Water vapor shows nonlinear permeation due to entropy loss.

All gases exhibit an activation energy barrier correlated with their size.

Abstract

Atomically thin molecular carbon nanomembranes (CNMs) with intrinsic sub-nanometer porosity are considered as promising candidates for next generation filtration and gas separation applications due to their extremely low thickness, energy efficiency and selectivity. CNMs are intrinsically porous which is advantageous over other 2D materials such as graphene and transition metal dichalcogenides where defects and pores need to be introduced after synthesis. It was already discovered that water and helium permeate through 4,4-terphenylthiol (TPT) CNM above the limit of detection. Additionally, the permeation of water vapour was nonlinear against its pressure and 1000 stronger than permeation of helium despite their similar kinetic diameters. However, there was no clear permeation mechanism which could explain permeation of both species. Here, we demonstrate that permeation of all gas species is defined by their adsorption. We performed gas permeation measurements through TPT CNM at different temperatures and found that all measured gases experienced an activation energy barrier which correlated with their kinetic diameters. Furthermore, we identified that entropy loss during adsorption and permeation is the fundamental reason of strong nonlinear permeation of water. Our results also demonstrated that adsorption plays a major role in permeation of all gases, not just water.