Local grafting heterogeneities control water intrusion and extrusion in nanopores

TL;DR

This study investigates how microscopic heterogeneities in hydrophobic grafting influence water intrusion and extrusion in nanopores, revealing that such heterogeneities significantly affect pressure thresholds and interface dynamics.

Contribution

It demonstrates that subnanometric grafting heterogeneities critically control water intrusion/extrusion behavior in nanoporous materials, providing new microscopic insights.

Findings

Intrusion/extrusion pressures vary by over 20 MPa due to grafting heterogeneities.

Local radius and contact angle changes can pin interfaces or promote bubble nucleation.

Microscopic heterogeneities significantly impact material design and experimental interpretation.

Abstract

Hydrophobic nanoporous materials can be intruded by water only by exerting an external action, typically increasing pressure. For some materials, water extrudes when the pressure is lowered again. Controlling intrusion/extrusion hysteresis is central in a number of technological applications, including materials for energy applications and for high performance liquid chromatography, and experimental techniques, as liquid porosimetry, but is still far from being understood. In this work, we consider water intrusion and extrusion in common mesoporous materials grafted with hydrophobic chains, showing that the macroscopic properties of the system are significantly affected by subnanometric heterogeneities in the grafting. For example, intrusion and extrusion pressures can vary more than 20 MPa depending on the chain length and density of the grafting. Coarse-grained molecular dynamics simulations reveal that local changes of radius and contact angle produced by grafting heterogeneities can pin the interface during intrusion or facilitate bubble nucleation in extrusion. These unprecedented microscopic insights can directly impact the design of energy materials and chromatography columns, as well as the interpretation of porosimetry results.