Unveiling the spontaneous conversion of layered MAX phases to 2D MXenes

TL;DR

This study uncovers the atomic-scale mechanism of transforming layered MAX phases into 2D MXenes using density functional theory and operando monitoring, revealing key factors influencing etching efficiency and kinetics.

Contribution

It provides a detailed mechanistic understanding of MAX to MXene conversion and introduces thermodynamic descriptors for selecting effective etchants.

Findings

Sigmoidal etching kinetics with self-accelerating behavior.

Activation energy of ~60 kJ/mol linked to Al transport.

Thermodynamic matching of A element and etchant is crucial.

Abstract

Topochemically transforming layered non-van der Waals solid into two dimensional (2D) materials involves selective etching reactions with atomic precision. The element-specific, structure-sensitive etching at nanoscale urgently requires in-depth understanding. Here, by means of density functional theory calculations and a laboratory-made operando reaction monitoring platform, the mechanism of instantaneous transforming MAX phase into MXenes is unraveled. The overall etching kinetics exhibits a sigmoidal curve, following self-accelerating reaction character with a small activation energy of ca. 60 kJ/mol. Interestingly, this activation energy corresponds to the Al transport through Ti3C2 slits. Therefore the reaction of Al with hydrofluoric acid solution in the confined interlayer space is recognized as the rate-determining step. Last but not the least, we found that the match of A element and etchants to form stable products is critical for the etching reaction, and reaction energy derived from the thermodynamics provides an easy yet effective descriptor for screening efficient etchants.