Upscaled Synthesis Protocol for Phase-Pure, Colloidally Stable MXenes with Long Shelf Lives.

MXenes are electrically conductive 2D transition metal carbides/nitrides obtained by the etching of nanolaminated MAX phase compounds, followed by exfoliation to single- or few-layered nanosheets. The mainstream chemical etching processes have evolved from pure hydrofluoric acid (HF) etching into the innovative "minimally intensive layer delamination" (MILD) route. Despite their current popularity and remarkable application potential, the scalability of MILD-produced MXenes remains unproven, excluding MXenes from industrial applications. This work proposes a "next-generation MILD" (NGMILD) synthesis protocol for phase-pure, colloidally stable MXenes that withstand long periods of dry storage. NGMILD incorporates the synergistic effects of a secondary salt, a richer lithium (Li) environment, and iterative alcohol-based washing to achieve high-purity MXenes, while improving etching efficiency, intercalation, and shelf life. Moreover, NGMILD comprises a sulfuric acid (H2 SO4 ) post-treatment for the selective removal of the Li3 AlF6 impurity that commonly persists in MILD-produced MXenes. This work demonstrates the upscaled NGMILD synthesis of (50 g) phase-pure Ti3 C2 Tz MXene clays with high extraction yields (>22%) of supernatant dispersions. Finally, NGMILD-produced MXene clays dry-stored for six months under ambient conditions experience minimal degradation, while retaining excellent redispersibility. Overall, the NGMILD protocol is a leap forward toward the industrial production of MXenes and their subsequent market deployment.

Effect of terminal groups on the degradation stability of Ti3C2Tz MXenes.

MXenes are 2D nanomaterials which have gained considerable attention from researchers since their discovery in 2011. However, the propensity of these 2D nanomaterials to degrade affects their shelf life. While many studies have focused on the external factors affecting the degradation of MXenes, the effect of internal factors such as terminal groups is not well understood. In this paper, we use -Br and -Cl terminations as model terminal groups to compare the degradation stability of MXenes. From our experiments we observe that -Br terminated ML-Ti3C2Tz degrades faster than -Cl terminated ML-Ti3C2Tz. Our study confirms that terminal groups do affect the degradation rate of Ti3C2Tz. The results suggest that the differences in bond dissociation energy of the M-X bond are responsible for variations in the degradation stability of MXenes. This model study can be generalized to compare the effect of terminal groups on the degradation stability of MXenes.

Advances in the Chemical Stabilization of MXenes.

MXenes are 2D nanomaterials with a wide array of possible compositions; they feature a unique combination of properties such as high electrical conductivity, hydrophilicity, and colloidal stability which makes them attractive for a variety of applications. However, the shelf life and industrial utility of MXenes face challenges due to their tendency to oxidize and disintegrate, particularly in dispersions. Thus, it is crucial to find effective ways to ensure the degradation stability of MXenes. This feature article reviews the key factors affecting the degradation of MXenes such as pH, concentration of the dispersion, humidity, and storage temperature. In addition, we review our group's progress in mitigating the degradation of MXenes such as low-temperature storage, the use of antioxidants, and thermal annealing, particularly for Ti3C2Tz. These simple approaches may allow for applications of MXenes on a commercial scale.