Assessing the Surface Chemistry of 2D Transition Metal Carbides (MXenes): A Combined Experimental/Theoretical 13C Solid State NMR Approach

The surface functionalization of 2D transition metal carbides or nitrides, so-called MXenes, is one of the fundamental levers allowing to deeply modify their physicochemical properties. Beyond new approaches to control this pivotal parameter, the ability to unambiguously assess their surface chemistry is thus key to expand the application fields of this large class of 2D materials. Using a combination of experiments and state of the art density functional theory calculations, we show that the NMR signal of the carbon -the element common to all MXene carbides and corresponding MAX phase precursors -is extremely sensitive to the MXene functionalization, although carbon atoms are not directly bonded to the surface groups. The simulations include the orbital part to the NMR shielding and the contribution from the Knight shift, which is crucial to achieve good correlation with the experimental data, as demonstrated on a set of reference MXene precursors. Starting with the Ti3C2Tx MXene benchmark system, we confirm the high sensitivity of the 13C NMR shift to the exfoliation process. Developing a theoretical protocol to straightforwardly simulate different surface chemistries, we show that the 13C NMR shift variations can be quantitatively related to different surface compositions and number of surface chemistry variants induced by the different etching agents. In addition, we propose that the etching agent affects not only the nature of the surface groups but also their spatial distribution. The direct correlation between surface chemistry and 13C NMR shift is further confirmed on the V2CTx, Mo2CTx, and Nb2CTx MXenes.

Automated summary

The functionalization of MXenes, a class of 2D materials, can significantly modify their physicochemical properties. Through experiments and theoretical calculations, we found that the carbon NMR signal in MXenes is highly sensitive to functionalization, even though carbon atoms are not directly bonded to the surface groups. We developed a theoretical model to quantitatively relate the 13C NMR shift to different surface compositions and the number of surface chemistry variants induced by different etching agents.