Electronic Structure Sensitivity to Surface Disorder and Nanometer-Scale Impurity of 2D Titanium Carbide MXene Sheets as Revealed by Electron Energy-Loss Spectroscopy
Résumé
Two-dimensional (2D) carbides and/or nitrides (so-called MXenes) are among the latest and largest family of 2D materials. Due to their 2D nature and their unique properties of hydrophilicity, good metallic conductivity, and structural diversity, these materials are intensively studied for sensing applications or as supports for nanomaterials toward, e.g., plasmonics, catalytic, or energy storage applications. For these potential usages, the extent to which the electronic properties of MXene sheets are modified upon functionalization or intercalation is critical, and an optimized nondestructive probing of the interaction between MXene layers and functionalization is important to be determined. Here, these issues are addressed using a combination of first-principles simulations and electron energy loss spectroscopy (EELS) experiments performed at the nanoscale on Ti3C2Tx and Ti2CTx MXene multilayers, where T denotes the surface functionalization groups. Based on a detailed analysis of the carbon and surface group K edge fine structure, we show that the C-K edge is an ideal marker for surface-induced electronic structure modifications in the Tin+1Cn conducting core. These results highlight how a nanometer-scale impurity can very locally interact with a Ti3C2Tx multilayer and modify its electronic structure. This approach allows discrimination between the surface and core alteration of the Ti3C2Tx layers. Finally, the higher sensitivity to surface states of the Tin+1Cn conducting core in Ti2CTx as compared to Ti3C2Tx is discussed. We expect these results to offer an approach for understanding MXenes’ behavior and especially characterize their interactions with other nanomaterials when used in composites
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