Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

Abstract MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (T x ), necessitating new design approaches for MXenes that are independent of surface terminations. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-containing MXenes (Ti 2 CT x , Ti 3 C 2 T x , Cr 2 TiC 2 T x , and Mo 2 TiC 2 T x ) using soft x-ray absorption spectroscopy. For MXenes with no Ti atoms on the surface transition metal layers, such as Mo 2 TiC 2 T x and Cr 2 TiC 2 T x , our results show minimal changes in the spectral features between the parent MAX phase and its MXene. In contrast, for MXenes with surface Ti atoms, here Ti 3 C 2 T x and Ti 2 CT x , the Ti L -edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and sub-surface Ti atoms, corroborating the spectroscopic measurements. These results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface terminations, indicating a relatively short length scale over which the T x terminations alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts.