A critical analysis of the X-ray photoelectron spectra of Ti3C2Tz MXenes

Since their discovery in 2011, MXenes have garnered worldwide interest. Given their 2D structure, surface, or termination, chemistries play a vital role in most applications. X-ray photoelectron spectroscopy (XPS) is one of the most common characterization tools for quantifying surface terminations and overall chemistry. Herein, we critically review the XPS fitting models proposed for Ti3C2Tz MXene in the literature and make the case that they are at best incomplete and at worst contradictory. We propose a new fitting algorithm based on all the data obtained from previously published studies and propose a new method for quantifying the surface terminations in Ti3C2Tz. In our approach, we assign the Ti 2p peak at 455.1 eV to the C-Ti-O\O\O, and the peaks at 456.0, 457.0, 457.9, and 459.6 eV are assigned to C-Ti-O\O\F, C-Ti-O\F\F, C-Ti-F\F\F, and TiO2-xF2x, respectively. The first four represent possible Ti atom terminations; the last is an oxyfluoride. The C 1s peak at 282 eV, ascribed to C atoms surrounded by 6 Ti atoms, is so universal that it can almost be used as a reference.