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One-dimensional lepidocrocite, 1DL, titania, TiO2, is a recently discovered form of this ubiquitous oxide that is of interest in a variety of applications ranging from photocatalysis to water purification, among others. The fundamental building blocks of these materials are snippets (30 nm long) of individual 1DLs that self-assemble into nanobundle, NB, structures. These NBs can then be driven to self-assemble into quasi-two-dimensional, 2D, sheets, films, or free-flowing mesoscopic particles. Here, we use analytical atomic-resolution scanning transmission electron microscopy (STEM) and first-principles density functional theory (DFT) calculations to demonstrate that the arrangement of the neighboring NFs can be altered through ion exchange with Li, Na, and tetramethylammonium hydroxide (TMA) cations. Moreover, using cryogenic electron energy-loss spectroscopy (EELS), we show that the introduction of different ion species results in a change in the local occupancy of the TiO2 t2g and eg orbitals. Both experimental findings are predicted by ground-state energy simulations of two-dimensional lepidocrocite TiO2. 

Abstract MXenes are a rapidly growing family of 2D transition metal carbides and nitrides that are promising for various applications, including energy storage and conversion, electronics, and healthcare. Hydrofluoric‐acid‐based etchants are typically used for large‐scale and high‐throughput synthesis of MXenes, which also leads to a mixture of surface terminations that impede MXene properties. Herein, a computational thermodynamic model with experimental validation is presented to explore the feasibility of fluorine‐free synthesis of MXenes with uniform surface terminations by dry selective extraction (DSE) from precursor MAX phases using iodine vapors. A range of MXenes and respective precursor compositions are systematically screened using first‐principles calculations to find candidates with high phase stability and low etching energy. A thermodynamic model based on the “CALculation of PHAse Diagrams” (CALPHAD) approach is further demonstrated, using Ti₃C₂I₂as an example, to assess the Gibbs free energy of the DSE reaction and the state of the byproducts as a function of temperature and pressure. Based on the assessment, the optimal synthesis temperature and vapor pressure are predicted and further verified by experiments. This work opens an avenue for scalable, fluorine‐free dry synthesis of MXenes with compositions and surface chemistries that are not accessible using wet chemical etching.