Molecularly Confined Topochemical Transformation of MXene Enables Ultrathin Amorphous Metal-Oxide Nanosheets.

Two-dimensional (2D) amorphous nanosheets with ultrathin thicknesses have properties that differ from their crystalline counterparts. However, conventional methods for growing 2D materials often produce either crystalline flakes or amorphous nanosheets with an uncontrollable thickness. Here, we report that ultrathin amorphous metal-oxide nanosheets featuring superior flatness can be realized through the molecularly confined topochemical transformation of MXene. Using MXene TiCT as an example, we show that surface modification of TiCT nanosheets with molecular ligands, such as oleylamine (OAm) and oleic acid (OA), not only imparts notable colloidal dispersity to TiCT nanosheets in nonpolar organic solvents but also confines their subsequent oxidation to in-plane configurations. We demonstrate that unlike the drastic oxidation conventionally observed for pristine MXene, hydrophobizing MXene with OAm and OA ligands enables individual TiCT nanosheets to undergo independent oxidation in a nondestructive manner, resulting in amorphous titanium oxide (am-TiO) nanosheets that faithfully retain the dimension and flatness of pristine MXene. These am-TiO nanosheets exhibit exceptional activity as substrates for surface-enhanced Raman scattering. Importantly, this molecular confinement strategy can be extended to other MXene materials, providing a versatile approach for synthesizing ultrathin amorphous metal-oxide nanosheets with tailored compositions and functionalities.