Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its...

The studies on mechanical treatments of layered alkali metal oxides are limited despite their diverse compositions/structures and potential for property tuning. In this work, we vibratory mill Cs_0.7Zn_0.35Ti_1.65O₄, K_0.8Zn_0.4Ti_1.6O₄, and Cs₂Ti₆O₁₃ for up to 4 h, during which the lepidocrocite-type structure and the plate-like morphology are well preserved. X-ray diffraction (XRD) indicates a tiny (≤0.6 Å) interlayer expansion accompanied by the enhancement of the preferred orientation along the stacking direction. Chemical analyses across multiple length scales suggest Cs deintercalation, elemental redistributions, and bulk-to-surface (or crystal edge) Cs migration. This ball-milling-induced Cs-rich moiety partially blocks the surface acid sites, although the solids still show a dominating acidic character. The ball-milled samples Cs_0.7-Zn_0.35-Ti_1.65O_4-δ contain vacancies between the sheets (p) and at the sheets (q and δ). It is deduced from Sanderson's electronegativity equalization principle and experimentally verified by X-ray photoelectron spectroscopy (XPS) that ball milling increases (decreases) the partial charge at the surface acidic Ti⁴⁺/Zn²⁺ (basic O^2-) sites. These nonporous solids (≤20 m²·g^-1) contain water sorbed on the external surface as high as 1.1 mol·mol^-1, which is comparable to that in a water-intercalated sample. Our work expands the current understanding of the reactivity vs robustness in layered alkali titanates under physically demanding conditions, complementing knowledge gathered via the soft chemistry approach.