Solid-State ²³Na and ⁷Li NMR Investigations of Sodium- and Lithium-Reduced Mesoporous Titanium Oxides

Mesoporous titanium oxide synthesized using a dodecylamine template was treated with 0.2, 0.6, and 1.0 equiv of Li− or Na−naphthalene. The composite materials were characterized by nitrogen adsorption, powder X-ray diffraction, X-ray photoelectron spectroscopy, elemental analysis, thermogravimetric analysis, and solid-state ²³Na and ⁷Li NMR spectroscopy. In all cases the wormhole mesoporosity was retained as evidenced by BET surface areas from 400 to 700 m²/g, Horvath−Kawazoe pore sizes in the 20 Å range, and a lack of hysteresis in the nitrogen adsorption isotherms. Variable-temperature conductivity studies show that the Li-reduced materials are semiconductors, with conductivity values 3 orders of magnitude higher than those of the Na-reduced materials. Electrochemical measurements demonstrate reversible intercalation/deintercalation of Li⁺ ions into pristine mesoporous Ti oxides with good cycling capacity. Solid-state ²³Na NMR reveals two distinct Na environments:  one corresponding to sodium ions in the mesoporous channels and the other corresponding to sodium ions intercalated into the metal framework. ²³Na NMR spectra also indicate that the relative population of the framework site increases with increased reduction levels. Solid-state ⁷Li NMR spectra display a single broad resonance, which increases in breadth with increased reduction levels, though individual resonances inferring the presence of channel and framework Li species are not resolved. Comparisons of the lithium chemical shifts with published values suggests an “anatase-like structure” with no long-range order in the least-reduced samples but a “lithium titanate-like structure” with no long-range order in the higher reduced materials.