Abstract
The reactions of methylamine, dimethylamine, and trimethylamine with TiS2 were characterized by several techniques. Detailed studies of the intercalation of methylamine demonstrated that the reaction was of the redox-rearrangement type, where the intercalate is best described as (CH3NH+3)y′ (CH3NH2)y″ TiS2y′−, with y′=0.25±0.02 and y″ dependent on sample history. For y′=0.25 and y″=0.15, this intercalate is a mixed-phase stage 1 [a=3.422(5) Å and c=28.06(10) Å] and stage 2 [a=3.4265 Å and c=42.48(10) Å] compound having R3m symmetry. Visual observation and thermogravimetric analysis of dimethylamine intercalation also suggest a redox-rearrangement mechanism. In contrast, no intercalation was observed for trimethylamine. The onset time for intercalation of liquid amines into TiS2 at ambient temperature follows the general trend: N2H4<NH3<CH3NH2<(CH3)2NH⪡(CH3)3N. This trend is consistent with an increase in steric hindrance about the N atom and decrease in the number of amine hydrogen atoms that effectively reduces the nucleophilic reaction rate of the intercalant.
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