Insights into the Unanticipated Chemical Reactivity of Functionalized Nanosheets Derived from TiB₂

Titanium diboride (TiB₂) is a member of the AlB₂-type layered metal boride family; the materials of this family are receiving renewed research interest owing to their amenability to nanoscaling. Earlier, we showed that TiB₂ can be nanoscaled to yield quasi 2D nanostructures following a dissolution-recrystallization approach. This approach yielded nanosheets that were chemically functionalized with oxy-functional groups. Also, these nanosheets could inherently form a gel-like substance. In this work, we show that these functionalized nanosheets can interact with ascorbic acid in a way that first imparts a characteristic orange hue to the original yellowish nanosheet dispersion. Second, this interaction results in the loss of gel-like behavior of the nanosheet dispersion. We utilize several spectroscopic techniques such as UV-visible, FT-IR, NMR, EPR, XPS, and XANES to unravel this unexplored chemical interaction. The findings show that both titania as well as oxy-boron species react with ascorbic acid, leading to a profound modification of the nanosheets. This modification results in an augmented electrochemical response, implying that the modified nanosheets can be used in novel applications. This study is therefore a step toward gaining an even deeper understanding of the chemical opportunities that these nanoscaled borides can provide.