New Approach to Accomplish the Covalent Functionalization of Boron Nitride Nanosheets: Cycloaddition Reactions

Abstract

We investigated the occurrence of cycloadditions on dimensional boron nitride. Our results indicated that the [2 + 2] cycloaddition of benzynes, ethyne, and maleic anhydride is allowed both from thermodynamical and kinetic stand points. In fact, our results indicated that the reaction energy associated with the formation of the [2 + 2] cycloaddition product is more exothermic than that computed for graphene. The activation energy determined for the [2 + 2] path is 15.9 kcal/mol, suggesting the feasibility of the process. Furthermore, we found that the activation energy for the retro reaction is 30.6 kcal/mol. This value is large enough to guarantee the stability of the functional groups but not too high to impede their detachment upon heating. In addition to these findings, we found that cycloadditions can be used to reduce the band gap of boron nitride nanosheets. In light of these results, we propose the use of cycloaddition reactions to attain the temperature-controlled functionalization of boron nitri...