Enhanced photoreactivity of amine-functionalized carbon nanotubes under sunlight in the aquatic environment

To overcome the hydrophobic nature of pristine carbonaceous materials such as carbon nanotubes (CNTs) and to make them available for intended applications, chemically covalent functionalization tailoring these materials is widely applied. However, the addition of surface functional moieties often changes the fundamental properties of the parent materials and introduces great variations that hinder a full understanding of and unified conclusions about their environmental implications. In this work, we studied the photoactivity of covalently functionalized CNTs in the aquatic environment under sunlight irradiation. The results indicate an enhanced photoreactivity of CNTs with amine functional groups resulting from a greater excited triplet state formation and a restored electronic structure after the secondary functionalization. Photogenerated singlet oxygen was produced directly through a photosensitization process in which the photoexcited CNTs transferred energy to oxygen, as well as produced indirectly from the aqueous reactions of superoxide radical. The superior photoreactive behaviors of engineered nanomaterials with amine functionalization in terms of reactive oxygen species generation in aquatic environments not only raise ecological concerns, but also render these functionalized engineered nanomaterials useful as water treatment agents against pollutants or microorganisms that can be destroyed by singlet oxygen or hydroxyl radicals.