Single-wall carbon nanotubes (SWCNTs) are one-dimensional cylindrical structures that resemble a rolled-up graphene sheet. These artificial nanomaterials show unique chemical and physical properties that attract the interest of many basic and applied researchers. Most SWCNTs are semiconducting and emit sharp and characteristic band gap fluorescence in the near-infrared. A topic of great current interest is chemical modification of SWCNT optical properties. These chemical modifications can increase fluorescence quantum yields and shift emission further into the near-infrared region, allowing biomedical applications to benefit from improved tissue transparency and greatly reduced autofluorescence backgrounds. Here we present further studies on the use of photodissociated hypochlorite to produce SWCNTs with covalent oxygen doping. By removing dissolved O<sub>2</sub> from the aqueous SWCNT reaction system, we find greatly increased reaction rates and the appearance of new and further red-shifted emission bands. These results, combined with kinetic data, pH dependent studies, and quantum computations, provide new insights into the doping products and mechanism. This research will enable more efficient and controlled production of carbon nanotubes with tailored optical properties.

Mechanistic study of the functionalization of single-wall carbon nanotubes by photoexcited hypochlorite

ACS Spring 2022

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