Polyoxometalate steric hindrance driven chirality-selective separation of subnanometer carbon nanotubes

Subnanometer single-chirality single-walled carbon nanotubes (SWCNTs) are of particular interest in multiple applications. Inspired by the interdisciplinary combination of redox active polyoxometalates and SWCNTs, here we report a cluster steric hindrance strategy by assembling polyoxometalates on the outer surface of subnanometer SWCNTs via electron transfer and demonstrate the selective separation of monochiral (6,5) SWCNTs with a diameter of 0.75 nm by a commercially available conjugated polymer. The combined use of DFT calculations, TEM, and XPS unveils the mechanism that selective separation is associated with tube diameter-dependent interactions between the tube and clusters. Sonication drives the preferential detachment of polyoxometalate clusters from small-diameter (6,5) SWCNTs, attributable to weak tube-cluster interactions, which enables the polymer wrapping and separation of the released SWCNTs, while strong binding clusters with large-diameter SWCNTs provide steric hindrance and block the polymer wrapping. The polyoxometalate-assisted modulation, which can be rationally customized, provides a universal and robust pathway for the separation of SWCNTs.