Sorting of Cluster-Confined Metallic Single-Walled Carbon Nanotubes for Fabricating Atomically Vacant Uranium Oxide

Single-walled carbon nanotube (SWCNT) heterostructures have shown great potential in catalysis, magnetism, and nanofluidics, in which host SWCNTs with certain conductivity (metallic or semiconducting) are highly required. Herein, inspired by the large molecular weight and redox properties of polyoxometalate (POM) clusters, we reported the selective separation of POM encapsulated metallic SWCNTs (POM@m-SWCNTs) with a uniform diameter through density gradient ultracentrifugation (DGU). The confined POMs increased the SWCNT density and amplified the nanotubes' density difference, thus greatly lowering the centrifugal force (70,000g) of DGU. With this strategy, a series of POM@m-SWCNTs of ∼1.2 nm with high purity were sorted. The mechanism supported by theoretical and experimental evidence showed that the separation of m-SWCNTs depended on not only nanotube/cluster size but also the conductivity of SWCNTs. The smallest 1.2 nm m-SWCNT that can exactly accommodate a 0.9 nm-{Mo₆} cluster exhibited the maximum electron transfer to inner clusters; thus, intertube π-π stacking of such m-SWCNTs was greatly loosened, leading to the preferential dispersion into individual ones and partitioning in the uppermost layer after DGU. As a proof-of-concept application, this sorting strategy was extended to separate heavy-element ²³⁸U-encapsulated m-SWCNTs. The phase-pure, tiny (1-2.5 nm) U₄O₉ crystals with atomic vacancy clusters were fabricated on m-SWCNTs through growth kinetic control. This work may provide a general way to construct desired actinide materials on specific SWCNTs.