Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms
Chaonan Cui, Hanyu Zhang, Yuming Gu, Lijun Geng, Yuhan Jia, Shiquan Lin, Jing Ma, Zhixun Luo
Abstract
High Resolution Image Download MS PowerPoint Slide Tailoring materials with prescribed properties and regular structures is a critical and challenging research topic. Early transition metals were found to form supermagic M 8 C 12 metallocarbohedrenes (Met-Cars); however, stable metal carbides are not limited to this common stoichiometry. Utilizing self-developed deep-ultraviolet laser ionization mass spectrometry, here, we report a strategy to generate new titanium carbides by reacting pure Ti n clusters with acetylene. Interestingly, two products corresponding to Ti 17 C 2 and Ti 19 C 10 exhibit superior abundances in addition to the Ti 8 C 12 Met-Cars. Using global-minimum search, the structures of Ti 17 C 2 and Ti 19 C 10 are determined to be an ellipsoidal D 4d and a rod-shaped D 5h geometry, respectively, both with carbon-capped Ti 4 C moieties and superatomic features. We illustrate the electronic structures and bonding nature in these carbon-doped superatoms concerning their enhanced stability and local aromaticity, shedding light on a new class of metal-carbide nanomaterials with atomic precision.