Investigating the mechanism of phosphorene nanoribbon synthesis by discharging black phosphorus intercalation compounds

Phosphorene nanoribbons (PNRs) can be synthesised in intrinsically scalable methods from intercalation of black phosphorus (BP), however, the mechanism of ribbonisation remains unclear. Herein, to investigate the point at which nanoribbons form, we decouple the two key synthesis steps: first, the formation of the BP intercalation compound, and second, the dissolution into a polar aprotic solvent. We find that both the lithium intercalant and the negative charge on the phosphorus host framework can be effectively removed by addition of phenyl cyanide to return BP and investigate whether fracturing to ribbons occurred after the first step. Further efforts to exfoliate mechanically with or without solvent reveal that the intercalation step does not form ribbons, indicating that an interaction between the amidic solvent and the intercalated phosphorus compound plays an important role in the formation of nanoribbons.