Formation Mechanisms for Phosphorene and SnIP

Phosphorene—the monolayered material of the element allotrope black phosphorus (P(black))—and SnIP are 2D and 1D semiconductors with intriguing physical properties. P(black) and SnIP have in common that they can be synthesized via short way transport or mineralization using tin, tin(IV) iodide and amorphous red phosphorus. This top‐down approach is the most important access route to phosphorene. The two preparation routes are closely connected and differ mainly in reaction temperature and molar ratios of starting materials. Many speculative intermediates or activator side phases have been postulated especially for top‐down P(black)/phosphorene synthesis, such as Hittorf's phosphorus or Sn(24)P(19.3)I(8) clathrate. The importance of phosphorus‐based 2D and 1D materials for energy conversion, storage, and catalysis inspired us to elucidate the formation mechanisms of these two compounds. Herein, we report on the reaction mechanisms of P(black)/phosphorene and SnIP from P(4) and SnI(2) via direct gas phase formation.