Phase-Selective Chemical Extraction of Selenium and Sulfur from Nanoscale Metal Chalcogenides: A General Strategy for Synthesis, Purification, and Phase Targeting

Abstract

Controlling the composition and phase formation of bulk and nanoscale solids underpins efforts to control physical properties. Here, we introduce a powerful new chemical pathway that facilitates composition-tunable synthesis, post-synthesis purification, and precise phase targeting in metal chalcogenide systems. When metal selenides and sulfides react with trioctylphosphine (TOP) at temperatures that range from 65 to 270 °C, selenium and sulfur are selectively extracted to produce the most metal-rich chalcogenide that is stable in a particular binary system. This general approach is demonstrated for SnSe(2), FeS(2), NiSe(2), and CoSe(2), which convert to SnSe, FeS, Ni(3)Se(2), and Co(9)Se(8), respectively. In-depth studies of the Fe-Se system highlight the precise phase targeting and purification that is achievable, with PbO-type FeSe (the most metal-rich stable Fe-Se phase) forming exclusively when other Fe-Se phases, including mixtures, react with TOP. This chemistry also represents a new template-based nanoparticle "conversion chemistry" reaction, transforming hollow NiSe(2) nanospheres into hollow NiSe nanospheres with morphological retention.