title: 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.
authors.affiliation: Department of Chemistry and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
authors.forename: Ian T
authors.initials: IT
authors.lastname: Sines
authors.forename: Raymond E
authors.initials: RE
authors.lastname: Schaak