Phase-selective chemical extraction of selenium and sulfur from nanoscale metal chalcogenides

A general strategy for synthesis, purification, and phase targeting

Ian T. Sines, Raymond Edward Schaak

Research output: Contribution to journalArticle

40 Citations (Scopus)

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 SnSe2, FeS2, NiSe2, and CoSe2, which convert to SnSe, FeS, Ni3Se2, and Co9Se 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 NiSe2 nanospheres into hollow NiSe nanospheres with morphological retention.

Original languageEnglish (US)
Pages (from-to)1294-1297
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number5
DOIs
StatePublished - Feb 9 2011

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Chalcogenides
Selenium
Sulfur
Purification
Metals
Nanospheres
Conversion Disorder
Sulfides
Chemical analysis
Nanoparticles
Physical properties
Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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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 SnSe2, FeS2, NiSe2, and CoSe2, which convert to SnSe, FeS, Ni3Se2, and Co9Se 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 NiSe2 nanospheres into hollow NiSe nanospheres with morphological retention.",
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N2 - 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 SnSe2, FeS2, NiSe2, and CoSe2, which convert to SnSe, FeS, Ni3Se2, and Co9Se 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 NiSe2 nanospheres into hollow NiSe nanospheres with morphological retention.

AB - 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 SnSe2, FeS2, NiSe2, and CoSe2, which convert to SnSe, FeS, Ni3Se2, and Co9Se 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 NiSe2 nanospheres into hollow NiSe nanospheres with morphological retention.

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