Structure-Selective Synthesis of Wurtzite and Zincblende ZnS, CdS, and CuInS2 Using Nanoparticle Cation Exchange Reactions

Julie L. Fenton, Benjamin C. Steimle, Raymond Edward Schaak

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

For polymorphic solid-state systems containing multiple distinct crystal structures of the same composition, identifying rational pathways to selectively target one particular structure is an important synthetic capability. Cation exchange reactions can transform a growing library of metal chalcogenide nanocrystals into different phases by replacing the cation sublattice, often while retaining morphology and crystal structure. However, only a few examples have been demonstrated where multiple distinct phases in a polymorphic system could be selectively accessed using nanocrystal cation exchange reactions. Here, we show that roxbyite (hexagonal) and digenite (cubic) Cu2-xS nanoparticles transform upon cation exchange with Cd2+, Zn2+, and In3+ to wurtzite (hexagonal) and zincblende (cubic) CdS, ZnS, and CuInS2, respectively. These products retain the anion and cation sublattice features programmed into the copper sulfide template, and each phase forms to the exclusion of other known crystal structures. These results significantly expand the scope of structure-selective cation exchange reactions in polymorphic systems.

Original languageEnglish (US)
Pages (from-to)672-678
Number of pages7
JournalInorganic Chemistry
Volume58
Issue number1
DOIs
StatePublished - Jan 7 2019

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zincblende
wurtzite
Cations
Nanoparticles
cations
nanoparticles
synthesis
Crystal structure
Nanocrystals
sublattices
crystal structure
nanocrystals
copper sulfides
Sulfides
retaining
exclusion
Anions
Copper
templates
Metals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Structure-Selective Synthesis of Wurtzite and Zincblende ZnS, CdS, and CuInS2 Using Nanoparticle Cation Exchange Reactions",
abstract = "For polymorphic solid-state systems containing multiple distinct crystal structures of the same composition, identifying rational pathways to selectively target one particular structure is an important synthetic capability. Cation exchange reactions can transform a growing library of metal chalcogenide nanocrystals into different phases by replacing the cation sublattice, often while retaining morphology and crystal structure. However, only a few examples have been demonstrated where multiple distinct phases in a polymorphic system could be selectively accessed using nanocrystal cation exchange reactions. Here, we show that roxbyite (hexagonal) and digenite (cubic) Cu2-xS nanoparticles transform upon cation exchange with Cd2+, Zn2+, and In3+ to wurtzite (hexagonal) and zincblende (cubic) CdS, ZnS, and CuInS2, respectively. These products retain the anion and cation sublattice features programmed into the copper sulfide template, and each phase forms to the exclusion of other known crystal structures. These results significantly expand the scope of structure-selective cation exchange reactions in polymorphic systems.",
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Structure-Selective Synthesis of Wurtzite and Zincblende ZnS, CdS, and CuInS2 Using Nanoparticle Cation Exchange Reactions. / Fenton, Julie L.; Steimle, Benjamin C.; Schaak, Raymond Edward.

In: Inorganic Chemistry, Vol. 58, No. 1, 07.01.2019, p. 672-678.

Research output: Contribution to journalArticle

TY - JOUR

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AU - Steimle, Benjamin C.

AU - Schaak, Raymond Edward

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N2 - For polymorphic solid-state systems containing multiple distinct crystal structures of the same composition, identifying rational pathways to selectively target one particular structure is an important synthetic capability. Cation exchange reactions can transform a growing library of metal chalcogenide nanocrystals into different phases by replacing the cation sublattice, often while retaining morphology and crystal structure. However, only a few examples have been demonstrated where multiple distinct phases in a polymorphic system could be selectively accessed using nanocrystal cation exchange reactions. Here, we show that roxbyite (hexagonal) and digenite (cubic) Cu2-xS nanoparticles transform upon cation exchange with Cd2+, Zn2+, and In3+ to wurtzite (hexagonal) and zincblende (cubic) CdS, ZnS, and CuInS2, respectively. These products retain the anion and cation sublattice features programmed into the copper sulfide template, and each phase forms to the exclusion of other known crystal structures. These results significantly expand the scope of structure-selective cation exchange reactions in polymorphic systems.

AB - For polymorphic solid-state systems containing multiple distinct crystal structures of the same composition, identifying rational pathways to selectively target one particular structure is an important synthetic capability. Cation exchange reactions can transform a growing library of metal chalcogenide nanocrystals into different phases by replacing the cation sublattice, often while retaining morphology and crystal structure. However, only a few examples have been demonstrated where multiple distinct phases in a polymorphic system could be selectively accessed using nanocrystal cation exchange reactions. Here, we show that roxbyite (hexagonal) and digenite (cubic) Cu2-xS nanoparticles transform upon cation exchange with Cd2+, Zn2+, and In3+ to wurtzite (hexagonal) and zincblende (cubic) CdS, ZnS, and CuInS2, respectively. These products retain the anion and cation sublattice features programmed into the copper sulfide template, and each phase forms to the exclusion of other known crystal structures. These results significantly expand the scope of structure-selective cation exchange reactions in polymorphic systems.

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