Synthesis and crystallographic analysis of shape-controlled SnS nanocrystal photocatalysts: Evidence for a pseudotetragonal structural modification

Adam J. Biacchi, Dimitri D. Vaughn, Raymond Edward Schaak

Research output: Contribution to journalArticle

92 Citations (Scopus)

Abstract

Tin sulfide, SnS, is a narrow band gap semiconductor comprised of inexpensive, earth abundant, and environmentally benign elements that is emerging as an important material for a diverse range of applications in solar energy conversion, energy storage, and electronics. Relative to many comparable systems, much less is known about the factors that influence the synthesis or morphology-dependent properties of SnS nanostructures. Here, we report the synthesis of colloidal SnS cubes, spherical polyhedra, and sheets and demonstrate their activity for the photocatalytic degradation of methylene blue. We also study their morphology-dependent polymorphism using an in-depth crystallographic analysis that correlates high-resolution TEM data of individual nanocrystals with ensemble-based electron diffraction and powder XRD data. These studies reveal that the crystal structure adopted by the SnS cubes and spherical polyhedra is expanded along the a and b axes and contracted along c, converging on a pseudotetragonal cell that is distinct from that of orthorhombic α-SnS, the most stable polymorph. All of the peaks observed in powder XRD patterns that are often interpreted as originating from a mixture of metastable zincblende-type SnS and α-SnS can instead be accounted for by this single-phase pseudotetragonal modification, and this helps to rationalize discrepancies that exist between theoretical predictions of SnS polymorph stability and interpretations of experimental diffraction data. This same crystallographic analysis also indicates the morphologies of the nanocrystals and the facets by which they are bound, and it reveals that the SnS cubes form through selective overgrowth of spherical polyhedral seeds.

Original languageEnglish (US)
Pages (from-to)11634-11644
Number of pages11
JournalJournal of the American Chemical Society
Volume135
Issue number31
DOIs
StatePublished - Aug 7 2013

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Photocatalysts
Polymorphism
Nanoparticles
Nanocrystals
Solar Energy
Powder Diffraction
Powders
Semiconductors
Nanostructures
Methylene Blue
Seeds
Electrons
Energy conversion
Electron diffraction
Energy storage
Solar energy
Tin
Seed
Electronic equipment
Diffraction

All Science Journal Classification (ASJC) codes

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

Cite this

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abstract = "Tin sulfide, SnS, is a narrow band gap semiconductor comprised of inexpensive, earth abundant, and environmentally benign elements that is emerging as an important material for a diverse range of applications in solar energy conversion, energy storage, and electronics. Relative to many comparable systems, much less is known about the factors that influence the synthesis or morphology-dependent properties of SnS nanostructures. Here, we report the synthesis of colloidal SnS cubes, spherical polyhedra, and sheets and demonstrate their activity for the photocatalytic degradation of methylene blue. We also study their morphology-dependent polymorphism using an in-depth crystallographic analysis that correlates high-resolution TEM data of individual nanocrystals with ensemble-based electron diffraction and powder XRD data. These studies reveal that the crystal structure adopted by the SnS cubes and spherical polyhedra is expanded along the a and b axes and contracted along c, converging on a pseudotetragonal cell that is distinct from that of orthorhombic α-SnS, the most stable polymorph. All of the peaks observed in powder XRD patterns that are often interpreted as originating from a mixture of metastable zincblende-type SnS and α-SnS can instead be accounted for by this single-phase pseudotetragonal modification, and this helps to rationalize discrepancies that exist between theoretical predictions of SnS polymorph stability and interpretations of experimental diffraction data. This same crystallographic analysis also indicates the morphologies of the nanocrystals and the facets by which they are bound, and it reveals that the SnS cubes form through selective overgrowth of spherical polyhedral seeds.",
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Synthesis and crystallographic analysis of shape-controlled SnS nanocrystal photocatalysts : Evidence for a pseudotetragonal structural modification. / Biacchi, Adam J.; Vaughn, Dimitri D.; Schaak, Raymond Edward.

In: Journal of the American Chemical Society, Vol. 135, No. 31, 07.08.2013, p. 11634-11644.

Research output: Contribution to journalArticle

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