Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb2S3)Cl

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Wilder Carrillo-Cabrera - , Max Planck Institute for Chemical Physics of Solids (Author)
  • Oliver Dreimann - , Chair of Inorganic Chemistry II (Author)
  • Matthias A. Grasser - , Chair of Inorganic Chemistry II (Author)
  • Prosun Santra - , Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Silvan Kretschmer - , Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Arkady V. Krasheninnikov - , Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Michael Ruck - , Chair of Inorganic Chemistry II, Max Planck Institute for Chemical Physics of Solids (Author)

Abstract

The dark red semiconductor Cu(Sb2S3)Cl was obtained by leaching the layered precursor Cu(Sb2S3)[AlCl4] in a 0.1 M aqueous HCl solution. The selective extraction of AlCl3 yielded a mica-like lamellar product of poor crystallinity. Misalignment of lamellae down to the nanoscale prevented structure determination by conventional single-crystal X-ray diffraction, but a combination of transmission electron microscopy, selected area electron diffraction, and selected area electron precession diffraction tomography on a nanoscale spot with largely ordered crystalline lamellae revealed the crystal structures of two intergrown modifications. Orthorhombic o-Cu(Sb2S3)Cl and monoclinic m-Cu(Sb2S3)Cl have similar layers to the precursor and differ only in the stacking of the layers. These consist of uncharged Sb2S3 strands, whose sulfide ions, together with chloride ions, coordinate the copper(I) cations. Only one chloride ion remained from the [AlCl4] group. DFT calculations confirm the structure solution for the orthorhombic form and suggest that the monoclinic structure is metastable against transformation to o-Cu(Sb2S3)Cl.

Details

Original languageEnglish
Pages (from-to)14459-14467
Number of pages9
JournalInorganic chemistry
Volume63
Issue number31
Publication statusPublished - 5 Aug 2024
Peer-reviewedYes

External IDs

PubMed 38850238
ORCID /0000-0002-2391-6025/work/166325889