Ultra-High-Field 67 Zn and 33 S NMR Studies Coupled with DFT Calculations Reveal the Structure of ZnS Nanoplatelets Prepared by an Organometallic Approach

• Published in: Journal of physical chemistry. C Vol. 127; no. 36; pp. 17809 - 17819
• Main Authors: Bellan, Ekaterina, Maleki, Farahnaz, Jakoobi, Martin, Fau, Pierre, Fajerwerg, Katia, Lagarde, Delphine, Balocchi, Andrea, Lecante, Pierre, Trébosc, Julien, Xu, Yijue, Gan, Zhehong, Pautrot-d’Alençon, Lauriane, Le Mercier, Thierry, Nagashima, Hiroki, Pacchioni, Gianfranco, Lafon, Olivier, Coppel, Yannick, Kahn, Myrtil L.
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14.09.2023
• Subjects: Chemical Sciences; Material chemistry; Nanoparticles; Nuclear magnetic resonance spectroscopy; Layers; Defects in solids; Defects
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.3c02754

Herein, we report the successful characterization of sulfur vacancies in ZnS nanoplatelets by in-depth high-field and DNP-enhanced solid-state NMR of 33S and 67Zn nuclei and DFT modeling. This two-dimensional 1 nm-thick nanomaterial was obtained by reacting a dicyclohexyl zinc complex, ZnCy2, with (TMS)2S as the S source under mild conditions (45 °C) in dodecylamine. The joint experimental and theoretical studies on these nanoplatelets evidenced that a large fraction of the Zn and S atoms are located near the surface covered by dodecylamine and that the deviation from stoichiometry (agreeing with energy gap and photoluminescence properties of non-stoichiometric material) is due to sulfur vacancies. Additionally, this work reports the first 33S DNP-NMR spectrum reported in the literature alongside several ultra-high-field 33S and 67Zn solid-state NMR spectra.