TY  - JOUR
AU  - Klemeyer, Lars
AU  - Gröne, Tjark L. R.
AU  - Zito, Cecilia de Almeida
AU  - Vasylieva, Olga
AU  - Gumus Akcaalan, Melike
AU  - Harouna-Mayer, Sani Y.
AU  - Caddeo, Francesco
AU  - Steenbock, Torben
AU  - Hussak, Sarah-Alexandra
AU  - Kesavan, Jagadesh Kopula
AU  - Dippel, Ann-Christin
AU  - Sun, Xiao
AU  - Köppen, Andrea
AU  - Saveleva, Viktoriia A.
AU  - Kumar, Surender
AU  - Bester, Gabriel
AU  - Glatzel, Pieter
AU  - Koziej, Dorota
TI  - Utilizing High X-ray Energy Photon-In Photon-Out Spectroscopies and X-ray Scattering to Experimentally Assess the Emergence of Electronic and Atomic Structure of ZnS Nanorods
JO  - Journal of the American Chemical Society
VL  - 146
IS  - 49
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2025-00152
SP  - 33475-33484
PY  - 2024
AB  - The key to controlling the fabrication process of transition metal sulfide nanocrystals is to understand the reaction mechanism, especially the coordination of ligands and solvents during their synthesis. We utilize in situ high-energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) as well as in situ valence-to-core X-ray emission spectroscopy (vtc-XES) combined with density functional theory (DFT) calculations to identify the formation of a tetrahedral [Zn(OA)<sub>4</sub>]<sup>2+</sup> and an octahedral [Zn(OA)<sub>6</sub>]<sup>2+</sup> complex, and the ligand exchange to a tetrahedral [Zn(SOA)<sub>4</sub>]<sup>2+</sup> complex (OA = oleylamine, OAS = oleylthioamide), during the synthesis of ZnS nanorods in oleylamine. We observe in situ the transition of the electronic structure of [Zn(SOA)<sub>4</sub>]<sup>2+</sup> with a HOMO/LUMO gap of 5.0 eV toward an electronic band gap of 4.3 and 3.8 eV for 1.9 nm large ZnS wurtzite nanospheres and 2 × 7 nm sphalerite nanorods, respectively. Thus, we demonstrate how in situ multimodal X-ray spectroscopy and scattering studies can not only resolve structure, size, and shape during the growth and synthesis of NPs in organic solvents and at high temperature but also give direct information about their electronic structure, which is not readily accessible through other techniques.  
LB  - PUB:(DE-HGF)16
C6  - pmid:39585247
UR  - <Go to ISI:>//WOS:001362819700001
DO  - DOI:10.1021/jacs.4c10257
UR  - https://bib-pubdb1.desy.de/record/622040
ER  -