%0 Journal Article
%A Klemeyer, Lars
%A Caddeo, Francesco
%A Gröne, Tjark L. R.
%A Harouna-Mayer, Sani Y.
%A Jessen, Brian
%A Zito, Cecilia A.
%A Kopula Kesavan, Jagadesh
%A Dippel, Ann-Christin
%A Igoa Saldana, Fernando
%A Mathon, Olivier
%A Glatzel, Pieter
%A Koziej, Dorota
%T Spatially Resolved In Situ X-ray Absorption Spectroscopy Studies of ZnS Nanoparticle Synthesis at the Water–Toluene Interface
%J ACS nano
%V 19
%N 28
%@ 1936-0851
%C Washington, DC
%I Soc.
%M PUBDB-2025-03627
%P 25710 - 25719
%D 2025
%X Two-phase synthesis is a well-established approach for achieving precise control of the nanoparticle properties. However, studying and understanding chemical transformations in such a spatially heterogeneous system is challenging. In this work, we introduce a two-phase synthesis route for ZnS nanoparticles (ZnS NPs) at the water–toluene interface. By employing spatially resolved in situ high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) combined with density functional theory (DFT) calculations, we track the diffusion of Zn<sup>2+</sup> species at the interface, identify key reaction intermediates, and monitor the nucleation and growth of ZnS NPs within the toluene phase. We propose the formation of a [Zn(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> complex upon dissolving Zn(Ac)<sub>2</sub> in water and the diffusion of Zn<sup>2+</sup> ions from water to toluene driven by the formation of an octahedral [Zn(OA)<sub>6</sub>]<sup>2+</sup> complex (OA = oleylamine). Furthermore, by complementing HERFD-XAS with total X-ray scattering analysis, we show the formation of an intermediate tetrahedral [Zn(SR)4]<sup>2+</sup> complex at 60 °C and its successive transformation to noncrystalline ZnS nuclei at 80 °C and crystalline ZnS NPs starting at 100 °C. Thus, we demonstrate how in situ X-ray spectroscopy can elucidate the coordination and diffusion of Zn<sup>2+</sup> ions, and, in combination with X-ray scattering studies, identify the emergence of atomic and electronic structures during the two-phase synthesis of ZnS nanoparticles.  
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:40627349
%R 10.1021/acsnano.5c02875
%U https://bib-pubdb1.desy.de/record/636202