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@ARTICLE{Klemeyer:636202,
      author       = {Klemeyer, Lars and Caddeo, Francesco and Gröne, Tjark L.
                      R. and Harouna-Mayer, Sani Y. and Jessen, Brian and Zito,
                      Cecilia A. and Kopula Kesavan, Jagadesh and Dippel,
                      Ann-Christin and Igoa Saldana, Fernando and Mathon, Olivier
                      and Glatzel, Pieter and Koziej, Dorota},
      title        = {{S}patially {R}esolved {I}n {S}itu {X}-ray {A}bsorption
                      {S}pectroscopy {S}tudies of {Z}n{S} {N}anoparticle
                      {S}ynthesis at the {W}ater–{T}oluene {I}nterface},
      journal      = {ACS nano},
      volume       = {19},
      number       = {28},
      issn         = {1936-0851},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {PUBDB-2025-03627},
      pages        = {25710 - 25719},
      year         = {2025},
      abstract     = {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$^{2+}$ 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$_2$O)$_6$]$^{2+}$ complex upon dissolving Zn(Ac)$_2$
                      in water and the diffusion of Zn$^{2+}$ ions from water to
                      toluene driven by the formation of an octahedral
                      [Zn(OA)$_6$]$^{2+}$ 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]$^{2+}$ 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$^{2+}$ 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.},
      cin          = {DOOR ; HAS-User / FS-PETRA-D},
      ddc          = {540},
      cid          = {I:(DE-H253)HAS-User-20120731 /
                      I:(DE-H253)FS-PETRA-D-20210408},
      pnm          = {632 - Materials – Quantum, Complex and Functional
                      Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) /
                      LINCHPIN - A platform to LINk between CHemistry and PhysIcs
                      of colloidal Nanomaterials (818941) / AIM, DFG project
                      G:(GEPRIS)390715994 - EXC 2056: CUI: Advanced Imaging of
                      Matter (390715994) / GRK 2536 - GRK 2536: Hybridstrukturen
                      auf der Nanometerskala: Chemische Konzepte zur Herstellung
                      heterogener Nanostrukturen mit anisotropen
                      Materialeigenschaften (NANOHYBRID) (408076438)},
      pid          = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 /
                      G:(EU-Grant)818941 / G:(GEPRIS)390715994 /
                      G:(GEPRIS)408076438},
      experiment   = {EXP:(DE-H253)P-P21.1-20150101},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:40627349},
      doi          = {10.1021/acsnano.5c02875},
      url          = {https://bib-pubdb1.desy.de/record/636202},
}