Journal Article

PUBDB-2026-00365

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png In situ X-ray Synchrotron Studies Reveal the Nucleation and Topotactic Transformation of Iron Sulfide Nanosheets

Zito, C. A.Extern* ; Klemeyer, L.Extern*DESY* ; Caddeo, F.Extern* ; Jessen, B.Extern* ; Harouna-Mayer, S. Y.Extern* ; Lacroix, L.-M. ; Langfeldt, M. ; Gröne, T. L. R.Extern* ; Kesavan, J. K.Extern*XFEL.EU* ; Hsu, C.-S.Extern*XFEL.EU* ; Schwarz, A. ; Dippel, A.-C.DESY* ; Igoa Saldaña, F.XFEL.EU*DESY* ; Detlefs, B. ; Koziej, D. (Corresponding author)Extern*

2025
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/jacs.5c15843  doi:10.3204/PUBDB-2026-00365

Abstract: Iron sulfides (FexSy), including greigite (Fe$_3$S$_4$), are key materials in geological processes and technological applications. However, in the context of colloidal synthesis, the mechanism by which these nanoparticles form remains unexplored. Here, we employ in situ X-ray diffraction and photon-in photon-out spectroscopic studies to elucidate the reaction pathway of Fe(acac)$_3$ and thioacetamide (TAA) in benzyl alcohol (BA), which yields crumpled Fe$_3$S$_4$ nanosheets. Using powder X-ray diffraction (PXRD), we identify FeS (mackinawite) as a crystalline intermediate whose anisotropic growth, driven by its layered crystal structure, governs the crumpled nanosheet-like morphology of Fe$_3$S$_4$ (greigite) through a topotactic transition. By performing high-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy, we show that the formation of Fe$_3$S$_4$ proceeds through a multistep mechanism involving two intermediates. Supported by density functional theory (DFT), we find that Fe(acac)$_3$ is initially reduced in the presence of TAA in BA, forming a molecular intermediate [Fe(acac)$_2$(BA)$_2$], which subsequently transforms into FeS and ultimately into Fe$_3$S$_4$. Complementary valence-to-core X-ray emission spectroscopy (vtc-XES) reveals the evolution of the coordination environment from Fe–O to Fe–S throughout the reaction. Our work provides a comprehensive understanding of the formation mechanism of Fe$_3$S$_4$ nanosheets in solution, shedding light on how crystal growth dynamics and electronic structure evolution dictate their unique crumpled nanosheet morphology.

Note: European Research Council (ERC) LINCHPIN (grant no. 818941), the Deutsche Forschungsgemeinschaft (DFG) through the Cluster of Excellence “Advanced Imaging of Matter” (EXC 2056, project ID 390715994) and the Graduate School “Nanohybrid” (funding ID 408076438), and the Bundesministerium für Bildung und Forschung (BMBF) via the project 05K22GU7 (LUCENT II)

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Contributing Institute(s):

1. PETRA-D (FS-PETRA-D)
2. DOOR-User (DOOR ; HAS-User)
3. Universität Hamburg (UHH)

Research Program(s):

1. 632 - Materials – Quantum, Complex and Functional Materials (POF4-632) (POF4-632)
2. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
3. FS-Proposal: I-20230658 (I-20230658) (I-20230658)
4. DFG project G:(GEPRIS)390715994 - EXC 2056: CUI: Tiefe Einblicke in Materie (390715994) (390715994)
5. GRK 2536 - GRK 2536: Hybridstrukturen auf der Nanometerskala: Chemische Konzepte zur Herstellung heterogener Nanostrukturen mit anisotropen Materialeigenschaften (NANOHYBRID) (408076438) (408076438)
6. 05K22GU7 - Untersuchung photoaktiver Nanomaterialien durch Hochenergie-Röntgenstrahl Streumethoden: Messzellen für Atome, Cluster und Nanokristalle (BMBF-05K22GU7) (BMBF-05K22GU7)

Experiment(s):

1. PETRA Beamline P21.1 (PETRA III)

Appears in the scientific report 2025

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Database coverage:
; ; ; BIOSIS Previews ; Biological Abstracts ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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