Precursor Formulation Redirects Phase Competition and Thermal Evolution in Silver Multinary Chalcogenide Ag-M-Ch (M = Zr, Cr, Sn, Sb) Nanocrystals
- 1Department of Chemistry and Biochemistry
- 2Loyola University Chicago
Abstract
Multinary nanocrystal synthesis requires chemically dissimilar metals to enter a common framework while competing with binary crystallization and metal reduction. We examine this competition through 31 preparation records spanning nominal Ag8SnS6, Ag4Zr3S8, AgZrSe2, AgCrSe2, and Ag3SbS3 targets in an oleylamine–octadecene platform. In a matched Ag–Zr–S comparison at 240 °C for 20 min, replacing an elemental-sulfur-derived stock with trioctylphosphine sulfide redirects a dense diffraction fingerprint toward a sparse fcc-Ag-compatible series. Comparison with independently identified crystallographic records further reveals substantial overlap of the sulfide and selenide fingerprints with acanthite Ag2S and published metastable P21/n Ag2Se, respectively. Microscopy resolves condition-dependent morphology, local lattice order, and elemental association within selected fields. Calorimetric heating and cooling traces reveal preparation-dependent responses, with ten individually resolved higher-temperature events at 88.63–176.33 °C. Annealing at 300 °C for 2 h under Ar yields composition-dependent morphological endpoints; two interpretable diffraction pairs distinguish persistence of an Ag-compatible component from redistribution of a more complex Ag–Sb–S fingerprint. The results identify precursor formulation as a control over competing crystalline pathways and show why thermal sensitivity must be interpreted in the context of those pathways. This comparative library connects reaction design with structural discrimination and subsequent processing response in silver-containing chalcogenides.
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BibTeX
@misc{xu2026precursor,
title = {{Precursor Formulation Redirects Phase Competition and Thermal Evolution in Silver Multinary Chalcogenide Ag-M-Ch (M = Zr, Cr, Sn, Sb) Nanocrystals}},
author = {Yunhao Xu and Isabella Campbell and Simran Chaudhury and Oluwaseyi Saliu and Progna Banerjee},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010865/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010865/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Precursor Formulation Redirects Phase Competition and Thermal Evolution in Silver Multinary Chalcogenide Ag-M-Ch (M = Zr, Cr, Sn, Sb) Nanocrystals
AU - Yunhao Xu
AU - Isabella Campbell
AU - Simran Chaudhury
AU - Oluwaseyi Saliu
AU - Progna Banerjee
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010865/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010865/v1
AB - Multinary nanocrystal synthesis requires chemically dissimilar metals to enter a common framework while competing with binary crystallization and metal reduction. We examine this competition through 31 preparation records spanning nominal Ag8SnS6, Ag4Zr3S8, AgZrSe2, AgCrSe2, and Ag3SbS3 targets in an oleylamine–octadecene platform. In a matched Ag–Zr–S comparison at 240 °C for 20 min, replacing an elemental-sulfur-derived stock with trioctylphosphine sulfide redirects a dense diffraction fingerprint toward a sparse fcc-Ag-compatible series. Comparison with independently identified crystallographic records further reveals substantial overlap of the sulfide and selenide fingerprints with acanthite Ag2S and published metastable P21/n Ag2Se, respectively. Microscopy resolves condition-dependent morphology, local lattice order, and elemental association within selected fields. Calorimetric heating and cooling traces reveal preparation-dependent responses, with ten individually resolved higher-temperature events at 88.63–176.33 °C. Annealing at 300 °C for 2 h under Ar yields composition-dependent morphological endpoints; two interpretable diffraction pairs distinguish persistence of an Ag-compatible component from redistribution of a more complex Ag–Sb–S fingerprint. The results identify precursor formulation as a control over competing crystalline pathways and show why thermal sensitivity must be interpreted in the context of those pathways. This comparative library connects reaction design with structural discrimination and subsequent processing response in silver-containing chalcogenides.
ER -