Publication date: 15th December 2025
We will discuss our work to understand how phase is controlled in nanocrystal synthesis. Substituted thioureas were reacted with iron, cobalt and nickel and copper salts to isolate how reaction kinetics influences phase without the added complication of changing molecular decomposition mechanisms. By mapping out the effects of precursor reactivity and temperature on the phase of the metal sulfides, hypotheses can be developed about the predictable paths that occur between phases based on their anion stacking and hole filling patterns. We discovered that the synthetic behavior of the iron sulfides and cobalt sulfides can mostly be predicted by the anion stacking of hcp or ccp. The nickel sulfides instead show patterns based on the coordination number of the cations, be it 4, 5 or 6 in the product phases. Based on these maps, we developed hypothesis driven syntheses to pyrrhotite (Fe1-xS), mackinawite (Fe1+xS), smythite (Fe3+xS4), greigite (Fe3S4), marcasite (FeS2), pyrite (FeS2), jaipurite (CoS), cobalt pentlandite (Co8S9), linnaeite (Co3S4), cattierite (CoS2), a- NiS, millerite (NiS), godlevskite (Ni9S8), heazlewoodite (Ni3S2), polydymite (Ni3S4), vaesite (NiS2).
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