Conversion Reactions of Solids: From a Surprising Three‐Step Mechanism towards Directed Product Formation |
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| Authors: | Stefan Michael Rommel Alexander Krach Philipp Peter Prof Dr Richard Weihrich |
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| Institution: | 1. Institute for Materials Resource Management, University of Augsburg, Augsburg, Germany;2. Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany;3. Departement of Chemistry, TU Munich, Garching, Germany |
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| Abstract: | Directed conversion reactions from binary to multinary compounds are discovered from the reaction of Bi2S3 and Bi2Se3 with NiCl2 ? 6 H2O in polyol media under basic conditions. Control of the synthesis conditions allows the preparation of NiBiSe and superconducting Ni3Bi2S2 and Ni3Bi2Se2. The formation of Ni3Bi2S2 from Bi2S3 is found from an unexpected three‐step reaction path with Bi and NiBi as intermediates. In the more complex Ni/Bi/Se system, the mechanism found can be used to selectively direct the reaction between the competing ternaries and to suppress side‐product formation. Contrary to solid‐state reactions (500–900 °C) control of product formation is reached at reaction temperatures and times between 166–300 °C and 0.5–10 h, respectively. The formation of different phases is discussed from results of DFT calculations. |
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| Keywords: | formation mechanism nanoparticles polyol process synthetic methods ternary chalcogenide |
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