Zusammenfassung
Directed conversion reactions from binary to multinary compounds are discovered from the reaction of Bi2S3 and Bi2Se3 with NiCl2 center dot 6H(2)O 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 ...
Zusammenfassung
Directed conversion reactions from binary to multinary compounds are discovered from the reaction of Bi2S3 and Bi2Se3 with NiCl2 center dot 6H(2)O 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 sideproduct formation. Contrary to solid-state reactions (500-900 degrees C) control of product formation is reached at reaction temperatures and times between 166-300 degrees C and 0.5-10 h, respectively. The formation of different phases is discussed from results of DFT calculations.
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