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Conversion Reactions of Solids: From a Surprising Three-Step Mechanism towards Directed Product Formation

机译:固体转化反应:从令人惊讶的三步机制向直接产物形成

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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.
机译:在碱性条件下,由Bi2S3和Bi2Se3与NiCl2中心点6H(2)O在多元醇介质中的反应发现了从二元化合物到多元化合物的直接转化反应。控制合成条件允许制备NiBiSe以及超导Ni3Bi2S2和Ni3Bi2Se2。从Bi2S3形成Ni3Bi2S2是从以Bi和NiBi为中间体的意外三步反应路径中发现的。在更复杂的Ni / Bi / Se系统中,发现的机制可用于选择性地指导竞争三元之间的反应并抑制副产物的形成。与固态反应(500-900摄氏度)相反,分别在166-300摄氏度和0.5-10个小时之间的反应温度和时间控制产物形成。根据DFT计算的结果讨论了不同相的形成。

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