Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor
Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor
复制标题
二胺非无害嵌入四方 FeS 超导体
DOI：
10.1021/acsaem.0c02996
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发表时间：
2021
影响因子：
6.4
通讯作者：
Kovnir, Kirill
中科院分区：
文献类型：
--
作者：
Harmer, Colin P.;Pak, Chongin;Greenfield, Joshua T.;Adeyemi, Adedoyin N.;Gamage, Eranga H.;Kovnir, Kirill
我们报告了两种插层硫化铁[Fe8S10]Fe(en)3·en0.5(en = 乙二胺)的溶剂热途径，其特点是由[Fe(en)3]2+阳离子和游离乙二胺分子堆叠的[Fe8S10]2层。 [Fe8S10]Fe(en)3·en0.5 以乙二胺中的 Fe 和 S 为原料，添加 NH4Cl 矿化剂，并对四方 FeS 进行溶剂热处理，通过简单的一步法合成。原位同步加速器粉末 X 射线衍射实验表明，四方 FeS 与 [Fe8S10]Fe(en)3·en0.5 反应后明显转变为乙二胺。内部控制合成实验证实了化学过程，乙二胺仅从四方 Fe-S 层中浸出铁，形成 [Fe(en)3]2+ 复合物，从而将层内铁氧化为 Fe2.25+。我们的报告强调，在层状铁硫属化物中，二胺可以作为带电配位络合物与中性二胺分子串联插入。
We report two solvothermal pathways toward intercalated iron sulfide, [Fe8S10]Fe(en)3·en0.5(en = ethylenediamine), featuring [Fe8S10]2–layers stacked by [Fe(en)3]2+cations and free ethylenediamine molecules. [Fe8S10]Fe(en)3·en0.5is synthesized in a simple single-step method from Fe and S in ethylenediamine with addition of NH4Cl mineralizer as well as from solvothermal treatment of mackinawite, tetragonal FeS.In situsynchrotron powder X-ray diffraction experiments reveal a clear transformation of tetragonal FeS into [Fe8S10]Fe(en)3·en0.5upon reaction with ethylenediamine. In-house control synthetic experiments confirmed the chemical process, whereby ethylenediamine leaches iron solely from the tetragonal Fe–S layers to form [Fe(en)3]2+complexes and thereby oxidize the intralayer iron to Fe2.25+. Our report emphasizes that, in layered iron chalcogenides, diamines can intercalate as charged coordination complexes in tandem with neutral diamine molecules.