Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor

被引：11
作者：
Harmer, Colin P. [1 ,2 ]
Pak, Chongin [3 ]
Greenfield, Joshua T. [3 ]
Adeyemi, Adedoyin N. [1 ]
Gamage, Eranga H. [1 ,2 ]
Kovnir, Kirill [1 ,2 ]
机构：
[1] Iowa State Univ, Dept Chem, Ames, IA 50011 USA
[2] US DOE, Ames Lab, Ames, IA 50011 USA
[3] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
来源：
ACS APPLIED ENERGY MATERIALS | 2021年 / 4卷 / 01期
基金：
美国国家科学基金会;
关键词：
iron chalcogenide; solvothermal synthesis; intercalation; crystal structure; in situ;
D O I：
10.1021/acsaem.0c02996
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
We report two solvothermal pathways toward intercalated iron sulfide, [Fe8S10]Fe(en)(3)center dot en(0.5) (en = ethylenediamine), featuring [Fe8S11](2-) layers stacked by [Fe(en)(3)](2+) cations and free ethylenediamine molecules. [Fe8S10]Fe(en)(3)center dot en(0.5) is 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 situ synchrotron powder X-ray diffraction experiments reveal a clear transformation of tetragonal FeS into [Fe8S10]Fe(en)(3)center dot en(0.5) upon 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.
引用
收藏
页码：42 / 46
页数：5
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