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Structural Study of MgyAl(8+x–2y)/3O4–xNx (0 < x < 0.5, 0 < y < 1) Spinel Probed by X-ray Diffraction, 27Al MAS NMR, and First-Principles Calculations
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-20 , DOI: 10.1021/acs.inorgchem.0c02228 Xiao Zong 1 , Lu Ren 1 , Hao Wang 1 , Bingtian Tu 1 , Weimin Wang 1 , Zhengyi Fu 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-11-20 , DOI: 10.1021/acs.inorgchem.0c02228 Xiao Zong 1 , Lu Ren 1 , Hao Wang 1 , Bingtian Tu 1 , Weimin Wang 1 , Zhengyi Fu 1
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The deep understanding of the crystal structure and composition–structure relationship is important for modifying and designing solids to obtain functional materials with customized properties. However, because of multiple compositions and complex structures in some spinel solid solutions, the composition–structure relationship is unknown, or becomes very complicated and difficult to be controlled. In this work, the solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) technique and powder X-ray diffraction (XRD) Rietveld refinement were combined to characterize the crystal structure of quaternary disordered MgyAl(8+x–2y)/3O4–xNx solid solutions in detail, which was supported by the first-principles density functional theory calculations. Diffraction data indicate that Mg ions preferentially enter the tetrahedron structure in MgyAl(8+x–2y)/3O4–xNx solid solutions because the sum of the bond valence in tetrahedron is closer to the atomic valence of Mg. With the compositional change, the coordination polyhedra in the crystal structure will also adjust the volume according to the changes in lattice parameter, anion parameter, and inversion parameter. In addition, the populations, chemical shifts, and quadrupole coupling constants of Al located in different coordinated environments of the solid solutions were detected through the simulation and integration of 27Al MAS NMR spectra, which were related to the structural parameters by the bond valence method. It turns out that 27Al MAS NMR parameters are highly sensitive to the subtle changes in the local environment of Al caused by the preferential occupation of Mg in the tetrahedron. These results provide deep insights into the crystal structural details of novel spinel materials with multiple disorders.
中文翻译：
Mg y Al （8+ x –2 y）/ 3 O 4– x N x（0 < x < 0.5，0 < y <1）尖晶石的结构研究X射线衍射，27 Al MAS NMR和第一-原理计算
对晶体结构和成分-结构关系的深刻理解对于修改和设计固体以获得具有定制特性的功能材料非常重要。但是，由于某些尖晶石固溶体中存在多种成分和复杂的结构，因此成分-结构关系未知，或者变得非常复杂且难以控制。在这项工作中，固态魔角旋转核磁共振技术（MAS NMR）和粉末X射线衍射（XRD）Rietveld精制技术相结合来表征四级无序Mg y Al （8+ x –2 y）/ 3 O 4– x N x第一原理密度泛函理论计算支持了详细的固体解决方案。衍射数据表明，Mg离子优先进入Mg y Al （8+ x –2 y）/ 3 O 4– x N x中的四面体结构。固溶体，因为四面体中的键价之和更接近Mg的原子价。随着组成的变化，晶体结构中的配位多面体也会根据晶格参数，阴离子参数和转化参数的变化来调节体积。另外，通过27价Al MAS NMR谱的模拟和积分，检测了固溶体不同配位环境中Al的种群，化学位移和四极偶合常数，这些键均通过键合价法与结构参数有关。 。原来27Al MAS NMR参数对由于四面体中Mg的优先占据而引起的Al局部环境的细微变化高度敏感。这些结果提供了对具有多种疾病的新型尖晶石材料的晶体结构细节的深刻见解。
更新日期：2020-12-07
中文翻译：
Mg y Al （8+ x –2 y）/ 3 O 4– x N x（0 < x < 0.5，0 < y <1）尖晶石的结构研究X射线衍射，27 Al MAS NMR和第一-原理计算
对晶体结构和成分-结构关系的深刻理解对于修改和设计固体以获得具有定制特性的功能材料非常重要。但是，由于某些尖晶石固溶体中存在多种成分和复杂的结构，因此成分-结构关系未知，或者变得非常复杂且难以控制。在这项工作中，固态魔角旋转核磁共振技术（MAS NMR）和粉末X射线衍射（XRD）Rietveld精制技术相结合来表征四级无序Mg y Al （8+ x –2 y）/ 3 O 4– x N x第一原理密度泛函理论计算支持了详细的固体解决方案。衍射数据表明，Mg离子优先进入Mg y Al （8+ x –2 y）/ 3 O 4– x N x中的四面体结构。固溶体，因为四面体中的键价之和更接近Mg的原子价。随着组成的变化，晶体结构中的配位多面体也会根据晶格参数，阴离子参数和转化参数的变化来调节体积。另外，通过27价Al MAS NMR谱的模拟和积分，检测了固溶体不同配位环境中Al的种群，化学位移和四极偶合常数，这些键均通过键合价法与结构参数有关。 。原来27Al MAS NMR参数对由于四面体中Mg的优先占据而引起的Al局部环境的细微变化高度敏感。这些结果提供了对具有多种疾病的新型尖晶石材料的晶体结构细节的深刻见解。
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