双金属金属有机框架 (MOF) 的电子特性：通过 MOF 模块化调整电子态的密度,Journal of the American Chemical Society

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双金属金属有机框架 (MOF) 的电子特性：通过 MOF 模块化调整电子态的密度
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-03-31 , DOI: 10.1021/jacs.7b01125
Ekaterina A. Dolgopolova , Amy J. Brandt , Otega A. Ejegbavwo , Audrey S. Duke , Thathsara D. Maddumapatabandi , Randima P. Galhenage , Bryon W. Larson ₁ , Obadiah G. Reid _{1,

2} , Salai C. Ammal , Andreas Heyden , Mvs Chandrashekhar , Vitalie Stavila ₃ , Donna A. Chen , Natalia B. Shustova

Affiliation

多孔明确定义的混合材料（例如，金属有机框架或 MOF）的开发将为从超级电容器和电极到“智能”膜和热电器件的广泛应用增加新的维度。从这个角度来看，理解和调整 MOF 的电子特性是关键的基本挑战，可以释放这些材料的全部潜力。在这项工作中，我们专注于负责三种不同类型双金属系统的电子特性的基本见解，Mx-yM'y-MOFs、MxM'y-MOFs 和 Mx(ligand-M'y)-MOFs，在其中第二个金属 (M') 掺入是通过 (i) 框架节点中的金属 (M) 置换（I 型），（ii）金属节点延伸（II 型）和 (iii) 金属与有机配体的配位而发生的（类型 III), 分别。我们采用微波电导率、X 射线光电子能谱、漫反射光谱、粉末 X 射线衍射、电感耦合等离子体原子发射光谱、压制颗粒电导率和理论模型来阐明负责 MOF 电子可调性的关键因素。结构。MOFs 的实验预筛选是基于费米边缘附近电子态密度的变化进行的，这被用作进一步选择合适的 MOFs 的起点。因此，我们证明了 MOF 电子特性的定制可以作为金属节点工程、框架拓扑和/或不饱和金属位点的存在的函数来执行，同时保持框架孔隙率和结构完整性。

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Electronic Properties of Bimetallic Metal–Organic Frameworks (MOFs): Tailoring the Density of Electronic States through MOF Modularity

The development of porous well-defined hybrid materials (e.g., metal-organic frameworks or MOFs) will add a new dimension to a wide number of applications ranging from supercapacitors and electrodes to "smart" membranes and thermoelectrics. From this perspective, the understanding and tailoring of the electronic properties of MOFs are key fundamental challenges that could unlock the full potential of these materials. In this work, we focused on the fundamental insights responsible for the electronic properties of three distinct classes of bimetallic systems, Mx-yM'y-MOFs, MxM'y-MOFs, and Mx(ligand-M'y)-MOFs, in which the second metal (M') incorporation occurs through (i) metal (M) replacement in the framework nodes (type I), (ii) metal node extension (type II), and (iii) metal coordination to the organic ligand (type III), respectively. We employed microwave conductivity, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, pressed-pellet conductivity, and theoretical modeling to shed light on the key factors responsible for the tunability of MOF electronic structures. Experimental prescreening of MOFs was performed based on changes in the density of electronic states near the Fermi edge, which was used as a starting point for further selection of suitable MOFs. As a result, we demonstrated that the tailoring of MOF electronic properties could be performed as a function of metal node engineering, framework topology, and/or the presence of unsaturated metal sites while preserving framework porosity and structural integrity. These studies unveil the possible pathways for transforming the electronic properties of MOFs from insulating to semiconducting, as well as provide a blueprint for the development of hybrid porous materials with desirable electronic structures.

更新日期：2017-03-31

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