Degaga Gemechis D, Pandey Ravindra, Gupta Chansi, Bharadwaj Lalit
Department of Physics, Michigan Technological University 1400 Townsend Drive Houghton MI 49931 USA
Amity Institute of Nanotechnology, Amity University Noida UP-201303 India.
RSC Adv. 2019 May 7;9(25):14260-14267. doi: 10.1039/c9ra00687g.
Metal-organic frameworks (MOFs) are porous materials of recent interest due to their promising properties for technological applications. In this paper, the structure-property relationships of pristine and functionalized Zn-BTC (Zn(BTC)) MOFs are investigated. The results based on density functional theory (DFT) find that MOFs with coordinatively saturated secondary building units (SBU) are metallic, and MOFs with coordinatively unsaturated SBU are semi-conducting. The ligand functionalization with electron acceptor (-) and electron donor (-) groups appears to tailor the electronic properties of Zn-BTC MOFs; -functionalization led to a significant upward shift of the band-edges whereas -functionalization yields shifting of band-edges in the opposite direction, which led to a narrowing of the band gap. Modifying the electronic properties through such ligand functionalization design principles can be useful in engineering MOFs for gas sensing and device applications.
金属有机框架材料（MOFs）是近年来备受关注的多孔材料，因其在技术应用方面具有良好的性能。本文研究了原始的和功能化的Zn-BTC（Zn(BTC)）MOFs的结构-性能关系。基于密度泛函理论（DFT）的结果表明，具有配位饱和二级结构单元（SBU）的MOFs是金属性的，而具有配位不饱和SBU的MOFs是半导体性的。用电子受体（-）和电子供体（-）基团进行配体功能化似乎可以调节Zn-BTC MOFs的电子性质；-功能化导致带边显著上移，而-功能化使带边向相反方向移动，从而导致带隙变窄。通过这种配体功能化设计原则来修改电子性质，对于设计用于气体传感和器件应用的MOFs可能是有用的。
