光催化
光激发
原子轨道
分子轨道
电子结构
化学物理
材料科学
金属有机骨架
轨道重叠
光化学
金属
激子
轨道能级差
化学
电子
计算化学
物理化学
原子物理学
物理
分子
凝聚态物理
生物化学
有机化学
量子力学
吸附
冶金
激发态
催化作用
作者
Maxim Nasalevich,Christopher H. Hendon,Jara G. Santaclara,Katrine L. Svane,Bart van der Linden,Sergey L. Veber,Matvey V. Fedin,Arjan J. Houtepen,Monique A. Van Der Veen,Freek Kapteijn,Aron Walsh,Jorge Gascón
摘要
Abstract Metal-organic frameworks (MOFs) containing d 0 metals such as NH 2 -MIL-125(Ti), NH 2 -UiO-66(Zr) and NH 2 -UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH 2 -MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d -orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.
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