Cargando…

Metal Substitution as the Method of Modifying Electronic Structure of Metal–Organic Frameworks

[Image: see text] Targeted modification of electronic structure is an important step in the optimization of metal–organic frameworks (MOFs) for photovoltaic, sensing, and photocatalytic applications. The key parameters to be controlled include the band gap, the absolute energy position of band edges...

Descripción completa

Detalles Bibliográficos
Autores principales: Syzgantseva, Maria A., Ireland, Christopher Patrick, Ebrahim, Fatmah Mish, Smit, Berend, Syzgantseva, Olga A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6477807/
https://www.ncbi.nlm.nih.gov/pubmed/30915844
http://dx.doi.org/10.1021/jacs.8b13667
Descripción
Sumario:[Image: see text] Targeted modification of electronic structure is an important step in the optimization of metal–organic frameworks (MOFs) for photovoltaic, sensing, and photocatalytic applications. The key parameters to be controlled include the band gap, the absolute energy position of band edges, the excited state charge separation, and degree of hybridization between metal and ligand sites. Partial metal replacement, or metal doping, within secondary building units is a promising, yet relatively unexplored route to modulate these properties in MOFs. Therefore, in the present study, a general method for selecting metal dopant is worked out in theory and validated by experiment, retaining MIL-125 and UiO-66 as the model systems. Metal mixing enables targeted optimization of key electronic structure parameters. This method is applicable to any MOF architecture and can serve as a roadmap for future synthesis of MOFs with predefined properties.