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

Syzgantseva, Maria A.; Ireland, Christopher Patrick; Ebrahim, Fatmah Mish; Smit, Berend; Syzgantseva, Olga A.

doi:10.1021/jacs.8b13667

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

Journal Article · Wed Mar 27 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b13667· OSTI ID:1591808

Syzgantseva, Maria A. ^[1]; Ireland, Christopher Patrick ^[2]; Ebrahim, Fatmah Mish ^[2]; ^[2]; ^[2]

Moscow State Univ. M.V. Lomonosov, (Russia)
Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Sion (Switzerland)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: European Research Council (ERC); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1591808

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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