Tunable Mixed-Valence Doping toward Record Electrical Conductivity in a Three-Dimensional Metal-Organic Framework.

Autor: Xie LS; Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States., Sun L; Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States., Wan R; Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States., Park SS; Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States., DeGayner JA; Department of Chemistry , Northwestern University , Evanston , Illinois 60208 , United States., Hendon CH; Materials Science Institute, Department of Chemistry and Biochemistry , University of Oregon , Eugene , Oregon 97403 , United States., Dincă M; Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , Massachusetts 02139 , United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2018 Jun 20; Vol. 140 (24), pp. 7411-7414. Date of Electronic Publication: 2018 Jun 06.
DOI: 10.1021/jacs.8b03604
Abstrakt: Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe 2+ and Fe 3+ centers. These findings are consistent with low-lying Fe 3+ defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs.
Databáze: MEDLINE
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