Is iron unique in promoting electrical conductivity in MOFs?

Lei Sun, Christopher H. Hendon, Sarah S. Park, Yuri Tulchinsky, Ruomeng Wan, Fang Wang, Aron Walsh, Mircea Dincǎ

Research output: Contribution to journalArticlepeer-review

186 Scopus citations

Abstract

Identifying the metal ions that optimize charge transport and charge density in metal-organic frameworks is critical for systematic improvements in the electrical conductivity in these materials. In this work, we measure the electrical conductivity and activation energy for twenty different MOFs pertaining to four distinct structural families: M2(DOBDC)(DMF)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+); H4DOBDC = 2,5-dihydroxybenzene-1,4-dicarboxylic acid; DMF = N,N-dimethylformamide), M2(DSBDC)(DMF)2 (M = Mn2+, Fe2+; H4DSBDC = 2,5-disulfhydrylbenzene-1,4-dicarboxylic acid), M2Cl2(BTDD)(DMF)2 (M = Mn2+, Fe2+, Co2+, Ni2+; H2BTDD = bis(1H-1,2,3-Triazolo[4,5-b],[4′,5′-i]dibenzo[1,4]dioxin), and M(1,2,3-Triazolate)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Cu2+, Zn2+, Cd2+). This comprehensive study allows us to single-out iron as the metal ion that leads to the best electrical properties. The iron-based MOFs exhibit at least five orders of magnitude higher electrical conductivity and significantly smaller charge activation energies across all different MOF families studied here and stand out materials made from all other metal ions considered here. We attribute the unique electrical properties of iron-based MOFs to the high-energy valence electrons of Fe2+ and the Fe3+/2+ mixed valency. These results reveal that incorporating Fe2+ in the charge transport pathways of MOFs and introducing mixed valency are valuable strategies for improving electrical conductivity in this important class of porous materials.

Original languageEnglish
Pages (from-to)4450-4457
Number of pages8
JournalChemical Science
Volume8
Issue number6
DOIs
StatePublished - 2017

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2017.

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