Electronic Properties of Bimetallic Metal-Organic Frameworks (MOFs): Tailoring the Density of Electronic States through MOF Modularity

Bryon Larson, Obadiah Reid, Ekaterina Dolgopolova, Amy Brandt, Otega Ejegbavwo, Audrey Duke, Thathsara Maddumapatabandi, Randima Galhenage, Salai Ammal, Andreas Heyden, Mvs Chandrashekhar, Vitalie Stavila, Donna Chen, Natalia Shustova

Research output: Contribution to journalArticlepeer-review

174 Scopus Citations

Abstract

The development of porous well-defined hybrid materials (e.g., metal-organic frameworks or MOFs) will add a new dimension to a wide number of applications ranging from supercapacitors and electrodes to "smart" membranes and thermoelectrics. From this perspective, the understanding and tailoring of the electronic properties of MOFs are key fundamental challenges that could unlock the full potential of these materials. In this work, we focused on the fundamental insights responsible for the electronic properties of three distinct classes of bimetallic systems, M x-y M′ y -MOFs, M x M′ y -MOFs, and M x (ligand-M′ y )-MOFs, in which the second metal (M′) incorporation occurs through (i) metal (M) replacement in the framework nodes (type I), (ii) metal node extension (type II), and (iii) metal coordination to the organic ligand (type III), respectively. We employed microwave conductivity, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, pressed-pellet conductivity, and theoretical modeling to shed light on the key factors responsible for the tunability of MOF electronic structures. Experimental prescreening of MOFs was performed based on changes in the density of electronic states near the Fermi edge, which was used as a starting point for further selection of suitable MOFs. As a result, we demonstrated that the tailoring of MOF electronic properties could be performed as a function of metal node engineering, framework topology, and/or the presence of unsaturated metal sites while preserving framework porosity and structural integrity. These studies unveil the possible pathways for transforming the electronic properties of MOFs from insulating to semiconducting, as well as provide a blueprint for the development of hybrid porous materials with desirable electronic structures.

Original languageAmerican English
Pages (from-to)5201-5209
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number14
DOIs
StatePublished - 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

  • NREL/JA-5900-68210

Keywords

  • bimetallic systems
  • electronic states
  • MOF electronic structures

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