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A Combined Theoretical and Experimental Characterization of a Zirconium MOF with Potential Application to Supercapacitors

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Abstract

Among the many exciting potential applications for metal − organic frameworks (MOFs) is their use in electrodes for energy storage. Towards this goal, there have been many studies to evaluate MOFs in supercapacitors, including the work by Choi et al. (ACS Nano 8:7451, 2014. https://doi.org/10.1021/nn5027092) who evaluated a series of 23 porous MOFs. Here we present results from the synthesis and characterization of the Zr-MOF they identified as most promising, nMOF-867, Zr6O4(OH)4(BPYDC)6 (BPYDC = 2,2´-bipyridine-5,5·-dicarboxylate). Gas sorption measurements, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry were used to characterize our materials and results are compared to those in the literature. In addition, we used solid-state nuclear magnetic resonance (NMR) to determine the local structure of this material. Comparisons were made between the observed 13C NMR chemical shifts for the pure linker, BPYDC, the final Zr-MOF, and density function theory (DFT) calculations. Ultimately, while we found that the electrochemical performance of the materials prepared in this study was poor, possibly due to their low surface area and instability, we confirmed the applicability of solid-state NMR to characterize the local structure of these and similar materials as we move further towards full in situ studies of MOF-based electrodes.

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The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

Support for this research comes from the Office of Naval Research (ONR) through the base program NRL core funding.

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  1. Chemistry Division, U.S. Naval Research Laboratory, Washington, DC, USA

    Carlos M. Hangarter, Matthew Laskoski, Mark C. Palenik, Joel B. Miller & Christopher A. Klug

  2. Science & Technology Associates, Inc, Arlington, VA, USA

    Boris Dyatkin

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Hangarter, C.M., Dyatkin, B., Laskoski, M. et al. A Combined Theoretical and Experimental Characterization of a Zirconium MOF with Potential Application to Supercapacitors. Appl Magn Reson 53, 915–930 (2022). https://doi.org/10.1007/s00723-022-01471-1

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