Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation

Kentaro Kadota; Nghia Tuan Duong; Yusuke Nishiyama; Easan Sivaniah; Susumu Kitagawa; Satoshi Horike

doi:10.1039/C9SC00731H

Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation†

Kentaro Kadota,^a Nghia Tuan Duong,

^b Yusuke Nishiyama,

^bc Easan Sivaniah,

^ad Susumu Kitagawa^d and Satoshi Horike

*^defg

Author affiliations

* Corresponding authors

^a Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

^b RIKEN-JEOL Collaboration Center, Tsurumi, Yokohama, Kanagawa 230-0045, Japan

^c JEOL RESONANCE Inc., Musashino, Akishima, Tokyo 196-8558, Japan

^d Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
E-mail: horike@icems.kyoto-u.ac.jp

^e AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory (ChEM-OIL), National Institute of Advanced Industrial Science and Technology (AIST), Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501, Japan

^f Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

^g Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand

Abstract

Control of the reactivity of hydride (H⁻) in crystal structures has been a challenge because of its strong electron-donating ability and reactivity with protic species. For metal borohydrides, the dehydrogenation activity and air stability are in a trade-off, and control of the reactivity of BH₄⁻ has been demanded. For this purpose, we synthesize a series of BH₄⁻-based coordination polymers/metal–organic frameworks. The reactivity of BH₄⁻ in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH₄)₂(dipyridylpropane)] exhibits both high dehydrogenation reactivity (1.4 wt% at 179 °C) and high air stability (50 RH% at 25 °C, 7 days). Single crystal X-ray diffraction analysis reveals that H^δ+⋯H^δ− dihydrogen interactions and close packing of hydrophobic ligands are the key for the reactivity and stability. The dehydrogenation mechanism is investigated by temperature-programmed desorption, in situ synchrotron PXRD and solid-state NMR.

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DOI: https://doi.org/10.1039/C9SC00731H
Article type: Edge Article
Submitted: 12 Feb 2019
Accepted: 11 May 2019
First published: 13 May 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2019,10, 6193-6198

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Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation

K. Kadota, N. T. Duong, Y. Nishiyama, E. Sivaniah, S. Kitagawa and S. Horike, Chem. Sci., 2019, 10, 6193 DOI: 10.1039/C9SC00731H

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Chemical Science

Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation†

Abstract

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Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation

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