Ambient-Temperature Hydrogen Storage via Vanadium(II)-Dihydrogen Complexation in a Metal−Organic Framework

Published

April 28, 2021

Author(s)

David Jaramillo, Henry Jiang, Hayden Evans, Romit Chakraborty, Hiroyasu Furukawa, Craig Brown, Martin Head-Gordon, Jeffrey Long

Abstract

The widespread implementation of H₂ as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of −15 to −25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal–organic framework (MOF) V₂Cl_2.8(btdd) (H₂btdd, bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak π acids. Significantly, gas adsorption data reveal that this material binds H₂ with an enthalpy of −21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)–dihydrogen complexation is characterized by a combination of techniques. From powder neutron diffraction data, a V–D₂(centroid) distance of 1.966(8) Å is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the vibration of the vanadium-bound H₂ is identified, and it displays a red shift of 242 cm⁻¹ relative to free H₂. Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium dπ and H₂ σ* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly π-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.

Citation

Journal of the American Chemical Society

Volume

143

Issue

16

Pub Type

Journals

Download Paper

https://doi.org/10.1021/jacs.1c01883

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Keywords

MOF, hydrogen storage

Citation

Jaramillo, D. , Jiang, H. , Evans, H. , Chakraborty, R. , Furukawa, H. , Brown, C. , Head-Gordon, M. and Long, J. (2021), Ambient-Temperature Hydrogen Storage via Vanadium(II)-Dihydrogen Complexation in a Metal−Organic Framework, Journal of the American Chemical Society, [online], https://doi.org/10.1021/jacs.1c01883, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=932355 (Accessed May 4, 2024)