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Enhancing hydrogen storage by metal substitution in MIL-88A metal-organic framework

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Abstract

MIL-88A metal-organic framework with the unsaturated Fe metal coordination sites has demonstrated to be a promising material for gas storage and capture. However, the hydrogen storage capacity of MIL-88A has to be improved to meet the practical level at the ambient conditions. In this research, we elucidated the effects of transition metal substitution on the hydrogen storage capability of MIL-88A. The trivalent transition metals including Sc, Ti, V, Cr, Mn, and Ni have been selected to substitute for Fe in MIL-88A. Using the van der Waals dispersion-corrected density functional theory calculations, we explored the most favorable adsorption configurations of the hydrogen molecule in M-MIL-88A (M = Sc, Ti, V, Cr, Mn, Ni). We found that the V-MIL-88A has the strongest binding energy of 17 kJ mol−1 with the hydrogen molecule in the side-on configuration on the metal site. Besides, the grand canonical Monte Carlo simulations showed that the metal substitution greatly influences not only the favorable adsorption configuration and energy but also the hydrogen uptake due to the modification of the H2@MIL-88A interaction. Sc-MIL-88A was found to offer the highest gravimetric H2 uptake compared to the other M-MIL-88A. The value is 5.13 wt% at (cryogenic temperature 77 K, 50 bar) and 0.72 wt% at (room temperature 298 K, 100 bar) for the absolute; 4.63 wt% at (77 K, 10 bar) and 0.29 wt% at (298 K, 100 bar) for the excess capacity. Furthermore, Sc-MIL-88A also exhibited the highest volumetric uptake up to 52 g L−1 at 77 K and 7.1 g L−1 at 298 K for the absolute; 46 g L−1 at 77 K and 2.8 g L−1 at 298 K for the excess loading.

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Acknowledgments

This research was funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) under Grant Number 103.01-2017.04. We acknowledge the usage of the computer time and software granted by the Institute of Physical Chemistry of Romanian Academy, Bucharest (HPC infrastructure developed under the projects Capacities 84 Cp/I of 15.09.2007 and INFRANANOCHEM 19/01.03.2009).

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Authors and Affiliations

  1. Ho Chi Minh City University of Technology (HCMUT), Ho Chi Minh City, Vietnam

    Nguyen Thi Xuan Huynh & Do Ngoc Son

  2. Vietnam National University, Ho Chi Minh City, Vietnam

    Nguyen Thi Xuan Huynh & Do Ngoc Son

  3. Quy Nhon University, 170 An Duong Vuong, Quy Nhon City, Binh Dinh, Vietnam

    Nguyen Thi Xuan Huynh

  4. Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy, Splaiul Independentei 202, Sector 6, Bucharest, Romania, 060021

    Viorel Chihaia

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  1. Nguyen Thi Xuan Huynh
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Huynh, N.T.X., Chihaia, V. & Son, D.N. Enhancing hydrogen storage by metal substitution in MIL-88A metal-organic framework. Adsorption 26, 509–519 (2020). https://doi.org/10.1007/s10450-020-00213-8

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