Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework

Abstract

Metal–organic frameworks (MOFs)—microporous materials constructed by bridging metal centres with organic ligands—show promise for applications in hydrogen storage, which is a key challenge in the development of the ‘hydrogen economy’. Their adsorption capacities, however, have remained insufficient for practical applications, and thus strategies to enhance hydrogen–MOF interactions are required. Here we describe an anionic MOF material built from In(iii) centres and tetracarboxylic acid ligands (H4L) in which kinetic trapping behaviour—where hydrogen is adsorbed at high pressures but not released immediately on lowering the pressure—is modulated by guest cations. With piperazinium dications in its pores, the framework exhibits hysteretic hydrogen adsorption. On exchange of these dications with lithium cations, no hysteresis is seen, but instead there is an enhanced adsorption capacity coupled to an increase in the isosteric heat of adsorption. This is rationalized by the different locations of the cations within the pores, determined with precision by X-ray crystallography.

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Figure 1: Views of single crystal X-ray structures of triporous units of 1-ppz-solv and 1-Li-solv, and in situ infrared spectra of 1-Li-solv.
Figure 2: Views of framework structures of 1-ppz-solv and 1-Li-solv.
Figure 3: Gas adsorption isotherms of 1-ppz and 1-Li.
Figure 4: H2 adsorption kinetic profiles and Arrhenius plots for H2 uptake in 1-ppz.

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Acknowledgements

We thank the EPSRC and the University of Nottingham for support and funding, and the EPSRC-funded National Crystallography Services at the University of Southampton for data collection. We thank J. Burley for PXRD data collection, T. Liu for the help on ICPMAS measurements, and T. Price for infrared spectra. We also thank T. Düren for the assistance and advice on simulation of BET surface areas. M.S. acknowledges receipt of a Royal Society Wolfson Merit Award and an ERC Advanced Grant, and S.Y. thanks Shell-EPSRC for a DHPA scholarship.

Author information

S.Y. carried out syntheses, characterization, measurements and analysis of adsorption isotherms. X.L. and G.S.W. performed IR measurements and analysis of adsorption results. A.J.B. performed X-ray structural data analysis. P.H., N.R.C. and M.S. were responsible for overall design, direction and supervision of project. All authors co-wrote the paper.

Correspondence to Neil R. Champness or Martin Schröder.

Supplementary information

Supplementary information

Supplementary information (PDF 1662 kb)

Supplementary information

Crystallographic information for framework containing piperazinium ions (called 1-ppz-solv) (CIF 18 kb)

Supplementary information

Crystallographic information for framework containing lithium ions (called 1-Li-solv) (CIF 19 kb)

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Yang, S., Lin, X., Blake, A. et al. Cation-induced kinetic trapping and enhanced hydrogen adsorption in a modulated anionic metal–organic framework. Nature Chem 1, 487–493 (2009). https://doi.org/10.1038/nchem.333

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