Abstract
The storage of hydrogen is key to its applications. Developing adsorbent materials with high volumetric and gravimetric storage capacities, both of which are essential for the efficient use of hydrogen as a fuel, is challenging. Here we report a controlled catenation strategy in hydrogen-bonded organic frameworks (RP-H100 and RP-H101) that depends on multiple hydrogen bonds to guide catenation in a point-contact manner, resulting in high volumetric and gravimetric surface areas, robustness and ideal pore diameters (~1.2–1.9 nm) for hydrogen storage. This approach involves assembling nine imidazole-annulated triptycene hexaacids into a secondary hexagonal superstructure containing three open channels through which seven of the hexagons interpenetrate to form a seven-fold catenated superstructure. RP-H101 exhibits high deliverable volumetric (53.7 g l−1) and gravimetric (9.3 wt%) capacities for hydrogen under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar). This work illustrates the virtues of supramolecular crystals as promising candidates for hydrogen storage.
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Data availability
Data supporting the findings of this investigation are available from the paper and its Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition nos. CCDC 2298776 (RP-H100) and 2298777 (RP-H101). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.
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Acknowledgements
We acknowledge D. Kiska (Anton Paar), O. M. Yaghi and Z. Zheng (UC Berkeley), as well as Z. Lin, H. Xie and K. B. Idrees (Northwestern University), for experimental help and discussions. We also acknowledge support in carrying out the high-pressure characterization of RP-H101 by W. Wang, L. Long, Y.-B. Zhang and the Analytical Instrumentation Center (SPST-AIC10112914) at ShanghaiTech University. We thank Northwestern University (NU), the University of Hong Kong and H2MOF, Inc. for their financial support, and acknowledge the Integrated Molecular Structure Education and Research Centre at NU for providing access to equipment for relevant experiments. We acknowledge support from the US Department of Energy’s Office of Energy Efficiency and Renewable Energy under grant no. DE-EE0008816 (R.Q.S.). We also gratefully acknowledge the resources provided by the National Energy Research Scientific Computing Centre (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under contract no. DE-AC02-05CH11231 using NERSC award BES-ERCAP0023154 (R.Q.S.). H.D. is supported by the Scientific and Technological Research Council of Turkey (TUBITAK) 2214-A (decision no. 1059B142200109).
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Authors and Affiliations
Contributions
R.Z., C.T. and J.F.S. conceived the idea for this project. H.D. and R.Q.S. performed Monte Carlo and DFT calculations. R.Z. and C.T. synthesized and characterized the materials with the help of P.L., L.F., H.H., G.W., B.N.L., Y.W., S.Y. and A.X.-Y.C. C.L.S. performed the single-crystal X-ray diffraction. C.D.M. helped with the variable-temperature X-ray diffraction and thermal gravimetric analysis. R.Z., C.T. and J.F.S. wrote multiple drafts of the paper. J.F.S. directed the project. All authors participated in evaluating the results and commented on the paper.
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B.N.L. is an employee of H2MOF, Inc. Additionally, R.Z. and J.F.S. are inventors on a patent application related to this work filed by Northwestern University (US provisional patent application no. 63/673,595, filed 19 July 2024). The other authors declare no competing interests.
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Extended data
Extended Data Fig. 1 Structure analysis of hexagonal modules in RP-H101.
a, The crystal superstructure of RP-H101 shows that seven 6.4-nm hexagonal motifs denoted in different colours are interpenetrated with each other. After interpenetration, every 6.4-nm hexagonal motif forms seven smaller hexagonal modules. b, c, The top-view and side-view of how the small hexagonal module is assembled. The small hexagonal module shows a three-layer structure and a pore diameter of 1.8 nm, assembled with nine IATH-2 molecules. d, e, Based on the top view and side view of a small hexagonal module, there are 12 [N−H···O] and 12 [O−H···N] hydrogen bonds between these nine IATH-2 molecules, which direct the interpenetration and the formation of the highly catenated structure.
Extended Data Fig. 2 Structure analysis of triangular modules in RP-H101.
a, The crystal superstructure of RP-H101 shows the interpenetration of 6.4-nm hexagonal motifs denoted in different colours. After interpenetration, every 6.4-nm hexagonal motif forms 12 triangular modules. b, c, The top-view and side-view of how the triangular module is assembled. Each triangular module shows a three-layer structure assembled with five IATH-2 molecules. d, Each triangular module has a triangular prism-shaped pore, with a pore diameter of 1.5 nm. e, From the side-view of the triangular module, there are six [N−H···O] and six [O−H···N] hydrogen bonds between these 5 IATH-2 molecules, directing the formation of the highly catenated structure.
Supplementary information
Supplementary Information
Supplementary Figs. 1–40, Discussion and Tables 1–10.
Supplementary Table 11
Atomic positions of RP-H100 (ND-I).
Supplementary Table 12
Atomic positions of RP-H100 (ND-II).
Supplementary Data 1
Crystallographic data for RP-H100; CCDC number 2298776.
Supplementary Data 2
Crystallographic data for RP-H101; CCDC number 2298777.
Source data
Source Data Fig. 3
The data include PXRD patterns for as-synthesized, activated, and after-adsorption RP-H101 shown in Fig. 3a, PXRD patterns for RP-H101 after soaking in different solvents for 24 h depicted in Fig. 3b, variable-temperature PXRD patterns for RP-H101 presented in Fig. 3c, and thermogravimetric profiles for the as-synthesized and activated RP-H101 illustrated in Fig. 3d.
Source Data Fig. 4
The data include experimental and simulated N2 adsorption isotherms for RP-H100 and RP-H101 as depicted in Fig. 4a, pore-size distribution and pore volume data for RP-H101 presented in Fig. 4b, data demonstrating the trade-off between thermal stability and GSAs for all HOFs with GSAs higher than 1500 m2 g−1 shown in Fig. 4c, and data illustrating the trade-off between GSAs and VSAs for HOFs displayed in Fig. 4d.
Source Data Fig. 5
The data include experimental and simulated gravimetric total uptake of H2 in RP-H100 and RP-H101 as shown in Fig. 5a,b, volumetric total uptake of H2 in RP-H100 and RP-H101 depicted in Fig. 5c, and data illustrating the trade-off between gravimetric and volumetric deliverable capacities of H2 in RP-H100, RP-H101 and other MOFs presented in Fig. 5d.
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Zhang, R., Daglar, H., Tang, C. et al. Balancing volumetric and gravimetric capacity for hydrogen in supramolecular crystals. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01622-w
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DOI: https://doi.org/10.1038/s41557-024-01622-w
