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A robust large-pore zirconium carboxylate metal–organic framework for energy-efficient water-sorption-driven refrigeration

Nature Energy volume 3, pages 985–993 (2018)Cite this article

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Abstract

The discovery of more-efficient and stable water adsorbents for adsorption-driven chillers for cooling applications remains a challenge due to the low working capacity of water sorption, high regeneration temperature, low energy efficiency under given operating conditions and the toxicity risk of harmful working fluids for the state-of-the-art sorbents. Here we report the water-sorption properties of a porous zirconium carboxylate metal–organic framework, MIP-200, which features S-shaped sorption isotherms, a high water uptake of 0.39 g g−1 below P/P0 = 0.25, facile regeneration and stable cycling, and most importantly a notably high coefficient of performance of 0.78 for refrigeration at a low driving temperature (below 70 °C). A joint computational–experimental approach supports that MIP-200 may be a practical alternative to the current commercially available adsorbents for refrigeration when its water adsorption performance is combined with advantages such as the exceptional chemical and mechanical stability and the scalable synthesis that involves simple, cheap and green chemicals.

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Fig. 1: Crystal structure of MIP-200.
Fig. 2: Water-sorption performance of MIP-200 in comparison with other adsorbents.
Fig. 3: Simulation result of water adsorption process.
Fig. 4: Chemical stability of MIP-200 under various conditions.
Fig. 5: Mechanical resistance of MIP-200.

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Data availability

The X-ray crystallographic data for MIP-200 have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition number CCDC 1834834. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk. Further data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

S.W., G.M. and C.S. acknowledge the financial support of the European Community within the Seventh Framework Programme (FP7) under grant agreement no. 608490 (Project M4CO2). C.M.-C. and G.M. are grateful for financial support from Institut Universitaire de France (IUF). The Korean authors are grateful to the Global Frontier Center for Hybrid Interface Materials of Korea (GFHIM) (grant no. NRF-2013M3A6B1078879) and the National Research Council of Science & Technology (NST) of Korea (the R&D Convergence Program, Center for Convergent Chemical Process (CCP), CRC-14-1-KRICT) for financial support. E. Gkaniatsou and L. Zhou from the Institute of Porous Materials from Paris, and A. Orsi and P. Wright from the University of St Andrews are acknowledged for providing the MOF samples for the chemical stability tests under NH4OH vapour. J. W. Yoon, Y. K. Hwang, U-H. Lee and H. Wang are also acknowledged for their fruitful comments on adsorption and characterization experiments.

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Author notes

  1. These authors contributed equally: Sujing Wang, Ji Sun Lee, Mohammad Wahiduzzaman

Authors and Affiliations

  1. Institut des Matériaux Poreux de Paris, FRE 2000 CNRS, Ecole Normale Supérieure, Ecole Supérieure de Physique et de Chimie Industrielles de Paris, PSL Université, Paris, France

    Sujing Wang, Mégane Muschi, Antoine Tissot & Christian Serre

  2. Research Group for Nanocatalyst and Chemical Safety Research Center, Korea Research Institute of Chemical Technology (KRICT) , Daejeon, South Korea

    Ji Sun Lee, Jaedeuk Park, Kyung Ho Cho & Jong-San Chang

  3. Institut Charles Gerhardt, Montpellier UMR 5253 CNRS ENSCM UM, Université Montpellier, Montpellier , France

    Mohammad Wahiduzzaman & Guillaume Maurin

  4. Institut Lavoisier de Versailles, UMR 8180 CNRS, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris-Saclay, Versailles, France

    Charlotte Martineau-Corcos & Jérôme Marrot

  5. CEMHTI, UPR 3079 CNRS, Orléans , France

    Charlotte Martineau-Corcos

  6. Synchrotron SOLEIL-UR1, Gif-Sur-Yvette, France

    William Shepard

  7. Department of Chemistry, Sungkyunkwan University, Suwon, South Korea

    Jong-San Chang

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  1. Sujing Wang
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Contributions

S.W. contributed to the synthesis and general characterization of MIP-200 and contributed to the writing of the manuscript. M.W. performed the computational assisted structure determination of MIL-200, the calculation of the electronic energy for a series of Zr-based MOFs, the simulation of the water adsorption isotherms and the analysis of the mechanism in play, and he equally contributed to the writing of the manuscript. M.M. contributed to the characterization data collection and writing of the manuscript. A.T., J.M. and W.S. collected the synchrotron diffraction data on the single crystal and solved the crystal structure. C.M.-C. conducted the solid-state NMR characterizations. J.S.L. and K.H.C. collected water-sorption data. J.P. calculated the thermodynamic efficiency of MIP-200 for water sorption. J.-S.C. designed the study on water sorption, analysed data and led the writing of the manuscript. G.M. supervised the modelling part of this study and led the writing of the manuscript. C.S. coordinated the study and led the writing of the manuscript, and also closely supervised the synthesis and characterization part of the work.

Corresponding authors

Correspondence to Guillaume Maurin, Jong-San Chang or Christian Serre.

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Supplementary figures 1–40, Supplementary tables 1–5, Supplementary notes 1–3, Supplementary methods, Supplementary references

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Wang, S., Lee, J.S., Wahiduzzaman, M. et al. A robust large-pore zirconium carboxylate metal–organic framework for energy-efficient water-sorption-driven refrigeration. Nat Energy 3, 985–993 (2018). https://doi.org/10.1038/s41560-018-0261-6

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