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

Nature Energyvolume 3pages985993 (2018) | Download Citation


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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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 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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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.

Author information

Author notes

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


  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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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.

Competing interests

The authors declare no competing interests.

Corresponding authors

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

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  1. Supplementary Information

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

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