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

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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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.

Author information

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.

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

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Supplementary Information

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

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Further reading

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.