Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites

Abstract

Selective dinitrogen binding to transition metal ions mainly covers two strategic domains: biological nitrogen fixation catalysed by metalloenzyme nitrogenases1,2,3, and adsorptive purification of natural gas and air4,5,6. Many transition metal–dinitrogen complexes have been envisaged for biomimetic nitrogen fixation to produce ammonia3. Inspired by this concept, here we report mesoporous metal–organic framework materials containing accessible Cr(III) sites, able to thermodynamically capture N2 over CH4 and O2. This fundamental study integrating advanced experimental and computational tools confirmed that the separation mechanism for both N2/CH4 and N2/O2 gas mixtures is driven by the presence of these unsaturated Cr(III) sites that allows a much stronger binding of N2 over the two other gases. Besides the potential breakthrough in adsorption-based technologies, this proof of concept could open new horizons to address several challenges in chemistry, including the design of heterogeneous biomimetic catalysts through nitrogen fixation.

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Figure 1: Structure of MIL-100(Cr), in situ IR spectra, and gas adsorption isotherms.
Figure 2: Interactions between the accessible Cr(III) sites and the guests.
Figure 3: Adsorptive separation for a binary N2/CH4 mixture.
Figure 4: Adsorptive separation for a binary N2/O2 mixture.

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Acknowledgements

We would like to acknowledge the financial support from the R&D Convergence Program (CRC-14-1-KRICT) of MSIP (Ministry of Science, ICT and Future Planning) and NST (National Research Council of Science & Technology) of Republic of Korea. KRICT authors thank the Global Frontier Center for Hybrid Interface Materials (GFHIM) for its financial support (Grant No. NRF-2013M3A6B1078879). M.D., G.M. and C.S. thank CNRS (Centre National de la Recherche Scientifique) for its financial support. RGN members acknowledge the financial support through the DRC Program (SKM-1503) funded by NST (National Research Council of Science & Technology) of Korea. G.M. thanks Institut Universitaire de France for its support. Y.J. acknowledges the support from the National Research Foundation of Korea funded by the Korean Government (NRF-2016M3D1A1021147). We thank CCME members for their contributions to the synthesis and characterization of MIL-100(M) samples. J.-S.C. also thanks Y.-U. Kwon (SKKU) for his comment on artificial N2 fixation.

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J.-S.C. designed the study, analysed data and wrote the paper. J.W.Y. and D.-Y.H. performed IR investigations and breakthrough experiments besides the collection of sorption data. F.F., A.V. and M.D. supervised the in situ and operando IR and UV–vis investigations. Y.K.H., S.-K.L. and J.S.L. performed the synthesis of MIL-100(M) materials and their characterizations. Y.-S.B. contributed to the design of this work and to the paper writing. S.-J.L. and T.-U.Y. collected sorption data and performed simulations of breakthrough gas separation. G.M., R.S.P., H.C., S.J., K.K. and Y.J. performed molecular simulations, and G.M. wrote the paper. C.S. and G.F. contributed to the study and the paper writing. All authors discussed the results and commented on the manuscript.

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Correspondence to Guillaume Maurin or Youn-Sang Bae or Jong-San Chang.

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The authors declare no competing financial interests.

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Yoon, J., Chang, H., Lee, SJ. et al. Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites. Nature Mater 16, 526–531 (2017). https://doi.org/10.1038/nmat4825

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