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  • Solvent-Mediated Reconstruc...
    Majano, Gerardo; Martin, Oliver; Hammes, Markus; Smeets, Stef; Baerlocher, Christian; Pérez-Ramírez, Javier

    Advanced functional materials, July 2, 2014, Letnik: 24, Številka: 25
    Journal Article

    The principle of integral metal–organic framework (MOF) reconstruction is demonstrated for differently degraded HKUST‐1 via a facile, one‐step, solvent‐assisted treatment. Controlled MOF degradation by exposure to 77% humidity, liquid water, and diluted hydrochloric acid produces a mixture of non‐porous crystalline hybrid materials containing protonated linker and copper‐oxo species, which are then reconstructed back into high‐quality HKUST‐1 by contacting them with ethanol. X‐ray diffraction and sorption kinetics reveal a true memory effect of the system from completely degraded materials. The reconstruction approach is consequently extrapolated to gas‐ and liquid‐phase treatments in a fixed‐bed reactor with ethanol and ethanol/water mixtures for use in CO2 capture from a simulated pre‐combustion gas stream. Up to a maximum of 94% porosity and 85% CO2 sorption capacity can be recovered from a steamed material. A degradation‐reconstruction model is put forward based on X‐ray diffraction observations and structural analyses, microscopy, N2 sorption, thermogravitry–mass spectrometry and IR spectroscopy observations, particularly elucidating the influence of various degradation pathways on the reconstruction. Reconstruction of water‐degraded HKUST‐1 back into the original material is demonstrated through solvent‐assisted liquid‐ and gas‐phase treatments. Up to 94% poro­sity and 85% CO2 sorption capacity could be recovered from a completely collapsed metal–organic framework. The degradation routes affect the physicochemical features and the kinetics of reconstruction. This method opens promising directions for the large‐scale application of these materials.