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Solvent‐Mediated Reconstruction of the Metal–Organic Framework HKUST‐1 (Cu 3 (BTC) 2 )
Author(s) -
Majano Gerardo,
Martin Oliver,
Hammes Markus,
Smeets Stef,
Baerlocher Christian,
PérezRamírez Javier
Publication year - 2014
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.201303678
Subject(s) - sorption , metal organic framework , materials science , porosity , hydrochloric acid , chemical engineering , degradation (telecommunications) , solvent , diffraction , relative humidity , fourier transform infrared spectroscopy , organic chemistry , adsorption , composite material , chemistry , metallurgy , thermodynamics , telecommunications , physics , optics , computer science , engineering
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 CO 2 capture from a simulated pre‐combustion gas stream. Up to a maximum of 94% porosity and 85% CO 2 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, N 2 sorption, thermogravitry–mass spectrometry and IR spectroscopy observations, particularly elucidating the influence of various degradation pathways on the reconstruction.