TY - JOUR
T1 - Metal Organic Framework Crystals in Mixed-Matrix Membranes
T2 - Impact of the Filler Morphology on the Gas Separation Performance
AU - Sabetghadam, Anahid
AU - Seoane, Beatriz
AU - Keskin, Damla
AU - Duim, Nicole
AU - Rodenas, Tania
AU - Shahid, Salman
AU - Sorribas, Sara
AU - Guillouzer, Clément Le
AU - Clet, Guillaume
AU - Tellez, Carlos
AU - Daturi, Marco
AU - Coronas, Joaquin
AU - Kapteijn, Freek
AU - Gascon, Jorge
N1 - Funding Information:
A.S. and D.K. contributed equally to this work. The authors acknowledge the financial support of the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013), M4CO2 project and ERC Grant Agreement no. 335746, CrystEng-MOF-MMM, and the Laboratorio de Microscopías Avanzadas at the Instituto de Nanociencia de Aragón for offering access to their instruments and expertise.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/5/10
Y1 - 2016/5/10
N2 - Mixed-matrix membranes comprising NH2-MIL-53(Al) and Matrimid or 6FDA-DAM have been investigated. The metal organic framework (MOF) loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies, nanoparticles, nanorods, and microneedles has been dispersed in Matrimid. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e., NH2-MIL-53(Al) nanoparticles, into the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increases up to 85% with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with a CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modeling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by focused ion beam scanning electron microscopy analysis.
AB - Mixed-matrix membranes comprising NH2-MIL-53(Al) and Matrimid or 6FDA-DAM have been investigated. The metal organic framework (MOF) loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies, nanoparticles, nanorods, and microneedles has been dispersed in Matrimid. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e., NH2-MIL-53(Al) nanoparticles, into the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increases up to 85% with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with a CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modeling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by focused ion beam scanning electron microscopy analysis.
KW - NH-MIL-53(Al)
KW - gas separation
KW - metal-organic frameworks
KW - mixed-matrix membranes
KW - natural gas and biogas upgrading
UR - http://www.scopus.com/inward/record.url?scp=84967261228&partnerID=8YFLogxK
U2 - 10.1002/adfm.201505352
DO - 10.1002/adfm.201505352
M3 - Article
C2 - 29200991
AN - SCOPUS:84967261228
SN - 1616-301X
VL - 26
SP - 3154
EP - 3163
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 18
ER -