TY - JOUR
T1 - Metal-Organic Frameworks with a Bioinspired Porous Polymer Coating for Sieving Separation
AU - Su, Shengyi
AU - Zhou, Xuhao
AU - Gong, Xinyi
AU - Idrees, Karam B.
AU - Kirlikovali, Kent O.
AU - Islamoglu, Timur
AU - Farha, Omar K.
AU - Gianneschi, Nathan C.
N1 - Funding Information:
This study was supported by a MURI through the Air Force Office of Scientific Research (FA 9550-18-1-0142). N.C.G. acknowledges the Army Research Office for support of the development of TEM for MOFs (W911NF-15-1-0189) and the Department of Energy (DOE) Basic Energy Science (BES) Office for stability study (DE-SC0022332). O.K.F. is grateful for the financial support from the Army Research Office (W911NF1910340) for synthesis of MOFs and U.S. Department of Energy (DOE) Office of Science, Basic Energy Sciences Program for separation studies (DE-FG02-08ER15967). K.O.K. gratefully acknowledges support from the IIN Postdoctoral Fellowship and the Northwestern University International Institute for Nanotechnology. The work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (ShyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute of Nanotechnology (IIN).
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/6/21
Y1 - 2023/6/21
N2 - Polymer/metal-organic framework (MOF) composites have been widely studied for their favorable combination of polymer flexibility and MOF crystallinity. While traditional polymer-coated MOFs maximize the polymer properties at the surface, the dramatic loss of MOF porosity due to blockage by the nonporous polymeric coating remains a problem. Herein, we introduce intrinsically microporous synthetic allomelanin (AM) as a porous coating on the zirconium-based MOF (Zr-MOF) UiO-66 via an in situ surface-constrained oxidative polymerization of the AM precursor, 1,8-dihydroxynaphthalene (1,8-DHN). Transmission electron microscopy images verify the formation of well-defined nanoparticles with a core-shell morphology (AM@UiO-66), and nitrogen sorption isotherms indicate the porosity of the UiO-66 core remains constant and is not disturbed by the AM coating. Notably, such a strategy could be adapted to MOFs with larger pores, such as MOF-808 by generating porous AM polymer coatings from bulkier DHN oligomers, highlighting the versatility of this method. Finally, we showed that by tuning the AM coating thickness on UiO-66, the hierarchically porous structures of these AM@UiO-66 composites engender excellent hexane isomer separation selectivity and storage capacity.
AB - Polymer/metal-organic framework (MOF) composites have been widely studied for their favorable combination of polymer flexibility and MOF crystallinity. While traditional polymer-coated MOFs maximize the polymer properties at the surface, the dramatic loss of MOF porosity due to blockage by the nonporous polymeric coating remains a problem. Herein, we introduce intrinsically microporous synthetic allomelanin (AM) as a porous coating on the zirconium-based MOF (Zr-MOF) UiO-66 via an in situ surface-constrained oxidative polymerization of the AM precursor, 1,8-dihydroxynaphthalene (1,8-DHN). Transmission electron microscopy images verify the formation of well-defined nanoparticles with a core-shell morphology (AM@UiO-66), and nitrogen sorption isotherms indicate the porosity of the UiO-66 core remains constant and is not disturbed by the AM coating. Notably, such a strategy could be adapted to MOFs with larger pores, such as MOF-808 by generating porous AM polymer coatings from bulkier DHN oligomers, highlighting the versatility of this method. Finally, we showed that by tuning the AM coating thickness on UiO-66, the hierarchically porous structures of these AM@UiO-66 composites engender excellent hexane isomer separation selectivity and storage capacity.
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U2 - 10.1021/jacs.3c02195
DO - 10.1021/jacs.3c02195
M3 - Article
C2 - 37305923
AN - SCOPUS:85163789008
SN - 0002-7863
VL - 145
SP - 13195
EP - 13203
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 24
ER -