TY - JOUR
T1 - Interface-regulated NH2-UiO-66/ladder polysilsesquioxane hybrid membranes for synergistically enhanced CO2/CH4 separation and plasticization resistance
AU - Wang, Jiahui
AU - Guo, Zhenghua
AU - Wen, Manyu
AU - Liu, Wenqing
AU - Li, Xiaohu
AU - Yu, Liang
AU - Tsuru, Toshinori
N1 - Publisher Copyright:
© 2026 Elsevier B.V.
PY - 2026/8
Y1 - 2026/8
N2 - Plasticization induced by high-pressure CO2 remains a central challenge for polymer membranes in natural gas upgrading, because excessive CO2 sorption can increase chain mobility and eventually deteriorate separation selectivity and operational stability. Herein, we report an interface-regulated hybrid membrane platform by integrating amino-functionalized UiO-66 (NH2-UiO-66) nanoparticles into a side-chain-engineered ladder polysilsesquioxane matrix (LPG40). In this design, the semirigid ladder-like siloxane backbone provides an intrinsically stable framework against segmental relaxation, while NH2-UiO-66 contributes preferential CO2 sorption sites and microporous transport pathways. More importantly, the coupling between the MOF surface and the epoxy-containing side chains of LPG40 generates an interfacial confinement effect, which reduces non-selective interfacial defects and suppresses local chain mobility under elevated CO2 pressure. As a result, the optimized hybrid membrane containing 15 wt% NH2-UiO-66 exhibited a CO2 permeability of about 56.3 Barrer and a CO2/CH4 selectivity of 48.2, together with a plasticization pressure of 22.5 bar. Compared with the pristine LPG40 membrane, both gas transport performance and resistance to CO2-induced plasticization were simultaneously improved. Mixed-gas measurements further demonstrated stable separation behavior and enhanced tolerance to plasticization at reduced CO2 concentrations, indicating the potential of the membrane for elevated-pressure natural gas upgrading. The improved performance is attributed to the cooperative effects of the semirigid ladder backbone, CO2-preferential sorption in NH2-UiO-66, and interface-regulated confinement that promotes selective transport while mitigating chain relaxation. This work provides an effective strategy for designing robust hybrid membranes with balanced permeability, selectivity, and plasticization resistance.
AB - Plasticization induced by high-pressure CO2 remains a central challenge for polymer membranes in natural gas upgrading, because excessive CO2 sorption can increase chain mobility and eventually deteriorate separation selectivity and operational stability. Herein, we report an interface-regulated hybrid membrane platform by integrating amino-functionalized UiO-66 (NH2-UiO-66) nanoparticles into a side-chain-engineered ladder polysilsesquioxane matrix (LPG40). In this design, the semirigid ladder-like siloxane backbone provides an intrinsically stable framework against segmental relaxation, while NH2-UiO-66 contributes preferential CO2 sorption sites and microporous transport pathways. More importantly, the coupling between the MOF surface and the epoxy-containing side chains of LPG40 generates an interfacial confinement effect, which reduces non-selective interfacial defects and suppresses local chain mobility under elevated CO2 pressure. As a result, the optimized hybrid membrane containing 15 wt% NH2-UiO-66 exhibited a CO2 permeability of about 56.3 Barrer and a CO2/CH4 selectivity of 48.2, together with a plasticization pressure of 22.5 bar. Compared with the pristine LPG40 membrane, both gas transport performance and resistance to CO2-induced plasticization were simultaneously improved. Mixed-gas measurements further demonstrated stable separation behavior and enhanced tolerance to plasticization at reduced CO2 concentrations, indicating the potential of the membrane for elevated-pressure natural gas upgrading. The improved performance is attributed to the cooperative effects of the semirigid ladder backbone, CO2-preferential sorption in NH2-UiO-66, and interface-regulated confinement that promotes selective transport while mitigating chain relaxation. This work provides an effective strategy for designing robust hybrid membranes with balanced permeability, selectivity, and plasticization resistance.
KW - Anti-plasticization
KW - CO/CH separation
KW - Hybrid membrane
KW - Interface-regulated confinement
KW - Ladder-polysilsesquioxanes
KW - Natural gas upgrading
UR - https://www.scopus.com/pages/publications/105041010876
U2 - 10.1016/j.memsci.2026.125752
DO - 10.1016/j.memsci.2026.125752
M3 - Article
AN - SCOPUS:105041010876
SN - 0376-7388
VL - 756
JO - Journal of Membrane Science
JF - Journal of Membrane Science
M1 - 125752
ER -