Tailoring Gas Transport Properties in MOF-Based Mixed Matrix Membranes: The Role of Filler Morphology and Surface Functionalization
5 affiliations
- 1National Research Council of Italy - Institute on Membrane Technology “Enrico Drioli” (CNR-ITM, Via P. Bucci, 17/C, Rende (CS, Italy, 87036
- 2Department of Chemistry and Industrial Chemistry, University of Pisa, via G. Moruzzi 13, Pisa, Italy, 56124
- 3Department of Chemistry, NIS Centre, INSTM Research Unit, University of Turin, Via P. Giuria 7, Italy
- 4National Research Council of Italy - Institute of Chemistry of Organometallic Compounds (ICCOM-CNR, via G. Moruzzi 1, Pisa, Italy, 56124
- 5Center for the Integration of Scientific Instrumentation, University of Pisa (CISUP, Lungarno Pacinotti 43/44, Pisa, Italy, 56126
Abstract
The development of high‑performance mixed‑matrix membranes (MMMs) for gas separations relies on precise control of filler morphology and optimized polymer–filler interactions. In this study, we elucidate how crystal size, morphology, and surface functionalization of the perfluorinated metal-organic framework (MOF) F4_MIL‑140A(Ce) influence the gas transport properties of MMMs based on Pebax® 1657 and Matrimid® 9725 matrices. Through systematic modulation of reaction conditions, we synthesized sub‑micrometric F4_MIL‑140A(Ce) particles with tailored size and aspect ratio, achieving improved dispersion and interfacial contact within the polymer phases. A post‑synthetic grafting strategy using stearic acid further enhanced the compatibility of the MOF without altering crystallinity, pore accessibility, or CO 2 adsorption behavior, as confirmed by powder X-ray diffraction, scanning electron microscopy, and sorption analyses. MMMs prepared with the surface-functionalized MOF displayed improved polymer–filler adhesion, minimized interfacial voids, and significantly enhanced gas transport properties. In particular, the Pebax® 1657-based MMMs approached the 2008 Robeson upper bound for CO 2 /N 2 separation, driven primarily by increased CO 2 solubility. In contrast, Matrimid® 9725 MMMs exhibited substantial improvements in H 2 /N 2 and O 2 /N 2 selectivity, linked to enhanced diffusivity. The insights presented in this work provide a rational framework for engineering MOF–polymer interfaces and advancing membrane‑based gas separation and CO 2 capture technologies.
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BibTeX
@misc{rizzuto2026tailoring,
title = {{Tailoring Gas Transport Properties in MOF-Based Mixed Matrix Membranes: The Role of Filler Morphology and Surface Functionalization}},
author = {Carmen Rizzuto and Francesca Nerli and Virginia Guiotto and Francesca Nardelli and Lucia Calucci and Valentina Crocellà and Marco Lessi and Marco Taddei and Alessio Fuoco},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010982/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010982/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Tailoring Gas Transport Properties in MOF-Based Mixed Matrix Membranes: The Role of Filler Morphology and Surface Functionalization
AU - Carmen Rizzuto
AU - Francesca Nerli
AU - Virginia Guiotto
AU - Francesca Nardelli
AU - Lucia Calucci
AU - Valentina Crocellà
AU - Marco Lessi
AU - Marco Taddei
AU - Alessio Fuoco
PY - 2026
DA - 2026/10/23
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010982/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010982/v1
AB - The development of high‑performance mixed‑matrix membranes (MMMs) for gas separations relies on precise control of filler morphology and optimized polymer–filler interactions. In this study, we elucidate how crystal size, morphology, and surface functionalization of the perfluorinated metal-organic framework (MOF) F4_MIL‑140A(Ce) influence the gas transport properties of MMMs based on Pebax® 1657 and Matrimid® 9725 matrices. Through systematic modulation of reaction conditions, we synthesized sub‑micrometric F4_MIL‑140A(Ce) particles with tailored size and aspect ratio, achieving improved dispersion and interfacial contact within the polymer phases. A post‑synthetic grafting strategy using stearic acid further enhanced the compatibility of the MOF without altering crystallinity, pore accessibility, or CO 2 adsorption behavior, as confirmed by powder X-ray diffraction, scanning electron microscopy, and sorption analyses. MMMs prepared with the surface-functionalized MOF displayed improved polymer–filler adhesion, minimized interfacial voids, and significantly enhanced gas transport properties. In particular, the Pebax® 1657-based MMMs approached the 2008 Robeson upper bound for CO 2 /N 2 separation, driven primarily by increased CO 2 solubility. In contrast, Matrimid® 9725 MMMs exhibited substantial improvements in H 2 /N 2 and O 2 /N 2 selectivity, linked to enhanced diffusivity. The insights presented in this work provide a rational framework for engineering MOF–polymer interfaces and advancing membrane‑based gas separation and CO 2 capture technologies.
ER -