# Defect Engineering in Fluorinated Metal–Organic Frameworks Within Mixed-Matrix Membranes for Enhanced CO2 Separation

## TL;DR

This paper introduces a new method to improve CO2 separation using defect-engineered fluorinated metal-organic frameworks in membranes.

## Contribution

The novelty lies in using defect engineering in fluorinated MOFs to enhance CO2 separation performance beyond the Robeson upper bound.

## Key findings

- HP-ZU-61 nanoparticles showed a 267% increase in BET surface area compared to LP-ZU-61.
- HP-ZU-61/6FDA-DAM MMMs achieved CO2 permeability of 1626 barrer and CO2/CH4 selectivity of 33.
- Defects in MOFs created faster CO2 diffusion and stronger adsorption, improving separation efficiency.

## Abstract

Developing highly permeable and selective membranes for energy-efficient CO2/CH4 separation remains challenging. Mixed-matrix membranes (MMMs) integrating polymer matrices with metal–organic frameworks (MOFs) offer significant potential. However, rational filler–matrix matching presents substantial difficulties, constraining separation performance. In this work, defects were engineered within fluorinated MOF ZU-61 through the partial replacement of 4,4′-bipyridine linkers with pyridine modulators, producing high-porosity HP-ZU-61 nanoparticles exhibiting a 267% BET surface area enhancement (992.9 m2 g−1) over low-porosity ZU-61 (LP-ZU-61) (372.2 m2 g−1). The HP-ZU-61/6FDA-DAM MMMs (30 wt.%) demonstrated homogeneous filler dispersion and pre-served crystallinity, achieving a CO2 permeability of 1626 barrer and CO2/CH4 selectivity (33), surpassing the 2008 Robeson upper bound. Solution-diffusion modeling indicated ligand deficiencies generated accelerated diffusion pathways, while defect-induced unsaturated metal sites functioned as strong CO2 adsorption centers that maintained solubility selectivity. This study establishes defect engineering in fluorinated MOF-based MMMs as a practical strategy to concurrently overcome the permeability–selectivity trade-off for efficient CO2 capture.