Effect of VTMS-Modified TiO₂ Nanoparticles on CO₂ Separation Performance of Polysulfone-Based Mixed Matrix Membranes

Polysulfone (PSF), despite its excellent thermal and mechanical stability, exhibits moderate gas separation performance and poor compatibility with inorganic fillers, resulting in interfacial voids and structural defects. This study addressed these limitations by incorporating vinyltrimethoxysilane (VTMS)-functionalized TiO₂ nanoparticles into PSF matrix to develop mixed matrix membranes (MMMs) for selective CO₂/N₂ separation. Membranes with 1–5 wt.% VTMS@TiO₂ loadings were fabricated via solution casting, and their gas separation performance was systematically evaluated. VTMS modification enhanced the dispersion and interfacial adhesion of TiO₂ within the PSF matrix, as confirmed by SEM, FTIR, XRD, and TGA analyses. The 4 wt.% VTMS@TiO₂ loaded membrane showed optimal performance, with a CO₂ permeability of 8.48 barrer and a CO₂/N₂ selectivity of 26.50 due to stronger polymer–filler interactions and enhanced CO₂ affinity by VTMS functional groups. This membrane has shown stable transport behavior and favorable CO₂ selectivity as confirmed by pressure- and temperature-dependent permeation studies. Robeson plot analysis showed that the optimized membrane approached the upper bound, demonstrating a significant improvement over pure PSF. The study confirmed that VTMS-functionalized TiO₂ enhanced both permeability and selectivity through improved filler dispersion, interfacial integrity, and CO₂ affinity.