Oxygen Plasma-Modified Graphene Composite Membranes for Enhanced Forward Osmosis Performance: Mitigating Reverse Salt Flux and Improving Permeability

Forward osmosis (FO) membranes face challenges in balancing high water permeability, low reverse salt flux (RSF), and mechanical durability. Although nanopores in graphene have great theoretical potential, the existing methods make it difficult to independently optimize the nanopores of the graphene layer and the microstructure of the substrate without damaging each other. Here, we propose a defect engineering strategy based on oxygen plasma etching to address this collaborative optimization challenge. Monolayer porous graphene (PG) was integrated with polysulfone (Psf) substrates, followed by oxygen plasma etching to introduce nanopores and oxygen-containing functional groups (e.g., carboxyl, hydroxyl). By controlling the etching time to 10 s, the resulting membrane (S-PG10) exhibited a water flux of 0.24 LMH in 0.5 M NaCl, representing an order-of-magnitude increase compared to the pristine graphene membrane (S-G). Remarkably, S-PG10 maintained a high salt rejection (>96%) and a low <i>J_s</i>/<i>J_w</i> (<0.35 g·L^-1). Substrate modification via short-term plasma etching (5 min) further doubled the water flux of S*5-PG10 (0.47 LMH in 0.5 M NaCl) by increasing porosity (81.8%→85.6%) and hydrophilicity. However, prolonged etching (>15 min) degraded mechanical strength and increased RSF due to pore structure disruption. To enhance robustness, Poly(D,L-lactic acid) (PDLLA)-doped substrates (S^#-PG) were engineered, with 0.1 wt.% PDLLA optimizing mechanical properties while maintaining low RSF and high flux. Excessive PDLLA (10 wt.%) induced hydrophobicity and crystalline structures, reducing permeability. The study demonstrates that synergistic optimization of plasma etching duration on the graphene selective layer (5~10 s) and substrates (5 min) as well as PDLLA doping (0.1 wt.%) balances pore architecture, surface chemistry, and substrate integrity, achieving FO membranes with superior water-salt selectivity and mechanical stability. These findings provide critical insights into designing high-performance graphene-based membranes for sustainable desalination and water purification.