Development of Graphene Oxide Framework Membranes via the “from” and “to” Cross-Linking Approach for Ion-Selective Separations

Graphene oxide (GO) membranes with well-defined nanochannels formed between the stacked GO nanosheets find great interest in molecular separations. However, GO membranes are unstable in aqueous solution environments because of weak interactions between the stacked nanosheets. Herein, we developed a preparation method by diminishing the self-contained oxidized functional groups in GO and subsequent cross-linking to form GO framework (GOF) membranes with excellent aqueous solution stability. GOF membranes were fabricated by alternate deposition of branched polyethylenimine (BPEI) and a mixed solution of GO and thiourea (TU). Structural elucidation illustrated that the TU partially reduced the GO molecules and acted as a “to” cross-linker by bridging adjacent GO nanosheets through in-plane and out-of-plane of interactions. During the GO deposition, BPEI performed the role as a “from” cross-linker by binding the TU-linked GO laminates to form stable GOF membranes with well-defined nanochannels. Morphological studies confirmed the formation of the tightly packed structure for BPEI/GO_TU membranes due to the high Π–Π interactions between the GO nanosheets and bridging effect of TU. The GOF membranes exhibited a rejection of 99.5% for anionic dye methyl orange and cationic dye rhodamine B. The BPEI/GO_TU membranes fabricated from 12 bilayers using 0.25 mg/mL of GO solution have a pure water flux of 24 L m–² h–¹ and a Na₂SO₄ rejection of 94%; this permeability is 2.5 times higher than that of commercial nanofiltration membranes. Moreover, (BPEI/GO_TU)₁₂ GOF membranes exhibited excellent aqueous solution stability in acidic and basic conditions. The excellent separation performance and aqueous solution stability of the BPEI/GO_TU membranes are intricately linked to the partial reduction and cross-linking of GO nanosheets in GOF membranes. Thus, the “from” and “to” cross-linking approach developed in this work can be extended for the fabrication of structurally stable membranes from other 2D materials.