Molecular‐Level Hybridization of Nafion with Quantum Dots for Highly Enhanced Proton Conduction

Nanophase-separated membranes hold promise for fast molecule or ion transfer. However, development and practical application are significantly hindered by both the difficulty of chemical modification and nanophase instability. This can be addressed by organic-inorganic hybridization of functional fillers with a precise distribution in specific nanophase. Here, a molecular-level hybridization for nanophase-separated Nafion using 2-5 nm quantum dots (QDs) as a new smart filler is demonstrated. Two kinds of QDs are prepared and used: hydrophilic polymer-like QDs (PQDs) and hydrophobic graphene oxide QDs (GQDs). Because of selective interactions, QDs offer advantages of matched structural size and automatic recognition with the nanophase. A distinctive synthesis of subordinate-assembly, in which QDs are driven by the self-assembly of Nafion affinity chains, is reported. This results in a precise distribution of QDs in the ionic, or backbone, nanophases of Nafion. The resulting PQDs in the ionic nanophase significantly increase membrane proton conduction and device output-power without loss of mechanical stability. This is difficult to realize with conventional fillers. The GQDs in the backbone nanophase reduce the crystallinity and significantly augment membrane water uptake and swelling capacities.