Layer-by-Layer Assembly of Polyelectrolyte Multilayers in Three-Dimensional Inverse Opal Structured Templates

A novel means of layer-by-layer deposition (LbL) of polyelectrolyte multilayers on three-dimensionally porous inverse opal (3D-IO) structures is presented. The 3D-IO structures comprising UV-curable polymer are highly flexible and can be readily demonstrated as free-standing films with double-sided open porosity over a large scale. A conflict between the intrinsically hydrophobic polymeric structures and waterborne characteristics of the LbL deposition process is overcome by employing a mixed solvent system of water and alcohol. The deposition pH of the LbL assembly can strongly affect the charge density and the degree of entanglement of polyelectrolyte chains, resulting in contrastingly different film deposition and growth behaviors. Since this method utilizes a three-dimensionally structured surface as a deposition substrate, 3D-IO films with a thickness of tens of micrometers can be uniformly and completely deposited with polyelectrolyte multilayers using only several tens of bilayer depositions, which can offer a new pathway of fabricating functionalized polymeric films. Finally, the LbL treated 3D-IO films are applied to nanofiltration membranes for removing multivalent metallic cations. Due to the enhanced Donnan exclusion effect as a result of multiple interfaces formed inside the 3D-IO structures and the relatively large volumetric ratio of water-permeable polyelectrolyte complexes, outstanding membrane performance was observed. Specifically, a good rejection rate of metal ions was achieved even under highly diluted feed conditions without sacrificing the high permeation flux.