Ultrathin and stable active layer of dense composite membrane enabled by poly(dopamine).

We demonstrate that dopamine is able to self-polymerize and adhere firmly onto the substrate, which can create a hierarchical structure comprising an ultrathin active layer and a porous support layer. Such an approach opens a novel way to fabricating highly efficient and stable composite materials including composite membranes. More specifically, in this study the composite membranes are fabricated by simply dipping microporous substrate in aqueous dopamine solution under mild conditions. Nanoindentation measurement reveals the tight adhesion of dopamine onto microporous substrate, which is ascribed to numerous pi-pi and hydrogen-bonding interactions. The chemical composition of the active layer is analyzed by XPS, which demonstrates the self-polymerization of dopamine. The water contact angle of the dopamine coated membranes is reduced remarkably compared with that of the uncoated counterpart. Stylus profiler measurements display that the poly(dopamine) thickness increases as the coating time increases. FESEM images of the membranes' cross section show that an active layer (<100 nm) is deposited on the porous polysulfone (PS) substrate. Positron annihilation spectroscopy (PAS) is introduced to probe the fractional free volume properties throughout the cross section of the composite membranes and reveal that after dopamine double-coating the active layer becomes thicker and more compact. Moreover, pH and concentration of the dopamine solution exert notable influence on the fractional free volume of the composite membranes. The as-prepared membranes are tentatively employed for pervaporative desulfurization and exhibits satisfying separation performance as well as durability. This facile, versatile, and efficient approach enables a promising prospect for the wide applications of such novel kinds of ultrathin composite materials.