Ultrathin Films of Organic Networks as Nanofiltration Membranes via Solution-Based Molecular Layer Deposition

Ultrathin films of organic networks on various substrates were fabricated through the solution-based molecular layer deposition (MLD) technique. The rigid tetrahedral geometries of polyfunctional amine and acyl chloride involved in the reaction ensure the continuity of the polymerization process. A linear increase in film thickness with respect to cycle number was observed by UV-vis adsorption, ellipsometry, and quartz crystal microbalance. The growth rate per MLD cycle is 1.6 nm, which can be controlled at the single molecular level. For the first time, we develop the MLD method on the top of hydrolyzed PAN substrate, resulting in nanofiltration (NF) membranes. The stepwise growth was monitored via attenuated total reflectance infrared studies. The separation performance of the obtained membrane for various solutes was sensitive to the terminated layers and number of cycles. The rejection of NH2-terminated membranes follows the order of CaCl2 > Na2SO4 > NaCl, while the order for COOH-capped surface is Na2SO4 > CaCl2 > NaCl. The absolute value of zeta potential for the MLD membranes decreases with the addition of deposition layers. The moderate water flux for the resulting membrane is due to the reduced porosity of the support as well as the low roughness and hydrophilicity of the membrane surface. This bottom-up process provides a promising approach for construction of long-term steady NF membranes with nanoscale dimensions.