Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes

作者：Rahul Shevate, Vepa Rozyyev, Rajesh Pathak, Anil U. Mane, Kirti Sankhala, Feng Gao, Tamar Segal‐Peretz, Seth B. Darling, Jeffrey W. Elam · 发表于：Chemistry of Materials · 年份：2024 · DOI：10.1021/acs.chemmater.3c03090 · 被引用次数：15 · 研究领域：Semiconductor materials and devices、Advanced Sensor and Energy Harvesting Materials、Membrane Separation Technologies

Atomic layer deposition (ALD) is a powerful strategy to engineer hybrid organic–inorganic membranes with emergent functionalities. The combination of atomic-level thickness control, a wide materials palette, and unprecedented conformality allows the physiochemical properties (e.g., hydrophilicity) of mesoporous polymer membranes to be precisely tuned. The nucleation of ALD material growth on polymer surfaces relies on Lewis acid–base interactions and remains an overlooked motif with tremendous potential to accelerate ALD nucleation and growth. Strategies to enhance these interactions could enable desirable properties such as antifouling behavior to be imparted on inert polymer surfaces that lack the necessary functional groups for ALD nucleation. In this study, we demonstrate that the reactivity of polyacrylonitrile (PAN) membranes toward ALD metal oxide (MO) precursors with Lewis acid characteristics is enhanced by introducing strong Lewis base functional groups (amidoxime: Am) on the PAN backbone (Am-PAN). The resulting Lewis acid–base interactions accelerate the MO nucleation in Am-PAN and reduce the number of deposition cycles required to achieve hydrophilicity compared with the untreated PAN membrane. Unveiling the reaction mechanism, in situ Fourier transform infrared (FTIR) spectroscopy measurements established enhanced interaction dynamics between the ALD MO precursors and the Am-PAN membrane, unlike the PAN membrane. Spectroscopic ellipsometry and thermogravimetric a...