Rapid membrane surface functionalization with Ag nanoparticles via coupling electrospray and polymeric solvent bonding for enhanced antifouling and catalytic performance: Deposition and interfacial reaction mechanisms.

Electrospray is an effective, fast, and potentially scalable approach for membrane surface functionalization using various engineered nanomaterials (ENMs). However, the lack of fundamental understandings of the deposition process hinders the controlled deposition, efficient utilization, and long-term stabilization of the ENMs, and thus the practical applications of the nanocomposite membranes. To bridge this critical knowledge gap, advanced online characterization techniques (laser diffraction size measurement and laser doppler velocimetry) coupled with mathematical aerosol modeling are utilized to understand the three key process parameters: droplet size, deposition velocity, and evaporation rate. After deposition, polymeric solvent bonding (i.e., interdiffusion and subsequent entanglement of polymers) was found to substantially stabilize the deposited Ag NPs. We further provide a comprehensive description of such interfacial reaction mechanisms. Our results show a consistency between theoretical predication and measurement of the droplet size or deposition velocity, whereas realistic droplet evaporation rate is lower than the theoretical value due to the addition of the polymer. Successful stabilization of Ag NPs via interfacial polymeric bonding occurs under the conditions of large material contact area, high material compatibility, proper temperature (e.g., 22 °C), and polymer-to-solvent ratio (e.g., 3-5%). Our coupled approach achieves superior Ag NP coverage with high stability within minutes. Despite some reduction in water permeance, the resultant membrane shows markedly improved catalytic and antimicrobial (antibiofouling) performance (>90% enhancement) and maintained rejection. Taken together, our findings provide fundamental insights into the coupled process of electrospray deposition and polymeric solvent bonding to enable additive manufacturing of novel nanocomposite membranes with diverse structures and multiple functions.