Polyvinylidene fluoride (PVDF) membranes are extensively utilized in membrane distillation (MD) for water treatment. However, traditional methods easily form asymmetrical membranes with dense skin layers that are detrimental to membrane flux. Herein, an eco-friendly PVDF membrane was fabricated by utilizing a delayed phase separation process without using any pore-forming agents. In addition, methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (PolarClean) was used as a green solvent without posing risks to humans and the environment. It was demonstrated that the PVDF concentration is crucial in influencing the microstructures and performance of the resulting membranes. As the PVDF concentration increased, the morphology changed significantly, resulting in a reduction of pore size. When feeding the device with NaCl solution at a concentration of 35 g/L, the MD water vapor flux reached 18.49 kg·m⁻2·h⁻1, while maintaining a salt rejection of over 99.97% during the continuous operation for 24 h. This work presented a method for producing green PVDF membranes via delayed phase inversion with satisfactory water vapor flux and salt rejection, highlighting their prospect for effective applications in MD for water treatment.
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