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Composite electrospun fibrous membranes are widely studied for the application of membrane distillation. It is an effective approach to enhance the membrane distillation performance in terms of anti-wetting surface and permeate flux by fabricating composite fibrous membranes (CFMs) with a thin skin layer on a thick supporting layer. In this work, various membranes prepared with different pore sizes and porosities by polyacrylonitrile and polyvinylpyrrolidone were prepared. The membrane characteristics and membrane distillation performance were tested. The mass transfer across the membranes was analyzed experimentally and theoretically in detail. It is shown that the skin layer significantly increases liquid entry pressure of the CFM by 5 times. All the membranes have a similar permeate flux. The permeate flux of membranes is stable at 19.2 ± 1.2 kg/m2/h, and the salt rejection ratios remain above 99.98% at 78 ± 1 °C for 11 h. The pore size and porosity of membranes have an insignificant effect on the temperature distribution of membrane. The porosity and pore size of the skin layer have an insignificant effect on the mass transfer process of the CFM. The mass transfer process of the CFM is governed by the supporting layer.

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