Electrospinning evolved as a powerful technology to produce membranes consisting of nano- to micron-scaled fibers offering unique membrane properties due to the extremely high surface-to-volume ratio and high membrane porosity. However, this technology is often far removed from a green and environmentally-friendly process, as it employs solvents with issues such as high flammability, toxicity, difficult disposal, or energy-intensive synthesis. Indeed, the most commonly used solvents in the electrospinning field are halogenated (e.g. chloroform, trifluoroethanol) and toxic solvents (e.g. dimethylformamide), the use of which is now restricted by the Chemical Control Regulation in the European Union (REACH). This is especially important when considering the commercialization of electrospun products due to the more limited solvent choice. In order to render electrospinning more attractive as a commercial technique and further improve scalability, solvent alternatives and other green routes have to be established, which adhere to societal and legal restrictions especially in regard to the environmental and health impact. Therefore, this review provides the current ecological and economical context of this technology, and summarizes recent approaches towards green electrospinning. Since electrospinning from solutions and dispersions constitutes the predominantly used form of this technique both in research and industry, the focus of this work is set on the use of solvents or solvent mixtures classified exclusively by the term “green”. The approaches presented comprehensively cover the production of polymeric fibers via solution, emulsion, suspension, and in situ cross-linking electrospinning.

A profound understanding of how to tailor surface topographies of electrospun fibers is of great importance for surface sensitive applications including optical sensing, catalysis, drug delivery and tissue engineering. Hereby, a novel approach to comprehend the driving forces for fiber surface topography formation is introduced through inclusion of the dynamic solvent-polymer interaction during fiber formation. Thus, the interplay between polymer solubility as well as computed fiber jet surface temperature changes in function of time during solvent evaporation and the resultant phase separation behavior are studied. The correlation of experimental and theoretical results shows that the temperature difference between the polymer solution jet surface temperature and the dew point of the controlled electrospinning environment are the main influencing factors with respect to water condensation and thus phase separation leading to the final fiber surface topography. As polymer matrices with enhanced surface area are particularly appealing for sensing applications, we further functionalized our nanoporous fibrous membranes with a phosphorescent oxygen-sensitive dye. The hybrid membranes possess high brightness, stability in aqueous medium, linear response to oxygen and hence represent a promising scaffold for cell growth, contactless monitoring of oxygen and live fluorescence imaging in 3-D cell models.