Shiling Dong

Abstract:

Electrospinning has been applied to produce ceramic fibers using sol gel-based spinning solutions consisting of ceramic precursors, a solvent, and a polymer to control the viscosity of the solution. However, the addition of polymers to the spinning solution makes the process more complex, increases the processing time, and results in porous mechanically weak ceramic fibers. Herein, we develop a coelectrospinning technique, where a nonspinnable sol (<10 mPa s) consisting of only the ceramic precursor(s) and solvent(s) is encapsulated inside a polymeric shell, forming core-shell precursor fibers that are further calcined into ceramic fibers with reduced porosity, decreased surface defects, uniform crystal packing, and controlled diameters. We demonstrate the versatility of this method by applying it to a series of nonspinnable sols and creating high-quality ceramic fibers containing TiO₂, ZrO₂, SiO₂, and Al₂O₃. The polycrystalline TiO₂ fibers possess excellent flexibility and a high Young's modulus reaching 54.3 MPa, solving the extreme brittleness problem of the previously reported TiO₂ fibers. The single-component ZrO₂ fibers exhibit a Young's modulus and toughness of 130.5 MPa and 11.9 KJ/m³, respectively, significantly superior to the counterparts prepared by conventional sol-gel electrospinning. We also report the creation of ceramic fibers in micro- and nanospring morphologies and examine the formation mechanisms using thermomechanical simulations. The fiber assemblies constructed by the helical fibers exhibit a density-normalized toughness of 3.5-5 times that of the straight fibers due to improved fracture strain. This work expands the selection of the electrospinning solution and enables the development of ceramic fibers with more attractive properties.

Abstract:

Electrospun photoactive nanofibers hold significant potential for enhanced photon absorption and charge transport in organic photovoltaics. However, electrospinning conjugated polymers with fiber diameters comparable to exciton diffusion lengths for efficient dissociation, is difficult. Previously, spinning sub-100 nm poly(3-hexylthiophene) (P3HT) fibers has required the auxiliary polymer, poly(ethylene oxide) (PEO), and large antisolvent additions. Therefore, its success differs considerably across donor polymers, due to variable antisolvent addition limits before precipitation. Herein, plasmonic nanoparticle infusion into P3HT nanofibers is used to modulate viscosity and deliver a novel and unrivaled strategy to achieve reduced fiber diameters. Following PEO removal, the fibers measure 55 nm in diameter, 30% lower than any previous report – providing the shortest exciton diffusion pathways to the heterojunction upon electron acceptor infiltration. The nanoparticle-containing nanofibers present a 58% enhancement over their pristine thin-film counterparts. ~17% is ascribed to plasmonic effects, demonstrated in thin-films, and the remainder to along-fiber polymer chain alignment, introduced by electrospinning. The anisotropy of light absorbed when polarized parallel versus perpendicular to the fibers increases from 0.88 to 0.62, suggesting the diameter reduction improves the alignment, resulting in greater electrospinning-induced enhancements. Controlled by the electrospinning behavior of PEO, our platform may be adapted to contemporary donor-acceptor systems.

Abstract:

Ceramic aerogels are excellent ultralight-weight thermal insulators yet impractical due to their tendency towards structural degradation at elevated temperatures, under mechanical disturbances, or in humid environments. Here, we present flexible and durable alumina/zirconia fibrous aerogels (AZFA) fabricated using 3D sol–gel electrospinning — a technique enabling in situ formation of 3D fiber assemblies with significantly reduced time consumption and low processing cost compared to most existing methods. Our AZFAs exhibit ultralow density (> 3.4 mg cm−3), low thermal conductivity (> 21.6 mW m−1 K−1), excellent fire resistance, while remaining mechanically elastic and flexible at 1300 °C, and thermally stable at 1500 °C. We investigate the underlying structure-thermal conductivity relationships, demonstrating that the macroscopic fiber arrangement dictates the solid-phase thermal conduction, and the mesopores in the fiber effectively trap air thereby decreasing the gas conduction. We show experimentally and theoretically that directional heat transport, i.e., anisotropic thermal conductivity, can be achieved through compressing the fiber network. We further solve the moisture sensitivity problem of common fibrous aerogels through fluorination coating. The resulting material possesses excellent hydrophobicity and self-cleaning properties, which can provide reliable thermal insulation under various conditions, including but not limited to high-temperature conditions in vehicles and aircraft, humid conditions in buildings, and underwater environments for oil pipelines. Graphical Abstract: [Figure not available: see fulltext.]

Abstract:

Titanium dioxide (TiO2) nanomaterials are ideal for photocatalytic degradation of organic pollutants but remain infeasible for industrial and municipal wastewater treatment because they cannot simultaneously satisfy two essential criteria for practical application, i.e., high performance and good recyclability. Here, we design and create hierarchically porous TiO2 fibers by dual-polymer templating sol–gel electrospinning combined with precise control over crystallization. The produced fibers own unique interconnected macropores throughout the fiber body that enable significantly enhanced light absorption and unlimited mass transport, making them ideal hosts for anchoring plasmonic nanoparticles (NPs). The Au NP-coupled TiO2 fibers have photocatalytic efficiencies up to 6.6 times higher than plain TiO2 fibers, showing comparable ability as commercial P25 nanopowder in photodegrading methyl blue (MB) and achieving complete decomposition of methyl orange (MO) in 90 min while P25 degrades only 66% MO. Unlike P25 or anatase TiO2 nanopowders that non-reversibly disperse/aggregate in water, our composite fibers can be recollected through natural sedimentation, and their superior performance remains for at least six cycles. This work offers a practical and feasible design for high-performance recyclable photocatalysts for industrial-scale water treatment.

Abstract:

Electrospinning technique is well-known for the generation of different fibers. While it is a "simple" technique, it lies in the fact that the fibers are typically produced in the form of densely packed two-dimensional (2D) mats with limited thickness, shape, and porosity. The highly demanded three-dimensional (3D) fiber assemblies have been explored by time-consuming postprocessing and/or complex setup modifications. Here, we use a classic electrospinning setup to directly produce 3D fiber macrostructures only by modulating the spinning solution. Increasing solution conductivity modifies electrodynamic jet behavior and fiber assembling process; both are observed <i>in situ</i> using a high-speed camera. More viscous solutions render thicker fibers that own enhanced mechanical stiffness as examined by finite element analysis. We reveal the correlation between the universal solution parameters and the dimensionality of fiber assemblies, thereof, enlightening the design of more "3D spinnable" solutions that are compatible with any commercial electrospinning equipment. After a calcination step, ultralightweight ceramic fiber assemblies are generated. These inexpensive materials can clean up exceptionally large fractions of oil spillages and provide high-performance thermal insulation. This work would drive the development and scale-up production of next-generation 3D fiber materials for engineering, biomedical, and environmental applications.