Strong and Stiff Aramid Nanofiber/Carbon Nanotube Nanocomposites

Small but strong carbon nanotubes (CNTs) are fillers of choice for composite reinforcement owing to their extraordinary modulus and strength. However, the mechanical properties of the nanocomposites are still much below those for mechanical parameters of individual nanotubes. The gap between the expectation and experimental results arises not only from imperfect dispersion and poor load transfer but also from the unavailability of strong polymers that can be effectively utilized within the composites of nanotubes. Aramid nanofibers (ANFs) with analogous morphological features to nanotubes represent a potential choice to complement nanotubes given their intrinsic high mechanical performance and the dispersible nature, which enables solvent-based processing methods. In this work, we showed that composite films made from ANFs and multiwalled CNTs (MWCNTs) by vacuum-assisted flocculation and vacuum-assisted layer-by-layer assembly exhibited high ultimate strength of up to 383 MPa and Young’s modulus (stiffness) of up to 35 GPa, which represent the highest values among all the reported random CNT nanocomposites. Detailed studies using different imaging and spectroscopic characterizations suggested that the multiple interfacial interactions between nanotubes and ANFs including hydrogen bonding and π–π stacking are likely the key parameters responsible for the observed mechanical improvement. Importantly, our studies further revealed the attractive thermomechanical characteristics of these nanocomposites with high thermal stability (up to 520 °C) and ultralow coefficients of thermal expansion (2–6 ppm·K^–1). Our results indicated that ANFs are promising nanoscale building blocks for functional ultrastrong and stiff materials potentially extendable to nanocomposites based on other nanoscale fillers

Hybrid Au/ZnO Hexagonal Pyramid Nanostructures: Preferred Growth on the Apexes of the Basal Plane than on the Tip

Nanoscale materials having size- and shape-dependent interactions with light provide flexible opportunities for harvesting solar energy. Photocatalysts based on semiconductor nanoparticles (NPs) have been the most effective materials for the conversion of light into chemical energy, the efficiency of which can be further enhanced by the incorporation of metallic NPs forming hybrid nanostructures. The structural parameters of not only constituent components but also the resultant hybrid nanostructures are critical for the optimization of photocatalytic performance of composite catalysts. Here we demonstrated the successful size control over ZnO hexagonal pyramids (HPs) for the first time. The smallest HPs showing the best photocatalytic properties were used for further Au attachment. Interestingly, we found that most of the Au NPs preferred to grow on the apexes of the basal plane. Very occasionally, Au NPs at the tip of ZnO HPs can be observed. The role of light in promoting the reduction of gold salt by sodium citrate was also revealed. Quantum mechanical calculations were used to explain the site-specific growth of Au on the surface of ZnO HPs. Enhanced degradation rates over organic dyes were found for Au/ZnO hybrids under both UV and visible light irradiation

Hydrogen Bonding Stabilized Self-Assembly of Inorganic Nanoparticles: Mechanism and Collective Properties

Developing a simple and efficient method to organize nanoscale building blocks into ordered superstructures, understanding the mechanism for self-assembly and revealing the essential collective properties are crucial steps toward the practical use of nanostructures in nanotechnology-based applications. In this study, we showed that the high-yield formation of ZnO nanoparticle chains with micrometer length can be readily achieved by the variation of solvents from methanol to water. Spectroscopic studies confirmed the solvent effect on the surface properties of ZnO nanoparticles, which were found to be critical for the formation of anisotropic assemblies. Quantum mechanical calculations and all atom molecular dynamic simulations indicated the contribution of hydrogen bonding for stabilizing the structure in water. Dissipative particle dynamics further revealed the importance of solvent–nanoparticle interactions for promoting one-dimensional self-assembly. The branching of chains was found upon aging, resulting in the size increase of the ensembles and network formation. Steady-state and time-resolved luminescent spectroscopes, which probed the variation of defect-related emission, revealed stronger Forster resonance energy transfer (FRET) between nanoparticles when the chain networks were formed. The high efficiency of FRET quenching can be ascribed to the presence of multiple energy transfer channels, as well as the short internanoparticle distances and the dipole alignment