Surfactant-in-Polymer Templating for Fabrication of Carbon Nanofibers with Controlled Interior Substructures: Designing Versatile Materials for Energy Applications.

A simple, scalable, surfactant-in-polymer templating approach is demonstrated to create controlled long-range secondary substructures in a primary structure. A metal bis(2-ethylhexyl) sulfosuccinate (MAOT) as the surfactant is shown to be capable of serving as a sacrificial template and metal precursor in carbon nanofibers. The low interfacial tension and controllable dimensions of the MAOT are maintained in the solid-phase polymer, even during electrospinning and heat-treatment processes, allowing for the long-range uniform formation of substructures in the nanofibers. The MAOT content is found to be a critical parameter for tailoring the diameter of the nanofibers and their textural properties, such as size and volume of interior pores. The metal counterion species in the MAOT determine the introduction of metallic phases in the nanofiber interior. The incorporation of MAOT with Na as the counterion into the polymer phase leads to the formation of a built-in pore structure in the nanofibers. In contrast, MAOT with Fe as a counterion generates unique iron-in-pore substructures in the nanofibers (FeCNFs). The FeCNFs exhibit outstanding charge storage and water splitting performances. As a result, the MAOT-in-polymer templating approach can be extended to combinations of various metal precursors and thus create desirable functionalities for different target applications.

Anomalous restoration of sp2 hybridization in graphene functionalization.

The functionalization of nanocarbon materials such as graphene has attracted considerable attention over the past decades. In this work, we designed and synthesized a unique N-heterocyclic carbene compound with a pyrene tail group (NHCp) to investigate how carbene species can be used for the functionalization of graphene. Although the carbene moiety of NHCp has the ability to covalently bond to graphene, the pyrene tail can noncovalently interact with graphene and allows monitoring its surrounding microenvironment. The major characteristics of the resulting nanohybrids were highly dependent on the type of graphene and the NHCp-to-graphene weight ratio. Importantly, despite the covalent functionalization of graphene, an anomalous decrease in the intensity of the Raman D peak and improved conductivity were observed for the nanohybrids. It was found that the covalent bond of NHCp to the graphene edge may allow the hybridization of their orbitals, which affects electronic energy levels and alters the double resonance process that originates the D peak at the edge defect. Importantly, the NHCp compound can act as a π acceptor (not just as a σ donor) via the NHCp-graphene covalent bridge. This is the first report showing that the concept of π-backdonation can be realized in two-dimensional materials, such as graphene, and rationally designed carbene molecules can functionalize graphene without losing their beneficial sp2 hybridization characteristics.

Electrical monitoring of photoisomerization of block copolymers intercalated into graphene sheets.

Insulating polymers have received little attention in electronic applications. Here, we synthesize a photoresponsive, amphiphilic block copolymer (PEO-b-PVBO) and further control the chain growth of the block segment (PVBO) to obtain different degrees of polymerization (DPs). The benzylidene oxazolone moiety in PEO-b-PVBO facilitated chain-conformational changes due to photoisomerization under visible/ultraviolet (UV) light illumination. Intercalation of the photoresponsive but electrically insulating PEO-b-PVBO into graphene sheets enabled electrical monitoring of the conformational change of the block copolymer at the molecular level. The current change at the microampere level was proportional to the DP of PVBO, demonstrating that the PEO-b-PVBO-intercalated graphene nanohybrid (PGNH) can be used in UV sensors. Additionally, discrete signals at the nanoampere level were separated from the first derivative of the time-dependent current using the fast Fourier transform (FFT). Analysis of the harmonic frequencies using the FFT revealed that the PGNH afforded sawtooth-type current flow mediated by Coulomb blockade oscillation.

Zero reduction luminescence of aqueous-phase alloy core/shell quantum dots via rapid ambient-condition ligand exchange.

Quantum dots (QDs) have been widely studied as promising materials for various applications because of their outstanding photoluminescence (PL). Although ligand exchange methods for QDs have been developed over two decades, the PL quantum yield (QY) of aqueous phase QDs is still lower than that of their organic phase and the mechanism of quenching has not been clearly understood. In this study, we demonstrate for the first time that 3-mercaptopropionic-capped CdZnSeS/ZnS core/shell QDs obtained via ligand exchange in a ternary solvent system containing chloroform/water/dimethyl sulfoxide can enable the fast phase transfer and zero reduction of PL under ambient condition. The new solvent system allows the ligand-exchanged QDs to exhibit enhanced QYs up to 8.1% of that of the organic-phase QDs. Based on both theoretical calculation and experiment, it was found that control over the physical/chemical perturbation between the organic/aqueous phases by choosing appropriate solvents for the ligand exchange process is very important to preserve the optical properties of QDs. We believe that our new technologies and theoretical knowledge offer opportunities for the future design and optimization of highly stable and highly luminescent aqueous-phase QDs for various applications.