ABSTRACT
Herein, the development of new nanocomposite systems is reported based on one-part polyurea (PU) and aminopropyl isobutyl polyhedral oligomeric silsesquioxane (POSS)-functionalized graphene nanoplatelets (GNP-POSS) as compatible nanoreinforcements with the PU resin. GNP-POSS was effectively synthesized via a two-step synthesis protocol, including ultrasonication-assisted reaction and precipitation, and carefully characterized with respect to its chemical and crystalline structure, morphology, and thermal stability. FTIR and XPS spectroscopy analyses revealed that POSS interacts with the residual oxygen moieties of the GNPs through both covalent and noncovalent bonding. The X-ray diffraction pattern of GNP-POSS further revealed that the crystallinity of the GNPs was not altered after their functionalization with POSS. GNP-POSS was successfully incorporated in PU at contents of 1, 3, 5, and 10 wt % to yield PU/GNP-POSS nanocomposite films. An ATR-FTIR analysis of these films confirmed the presence of strong interfacial interactions between the urea groups of PU and the GNP-POSS functionalities. Moreover, the PU/GNP-POSS nanocomposite films exhibited enhanced thermal stability and mechanical properties compared to those of the neat PU film. The quasi-static tensile testing of the PU/GNP-POSS samples revealed remarkable enhancements in the tensile strength (from 7.9 for the neat PU to 25.1 MPa for PU/GNP-POSS) and Young's modulus (238-617 MPa), while elongation at break and toughness also showed 14 and 125% improvements, respectively. Finally, the effects of GNP-POSS content on the morphological, quasistatic tensile, and high-strain-rate dynamic behavior of the PU/GNP-POSS nanocomposite films were also investigated. Overall, the tests performed using a split-Hopkinson pressure bar setup revealed a large increase in the film strength (from 147.6 for the neat PU film to 199 MPa for the PU/GNP-POSS film) and a marginal increase in the energy density of the film (38.1-40.8 kJ/m3). These findings support the suitability of the PU/GNP-POSS nanocomposite films for force protection applications.
ABSTRACT
Since their emergence in 2014, graphitic carbon nitride quantum dots (g-C3N4 QDs) have attracted much interest from the scientific community due to their distinctive physicochemical features, including structural, morphological, electrochemical, and optoelectronic properties. Owing to their desirable characteristics, such as non-zero band gap, ability to be chemically functionalized or doped, possessing tunable properties, outstanding dispersibility in different media, and biocompatibility, g-C3N4 QDs have shown promise for photocatalysis, energy devices, sensing, bioimaging, solar cells, optoelectronics, among other applications. As these fields are rapidly evolving, it is very strenuous to pinpoint the emerging challenges of the g-C3N4 QDs development and application during the last decade, mainly due to the lack of critical reviews of the innovations in the g-C3N4 QDs synthesis pathways and domains of application. Herein, an extensive survey is conducted on the g-C3N4 QDs synthesis, characterization, and applications. Scenarios for the future development of g-C3N4 QDs and their potential applications are highlighted and discussed in detail. The provided critical section suggests a myriad of opportunities for g-C3N4 QDs, especially for their synthesis and functionalization, where a combination of eco-friendly/single step synthesis and chemical modification may be used to prepare g-C3N4 QDs with, for example, enhanced photoluminescence and production yields.
ABSTRACT
Carbon quantum dots (CQDs) have potential applications in many fields such as light-emitting devices, photocatalysis, and bioimaging due to their unique photoluminescence (PL) properties and environmental benignness. Here, we report the synthesis of nitrogen-doped carbon quantum dots (NCQDs) from citric acid and m-phenylenediamine using a one-pot hydrothermal approach. The environment-dependent emission changes of NCQDs were extensively investigated in various solvents, in the solid state, and in physically assembled PMMA-PnBA-PMMA copolymer gels in 2-ethyl-hexanol. NCQDs display bright emissions in various solvents as well as in the solid state. These NCQDs exhibit multicolor PL emission across the visible region upon changing the environment (solutions and polymer matrices). NCQDs also exhibit excitation-dependent PL and solvatochromism, which have not been frequently investigated in CQDs. Most CQDs are nonemissive in the aggregated or solid state due to the aggregation-caused quenching (ACQ) effect, limiting their solid-state applications. However, NCQDs synthesized here display a strong solid-state emission centered at 568 nm attributed to the presence of surface functional groups that restrict the π-π interaction between the NCQDs and assist in overcoming the ACQ effect in the solid state. NCQD-containing gels display significant fluorescence enhancement in comparison to the NCQDs in 2-ethyl hexanol, likely because of the interaction between the polar PMMA blocks and NCQDs. The application of NCQDs-Gel as a solid/gel state fluorescent display has been presented. This research facilitates the development of large-scale, low-cost multicolor phosphor for the fabrication of optoelectronic devices, sensing, and bioimaging applications.
ABSTRACT
A series of azomethine diol monomers containing naphthalene moiety were synthesized and oxidatively polymerized in aqueous alkaline medium using NaOCl as oxidant. The structure of the monomers and polymers was characterized by using various spectroscopic techniques. PL spectra of polymers are exhibiting good emission with high Stokes shift values than the monomers due to their polyconjugated structure. The electrical conductivity of polymers was measured by a two-point probe technique, and it increases with an increase in iodine vapour contact time up to 144 h. The electrical conductivity values were correlated with the charge density on azomethine nitrogen obtained from the Hückel calculation method. The dielectric properties of polymers were studied at different temperatures in the frequency range from 50 Hz to 5 MHz. The synthesized polyazomethines have recorded high thermal stability and are shown by carbon residue of around 50% at 800 °C in the thermogravimetric analysis.
ABSTRACT
The article reports a straightforward strategy for the design and synthesis of highly luminescent conjugated mesoporous oligomers (CMOs) with an "aggregation-induced enhanced emission" (AIEE) feature through Wittig polymerization of a molecular rotor. Typical molecular rotors such as triphenylamine (TPA) and tetraphenylethene (TPE) as B2-, and A4- and A3-type nodes have been used to construct AIEE-active CMOs, namely, CMO1 and CMO2. The quick dissipation of the excited photons is successfully controlled by the restriction of rotation of the phenyl units through the formation of a mesoporous network scaffold in a solid/thin film, which provides high quantum yields for the interlocked CMO system. Both the CMOs are sensitive and selective to the various nitroaromatic explosives, whereas CMO1 is more sensitive (Ksv = 2.6 × 106 M-1) toward picric acid. The increased quenching constant for CMO1 is due to its increased quantum yield and high energy-transfer efficiency. The mechanism for sensing has been studied in detail. The larger pore size and pore density in the mesoporous network of CMO1 are found to be responsible for the greater extent of energy transfer from CMO1 to picric acid. Furthermore, CMO1 has been employed for low-cost filter-paper-based detection of a trace amount of nitroaromatic explosive materials.
