RESUMO
Phonon splitting of the longitudinal and transverse optical modes (LO-TO splitting), a ubiquitous phenomenon in three-dimensional polar materials, will break down in two-dimensional (2D) polar systems. Theoretical predictions propose that the LO phonon in 2D polar monolayers becomes degenerate with the TO phonon, displaying a distinctive "V-shaped" nonanalytic behavior near the center of the Brillouin zone. However, the full experimental verification of these nonanalytic behaviors has been lacking. Here, using monolayer hexagonal boron nitride (h-BN) as a prototypical example, we report the comprehensive and direct experimental verification of the nonanalytic behavior of LO phonons by inelastic electron scattering spectroscopy. Interestingly, the slope of the LO phonon in our measurements is lower than the theoretically predicted value for a freestanding monolayer due to the screening of the Cu foil substrate. This enables the phonon polaritons in monolayer h-BN/Cu foil to exhibit ultra-slow group velocity (~5 × 10-6 c, c is the speed of light) and ultra-high confinement (~ 4000 times smaller wavelength than that of light). These exotic behaviors of the optical phonons in h-BN presents promising prospects for future optoelectronic applications.
RESUMO
Defect engineering leads to an effective manipulation of the physical and chemical properties of metal-organic frameworks (MOFs). Taking the common missing linker defect as an example, the defective MOF generally possesses larger pores and a greater surface area/volume ratio, both of which favor an increased amount of adsorption. When it comes to the self-diffusion of adsorbates in MOFs, however, the missing linker is a double-edged sword: the unsaturated metal sites, due to missing linkers, could interact more strongly with adsorbates and result in a slower self-diffusion. Therefore, it is of fundamental importance to evaluate the two competing factors and reveal which one is dominating, a faster self-diffusion due to larger volume or a slower self-diffusion owing to strong interactions at unsaturated sites. In this work, via Monte Carlo and molecular dynamics simulations, we investigate the behavior of isopropyl alcohol (IPA) in the Zr-based UiO-66 MOFs, with a specific focus on the missing linker effects. The results reveal that unsaturated Zr sites bind strongly with IPA molecules, which in return would significantly reduce the self-diffusion coefficient of IPA. Besides this, for the same level of missing linkers, the location of defective sites also makes a difference. We expect such a theoretical study will provide an in-depth understanding of self-diffusion under confinement, inspire better defect engineering strategics, and promote MOF based materials toward challenging real-life applications.
RESUMO
Styrene-butadiene styrene graphene oxide nanoplatelets (SBS-g-GOs)-modified asphalt was prepared by reacting thiolated GOs (GOs-SH) with SBS in asphalt using a thiol-ene click reaction. The temperature resistance and mechanical properties of asphalts were analyzed by dynamic shear rheology (DSR) and multiple-stress creep-recovery (MSCR) tests, which revealed that an optimum amount of GOs-SH (0.02%) can effectively improve the low temperature and anti-rutting performance of SBS asphalt. Segregation experiments showed that SBS-g-GOs possessed good stability and dispersion in base asphalt. Fluorescence microscopy results revealed that the addition of GOs-SH promoted the formation of SBS network structure. Textural and morphological characterization of GOs-SH and SBS were achieved by Fourier transform infra-red (FT-IR) spectroscopy, energy-dispersive X-ray spectroscopy (EDX), atomic-force microscopy (AFM), X-ray diffraction (XRD), and scanning electron microscopy (SEM), while surface chemical composition was tested by X-ray photoelectron spectroscopy (XPS). Based on textural characterization data, a suitable reaction mechanism was proposed that involved the preferential reaction between GOs-SH and 1,2 C=C of SBS. The currently designed GOs-SH incorporated asphalt via thiol-ene click reaction provides new ideas for the preparation of modified asphalt with enhanced mechanical properties for target-oriented applications.
