RESUMO
Single-crystal X-ray diffraction (SCXRD) is a widely used method for structural characterization. Generally, low temperature is of great significance for improving the crystallographic diffraction quality. Herein we observe that this practice is not always effective for flexible metal-organic frameworks (f-MOFs). An abnormal crystallography, that is, more diffraction spots at a high angle and better resolution of diffraction data as the temperature increases in the f-MOF (1-g), is observed. XRD results reveal that 1-g has a reversible anisotropic thermal expansion behavior with a record-high c-axial positive expansion coefficient of 1,401.8 × 10-6 K-1. Calculation results indicate that the framework of 1-g has a more stable thermodynamic configuration as the temperature increases. Such configuration has lower-frequency vibration and may play a key role in promoting higher Bragg diffraction quality at room temperature. This work is of great significance for how to obtain high-quality SCXRD diffraction data.
RESUMO
Multiemissive sensors are being actively pursued, because of their ratiometric luminescent detection capabilities, which demonstrates better sensitivity and selectivity than conventional single-emission sensors. Herein, we present a trichromatic white-light-emitting metal-organic framework (MOF) composite (Z3) by simultaneously incorporating red/green-emitting Pt/Ru complex cations into porous blue-emitting bio-MOF-1 through post-synthetic modification. With the help of a three-dimensional (3-D) dual-ratiometric luminescence recognition method, and unique turn-on responses of the red emission toward amine compounds (ACs), including NH3 and aliphatic amines, via confinement-induced luminescence enhancement effect, Z3 can work as a dual-ratiometric luminescent sensor for discrimination of 7 out of 11 AC vapors. This work not only provides a new AC sensing mechanism (confinement effect) that can induce a "turn-on" response but also proves that the accuracy and selectivity of composite sensor can be greatly improved through the combination of 3-D recognition method and the confinement effect. Thus, it open up fresh opportunities to develop composite sensors with excellent sensing and differentiating ability.
RESUMO
Hydro(solvo)thermal syntheses of quaternary copper sulfides containing alkaline earth metal ions remain a great challenge because of the low solubility of Cu-S compounds. Herein, a new facile solvothermal method was developed, and four quaternary copper sulfides, i.e., BaCu3InS4 (1), BaCu3GaS4 (2), BaCu2SnS4 (3), and BaCu2GeS4 (4), were prepared using excess sulfur as a mineralizer. Compound 1 possesses a novel three-dimensional (3D) anionic [Cu3InS4]2- framework constructed by an 8-membered ring of [Cu4S4] and [Cu2In2S4] alternatively. Compound 2 features a unique 3D anionic [Cu3GaS4]2- framework composed of [Cu3GaS10]n14n- anionic chains and 8-membered rings, in which [Cu4S4] and [Cu2Ga2S4] reside alternatively. Compounds 3 and 4 feature 3D anionic [Cu2MS4]2- (M = Sn, Ge) frameworks composed of CuS4 and MS4 tetrahedra with Ba2+ located in the channels. It is worth noting that different 3D Cu-S frameworks exist in the title crystal structures, in which main group ions are incorporated. This paper provides a new synthetic strategy for new quaternary sulfides.
RESUMO
Novel coaxial heterojunction carbon nanofibers, fabricated by electro-spinning a mixture of hydro-pitch and polyacrylonitrile, served as the counter electrode for dye-sensitized solar cells. Their high power conversion efficiency, being comparable to that of Pt CE, was achieved due to their good conductivity and high heteroatom content.
