A new
bismuth-based halide double perovskite Cs2LiBiCl6 was isolated successfully using solid-state reactions. The
crystal structure was investigated using X-ray diffraction and complemented
by 7Li solid-state nuclear magnetic resonance spectroscopy,
which indicated the highly ordered nature of Li and Bi ions in the B sublattice of double perovskite. Compared with the Na
analogue, the more moisture-sensitive Cs2LiBiCl6 has a smaller indirect band gap of 3.15(2) eV and red-shift luminescence
of around 612 nm as well as stronger intensities at Mn2+ doping. The stability mechanism of Cs2LiBiCl6 was discussed together with that of Cs2NaBiCl6 and their inaccessible Br counterparts based on the tolerance and
octahedral factors and density functional theory (DFT) calculations.
Owing to the small size of Li+ cations, Cs2LiBiCl6 has low tolerance and octahedral factors close to the boundary
between the stable perovskite and nonperovskite compounds, which possess
a small decomposition energy and thus easily coexist with other ternary
phases. The Br-based compositions of Cs2LiBiBr6 and Cs2NaBiBr6 have even smaller octahedral
factors and negative decomposition energies, and therefore their double
perovskite polymorphs are destabilized. DFT simulations indicate that
the moisture sensitivity of Cs2LiBiCl6 is related
to the coordination preference of Li+ due to its smaller
size and the steric effect from water molecules, in contrast with
the larger Na+ showing a more stable octahedral configuration
under the water incorporation. These mechanisms combining the geometry
factors and decomposition energies provide new insights into the stability
of halide double perovskites.
A rapid HPLC-UV method for the determination of three organic acids (neochlorogenic acid, chlorogenic acid, and cryptochlorogenic acid) in Polygoni Vivipari Rhizoma (PVR) by one marker was developed. The sample was prepared by effervescence-assisted matrix solid-phase dispersion (EA-MSPD). The separation of compounds was performed on a Poroshell column. The equal absorption wavelength was set as follows: 292 nm (0∼7 min) and 324 nm (7∼10 min). The analytical time including sample extraction and HPLC separation time was 12 min. The analytical method validation such as accuracy (recoveries 99.85%–106.29% and RSD < 2.9%), precision (RSD < 1.3%), reproducibility (RSD < 1.7%), and stability tests (RSD < 0.7% in 24 h) proved that the established HPLC method was suitable for determination of three organic acids in PVR. The contents of three analytes obtained by the external standard method with three markers and the equal absorption wavelength method with one marker were similar (RSD ≤ 2.0%). The developed method, which is rapid and reference compound saving, is an improved quality evaluation method of PVR.
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