5,7-Dichloro-3-O-methylnorlichexanthone

Chlorine-rich argyrodite-type solid electrolyte Li5.5PS4.5Cl1.5 has been a promising choice for solid-state batteries (SSBs) because of its ultrafast Li-ion conduction. However, the poor air/moisture stability and low electrochemical stability with pristine high-voltage cathodes hinder their applications. Herein, O-substituted Li5.5PS4.5-xOxCl1.5 (x = 0, 0.075, 0.175, and 0.25) solid electrolytes are successfully synthesized. Among them, Li5.5PS4.425O0.075Cl1.5 delivers high ionic conductivity, improved moisture resistance, and enhanced electrochemical stability in higher voltage windows. SSBs using Li5.5PS4.425O0.075Cl1.5 show higher capacities and superior cyclability than those using Li5.5PS4.5Cl1.5 combined with a pristine LiNi0.8Mn0.1Co0.1O2 cathode when operated at a high end-of-charge voltage of 4.5 V (vs Li+/Li0). Moreover, the batteries exhibit outstanding performance in a wide temperature range. This work provides a strategy to modify the inherent drawbacks of sulfide electrolytes, promoting their practical applications.

We herein describe the coupling of solid-solution and heterojunction in a 2D-1D BiOCl0.5I0.5/Bi5O7I hierarchical architecture for optimizing photoabsorption, energy band levels and charge separation, thereby promoting the photo-oxidation and molecular oxygen activation performance. BiOCl0.5I0.5/Bi5O7I shows a core-shell-like structure with BiOCl0.5I0.5 thin nanoflakes (~3 to 8 layers) homogeneously vertical coating on the surface of Bi5O7I strips. The photo-responsive range of BiOCl0.5I0.5/Bi5O7I can be orderly tuned from 450nm to 650nm by increasing the BiOCl0.5I0.5 content. Regardless of visible light (λ>420nm) or UV light (365nm) irradiation, BiOCl0.5I0.5/Bi5O7I casts highly promoted photocatalytic activity in decomposing methyl orange (MO) compared to the BiOCl0.5I0.5 and Bi5O7I. This enhancement on full-spectrum photoreactivity is attributable to the facilitated charge separation derived from BiOCl0.5I0.5/Bi5O7I heterojunction with intimate interfacial interaction, which is approved by transient photocurrent response under visible and UV-vis light. To probe the photocatalytic mechanism, active species trapping tests are performed over BiOCl0.5I0.5, Bi5O7I and BiOCl0.5I0.5/Bi5O7I, which reveal superoxide radical (O2-) and hole (h+) take dominant roles in photo-oxidation reaction. BiOCl0.5I0.5/Bi5O7I was also found possessing a stronger ability in molecular oxygen activation with a O2- production rate of 2.22×10-7molL-1h-1, which far outperforms Bi5O7I (1.35×10-7molL-1h-1) and BiOCl0.5I0.5 (1.54×10-7molL-1h-1). It further corroborates the efficient band charge transfer between BiOCl0.5I0.5 and Bi5O7I. This work may furnish a new concept on smart design of high-performance photocatalytic materials via manipulating multiple strategies.

The reaction of AgBF4 and [Rh(COD)Cl]2 (COD=1,5-cyclooctadiene) in presence of [NEt4 ][C5 (CF3 )5 ] afforded the fluorocarbon soluble complex [Rh(COD)(C5 (CF3 )5 )] by salt metathesis. This complex represents the first example for a successful coordination of the weakly basic [C5 (CF3 )5 ]- ligand, since its first synthesis in 1980. In addition to [Rh(COD)(C5 (CF3 )5 )] also the byproduct [Rh(COD)(C5 (CF3 )4 H)] was isolated and fully characterized. Accompanying DFT studies showed that the interaction energy of the [C5 (CF3 )5 ]- ligand towards the 12-electron fragment [Rh(COD)]+ is ≈70 kcal mol-1 lower in comparison to [C5 (CH3 )5 ]- due to reduced electrostatic interactions and weaker π-donor properties of the ligand. The quantitative but reversible substitution of the [C5 (CF3 )5 ]- ligand by toluene, converting it into a weakly coordinating anion, experimentally proved the extraordinary weak bonding interaction.