Efficient C(sp3)-H bond oxidation on perovskite quantum dots based on Ce-oxygen affinity.

Perovskite quantum dots (QDs) have shown attractive prospects in the field of visible photocatalysis, especially in the synthesis of high value-added chemicals. However, under aerobic conditions, the stable operation of QD catalysts has been limited by the reactive oxygen species (ROS) generated by photoexcitation, especially superoxide species. Here, we propose a strategy of Ce3+ doping in perovskite QDs to guide superoxide species for photocatalytic oxidation reactions. In C(sp3)-H bond oxidation of hydrocarbons, superoxide species were rapidly generated and efficiently utilized on the surface of perovskite QDs, which achieves the stable operation of the catalytic system and obtains a high product conversion rate (15.3 mmol/g/h for benzaldehydes). The mechanism studies show that the strong Ce-oxygen affinity accelerates the relaxation process of photoinduced exciton transfer to superoxide species and inhibits the radiative recombination pathway. This work provides a new idea of utilizing oxygen species on perovskite surface and broadens the design strategy of high-performance QD photocatalysts.

Orientation-polarization dependence of pressure-induced Raman anomalies in anisotropic 2D ReS2.

We report an in situ high-pressure (0-30.24 GPa) optical study of the 2D ReS2 crystal under four specific configurations of sample orientation and laser polarization. Unlike the horizontal measurement configuration that has been widely used, under the vertical sample configuration we observe the anomalous disappearance behavior of Raman modes. Through analyzing the peak evolution under different configurations with tensor calculations, we identify the effect of pressure on different components in the full 3 × 3 Raman tensor of the anisotropic ReS2 crystal. These results provide new evidence on the remarkable tunability of pressure engineering on the crystal structure, and our methods offer an additional degree of freedom for studying pressure engineering on 2D anisotropic materials.

Analyzing Anisotropy in 2D Rhenium Disulfide Using Dichromatic Polarized Reflectance.

In-plane anisotropy in 2D rhenium disulfide (ReS2 ) offers intriguing opportunities for designing future electronic and optical devices, and toward such applications, it is crucial to identify the crystal orientation in such 2D anisotropic materials. Existing spectroscopy or electron microscopy methods for determining the crystalline orientation often require complicated sample preparing procedures and specialized equipment, which could sometimes limit their application. In this work, a dichromatic polarized reflectance method is demonstrated, which can quickly and accurately resolve the crystal orientation (Re-Re chain) in 2D ReS2 crystals with different thicknesses. Furthermore, it can be readily extended to multi-chromatic schemes to achieve greater measurement capability and can be easily tailored to work for different 2D materials. The method offers a simple and effective approach for studying anisotropy in 2D materials.