The research of active and sustainable electrocatalysts toward oxygen reduction reaction (ORR) is of great importance for industrial application of fuel cells. Here, we report a remarkable ORR catalyst with both excellent mass activity and durability based on sub 2 nm thick Rh-doped Pt nanowires, which combine the merits of high utilization efficiency of Pt atoms, anisotropic one-dimensional nanostructure, and doping of Rh atoms. Compared with commercial Pt/C catalyst, the Rh-doped Pt nanowires/C catalyst shows a 7.8 and 5.4-fold enhancement in mass activity and specific activity, respectively. The combination of extended X-ray absorption fine structure analysis and density functional theory calculations reveals that the compressive strain and ligand effect in Rh-doped Pt nanowires optimize the adsorption energy of hydroxyl and in turn enhance the specific activity. Moreover, even after 10000 cycles of accelerated durability test in O condition, the Rh-doped Pt nanowires/C catalyst exhibits a drop of 9.2% in mass activity, against a big decrease of 72.3% for commercial Pt/C. The improved durability can be rationalized by the increased vacancy formation energy of Pt atoms for Rh-doped Pt nanowires.
As a 100% atom-economy process, direct oxidation of methane into methanol remains as a grand challenge due to the dilemma between activation of methane and over-oxidation of methanol. Here, we report that water enabled mild oxidation of methane into methanol with >99% selectivity over Au single atoms on black phosphorus (Au1/BP) nanosheets under light irradiation. The mass activity of Au1/BP nanosheets reached 113.5 μmol gcatal−1 in water pressured with 33 bar of mixed gas (CH4:O2 = 10:1) at 90 °C under light irradiation (1.2 W), while the activation energy was 43.4 kJ mol−1. Mechanistic studies revealed that water assisted the activation of O2 to generate reactive hydroxyl groups and •OH radicals under light irradiation. Hydroxyl groups reacted with methane at Au single atoms to form water and CH3* species, followed by oxidation of CH3* via •OH radicals into methanol. Considering the recycling of water during the whole process, we can also regard water as a catalyst.
Fundamental to understanding and predicting the optoelectronic properties of semiconductors is the basic parameters of excitons such as oscillator strength and exciton binding energy. However, such knowledge of CsPbBr perovskite, a promising optoelectronic material, is still unexplored. Here we demonstrate that quasi-two-dimensional (quasi-2D) CsPbBr nanoplatelets (NPLs) with 2D exciton behaviors serve as an ideal system for the determination of these parameters. It is found that the oscillator strength of CsPbBr NPLs is up to 1.18 × 10, higher than that of colloidal II-VI NPLs and epitaxial quantum wells. Furthermore, the exciton binding energy is determined to be of ∼120 meV from either the optical absorption or the photoluminescence analysis, comparable to that reported in colloidal II-VI quantum wells. Our work provides physical understanding of the observed excellent optical properties of CsPbBr nanocrystals and would benefit the prediction of high-performance excitonic devices based on such materials.
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