Boosting Oxygen Reduction Reaction Kinetics by Designing Rich Vacancy Coupling Pentagons in the Defective Carbon.

In the energy conversion context, the design and synthesis of high-performance metal-free carbon nanomaterials with topological defects for the oxygen reduction reaction (ORR) are essential. Herein, we first report a template-assisted strategy to fabricate carbon defect electrocatalysts with rich vacancy coupling pentagons (VP) as active sites in two-dimensional (2D) carbon nanosheets (VP/CNs). Experimental characterizations verify the presence of abundant VP active sites in the VP/CNs electrocatalyst, and the ORR activity is linearly related to the amounts of VP active sites. In situ spectroscopic results identify that the VP/CNs can catalyze direct O-O bond cleavage, bypassing the formation of traditional *OOH intermediates, resulting in the fast kinetics of ORR via a dissociative pathway. The as-prepared VP/CNs show outstanding intrinsic activity for alkaline ORR (half-wave potential of 0.86 V vs reversible hydrogen electrode) with an almost 99% efficiency for four-electron selectivity, outperforming that using the benchmark of Pt/C. Density functional theory calculations further reveal that the cooperative effect between carbon vacancy and adjacent pentagons significantly increases the charge transfer and achieves a lower ORR reaction energy barrier compared with the counterpart of adjacent pentagons or single pentagon. The well-designed carbon defects pave a new avenue for the rational design of metal-free electrocatalysts with high efficiency.

Facile Uniaxial Electrospinning Strategy To Embed CsPbBr3 Nanocrystals with Enhanced Water/Thermal Stabilities for Reversible Fluorescence Switches.

All-inorganic halide perovskite nanocrystals with their fascinating optical properties have drawn increasing attention as promising nanoemitters. However, due to the intrinsic poor colloidal stability against the external environment, the practical applications are greatly limited. Herein, a facile and effective strategy for the in situ encapsulation of CsPbBr3 NCs into highly dense multichannel polyacrylonitrile (PAN) nanofibers via a uniaxial electrospinning strategy is presented. Such a facile uniaxial electrospinning strategy enables the in situ formation of CsPbBr3 NCs in PAN nanofibers without the introduction of stabilizers. Significantly, the obtained CsPbBr3 nanofibers not only display intense fluorescence with a high quantum yield (≈48%) but also present high stability when exposed to water and air owing to the peripheral protecting matrix of PAN. After immersing CsPbBr3@PAN nanofiber films in water for 100 days, the quantum yield of CsPbBr3@PAN nanofibers maintained 87.5% of the original value, which was much higher than that using CsPbBr3 NCs. Furthermore, based on the spectral overlap between the electrochromic material of ruthenium purple and fluorescence of CsPbBr3@PAN nanofiber films with excellent water stability, a reversible fluorescence switch is constructed with good fatigue resistance, suggesting their promising applications.

Zinc Assisted Thermal Etching for Rich Edge-Located Fe-N4 Active Sites in Defective Carbon Nanofiber for Activity Enhancement of Oxygen Electroreduction.

Single-atom catalysts (SACs) with edge-located metal active sites exhibit superior oxygen reduction reaction (ORR) performance due to their narrower energy gap and higher electron density. However, controllably designing such active sites to fully reveal their advantages remains challenging. Herein, rich edge-located Fe-N4 active sites anchored in hierarchically porous carbon nanofibers (denoted as e1-Fe-N-C) are fabricated via an in situ zinc-assisted thermal etching strategy. The e1-Fe-N-C catalyst demonstrates superior alkaline ORR activity compared to counterparts with fewer edge-located Fe-N4 sites and commercial Pt/C. Density functional theory calculations show that the accumulation of more negative charges near the Fe-N and the formation of partially reduced Fe state in the edge-located Fe-N4 sites reduce the energy barrier for the ORR process. Additionally, the unique hierarchically porous structures with mesopores and macropores facilitate full utilization of the active sites and enhance long-range mass transfer. The zinc-air battery (ZAB) assembled with e1-Fe-N-C has a peak power density of 198.9 mW cm-2, superior to commercial Pt/C (152.3 mW cm-2). The present strategy by facile controlling the amount of the zinc acetate template systematically demonstrates the superiority of edge-located Fe-N4 sites, providing a new design avenue for rational defect engineering to achieve high-performance ORR.