A comparative investigation of an AB- and AA-stacked bilayer graphene sheet under an applied electric field:A density functional theory study

An AB-and AA-stacked bilayer graphene sheet （BLG） under an electric field is investigated by ab initio calculation. The interlayer distance between the two layers, band structures, and atomic charges of the system are investigated in the presence of different electric fields normal to the BLG. The AB-stacked BLG is able to tune the bandgap into 0.234 eV with the increase of the external electronic field to 1 V/nm, however, the AA-stacked BLG is not sensitive to the external electric field. In both the cases, the spacing between the BLG slightly change in terms of the electric field. The charges in the AB-stacked BLG are increased with the increase of the electric field, which is considered to be the reason that causes the bandgap opening in the AB-stacked BLG.

Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol（2-CTP） as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene（1-MCTA）, 1,6-dichlorothianthrene（1,6-DCTA）, 4,6-dichlorodibenzothiophene（4,6-DCDT）and 1,6-dichlorodibenzothiophene（1,6-DCDT）. The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.

A pH-universal ORR catalyst with atomic Fe-heteroatom(N,S)sites for high-performance Zn-air batteries

Developing innovative,easy-to-manufacture,and non-Pt-group-metal(non-PGM)electrocatalysts is essential for the highly efficient oxygen reduction reaction(ORR).Herein,we report a self-sacrificing post-synthetic strategy to synthesize highly loaded Fe-isolated single atoms anchored on the hierarchical porous N,S co-doped carbon matrix(Fe-SAs/S,N-C/rGO).The optimized Fe-SAs/S,N-C/rGO exhibits excellent ORR activity in the pH-universal range with half-wave potentials of 0.89,0.80,and 0.60 V in alkaline,acidic,and neutral media,comparable to the commercial Pt/C(0.85,0.81,and 0.64 V,respectively).The homemade liquid Zn-air battery(ZAB)with Fe-SAs/S,N-C/rGO as the cathode catalyst displays an open-circuit voltage(OCV)of~1.61 V,discharging specific capacity of 817.23 mAh·g^(-1),and long-term durability of~1865 cycles,outperforming those of the device with commercial Pt/C+RuO_(2)(1.49 V,657.32 mAh·g^(-1),and~120 cycles,respectively).Intriguingly,the corresponding flexible solidstate ZAB delivers satisfactory OCV,peak power density,foldability,and cycling stability at room temperature,as well as adaptability at a low temperature of -10℃.Besides,density functional theory(DFT)calculation reveals that the atomic FeN_(3)S moieties in Fe-SAs/S,N-C/rGO can cause charge redistribution and lower the binding strength of oxygen-containing intermediates,resulting in accelerated ORR kinetics and optimized catalytic activity.This work provides insights into experimental and theoretical guidance towards non-PGM electrocatalysts for efficient energy conversion.

Selective 3,4-Polymerization Mechanism of Isoprene Catalyzed by Rare Earth Alkyl Complexes

The mechanism of selective 3,4-polymerization reaction of isoprene catalyzed by the rare earth lutecium（Ⅲ） alkyl complexes [2,6-Me2Ph-N-CH2-C（CH2SiMe3）=N-PhMe2-2,6]Lu（CH2SiMe3）2（THF）was investigated by means of the M06/sdd method with solvation effects taken into account.The results show that the structure of the catalyst core remained almost unchanged as the isoprene molecules were alternatively inserted into the complex at two opposite sides.The Gibbs free energies of the coordination complexes,transition state and intermediates indicate that all the isoprene molecules prefer to insert into the complex with the 3,4-polymerization selectivity as catalyzed by the catalyst,which is consistent with the experimental observations.It is found that the insertion reaction of each isoprene is exothermic,which comes mainly from the coordination of the isoprene molecule to the lutecium（Ⅲ） atom.The solvation effects were confirmed important in predicting the Gibbs free energies of the present reaction system.

Single-atom Fe-N_(5)catalyst for high-performance zinc-air batteries

Developing innovative and efficient non-precious-metal-group(non-PMG)electrocatalysts is crucial for the wide use of zinc-air batteries(ZABs).Herein,a single-atom catalyst(termed as Fe-N-C/rGO SAC)with unique five N-coordinated Fe(Fe-N_(5))centers is prepared by pyrolyzing the composite of zeolitic-imidazolate-frameworks-8(ZIF-8)and graphene oxide(GO).Specifically,the individual Fe site is stabilized by four equatorial and one axial N atoms donated by the N-doped carbon matrix and imidazole ring,respectively,thus forming an asymmetric electron depletion zone over the metal center,which can effectively promote the generation of reactive intermediates and accelerate the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes for ZABs.The rechargeable liquid ZAB with Fe-N-C/rGO catalyst exhibits an extremely high energy density(928.25 Wh·kg^(−1)),a remarkable peak power density(107.12 mW·cm^(−2)),and a long cycle life(400 h).Additionally,the corresponding flexible solid-state ZAB displays superior foldability and remarkable cycling stability.This work provides both experimental and theoretical guidance for rational design of non-PMG electrocatalyst-driven ZABs.