Defect-Rich Amorphous Iron-Based Oxide/Graphene Hybrid-Modified Separator toward the Efficient Capture and Catalysis of Polysulfides.

The sluggish sulfur reduction reaction, severe shuttle effect, and poor conductivity of sulfur species are three main problems in lithium-sulfur (Li-S) batteries. Functional materials with a strong affinity and catalytic effect toward polysulfides play a key role in addressing these issues. Herein, we report a defect-rich amorphous a-Fe3O4-x/GO material with a nanocube-interlocked structure as an adsorber as well as an electrocatalyst for the Li-S battery. The composition and defect structure of the material are determined by X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy measurements. The distinctive open framework architecture of the as-engineered composite inherited from the metal-organic framework precursor ensures the stability and activity of the catalyst during extended cycles. The oxygen defects in the amorphous structure are capable of absorbing polysulfides and similarly work as catalytic centers to boost polysulfide conversion. Taking advantage of a-Fe3O4-x/GO on the separator surface, the Li-S battery shows a capacity over 610 mA h g-1 at 1 C and a low decay rate of 0.12% per cycle over 500 cycles and superior rate capability. The functional material made via the low-cost synthesis process provides a potential solution for advanced Li-S batteries.

DFT study on the reaction mechanisms and stereoselectivities of NHC-catalyzed [2 + 2] cycloaddition between arylalkylketenes and electron-deficient benzaldehydes.

In this paper, two possible mechanisms (mechanisms A and B) on the stereoselective [2 + 2] cycloaddition of aryl(alkyl)ketenes and electron-deficient benzaldehydes catalyzed by N-heterocyclic carbenes (NHCs) have been investigated using density functional theory (DFT). Our calculated results indicate that the favorable mechanism (mechanism A) includes three processes: the first step is the nucleophilic attack on the arylalkylketene by the NHC catalyst to form an intermediate, the second step is the [2 + 2] cycloaddition of the intermediate and benzaldehyde for the formation of a ß-lactone, and the last step is the dissociation of the NHC catalyst and the ß-lactone. Notably, the [2 + 2] cycloaddition, in which two chiral centers associated with four configurations (SS, RR, SR and RS) are formed, is demonstrated to be both the rate- and stereoselectivity-determining step. Moreover, the reaction pathway associated with the SR configuration is the most favorable pathway and leads to the main product, which is in good agreement with the experimental results. Furthermore, the analysis of global and local reactivity indexes has been performed to explain the role of the NHC catalyst in the [2 + 2] cycloaddition reaction. Therefore, this study will be of great use for the rational design of more efficient catalysts for this kind of cycloaddition.