The development of Li−S batteries is largely impeded by the complicated shuttle effect of lithium polysulfides (LiPSs) and sluggish reaction kinetics. In addition, the low mass loading/utilization of sulfur is another key factor that makes Li−S batteries difficult to commercialize. Here, a porous catalytic V 2 O 3 / V 8 C 7 @carbon composite derived from MIL-47 (V) featuring heterostructures is reported to be an efficient polysulfide regulator in Li−S batteries, achieving a substantial increase in sulfur loading while still effectively suppressing the shuttle effect and enhancing kinetics. Systematic mechanism analyses suggest that the LiPSs strongly adsorbed on the V 2 O 3 surface can be rapidly transferred to the V 8 C 7 surface through the built-in interface for subsequent reversible conversion by an efficient catalytic effect, realizing enhanced regulation of LiPSs from capture to conversion. In addition, the porous structure provides sufficient sulfur storage space, enabling the heterostructures to exert full efficacy with a high sulfur loading. Thus, this S−V 2 O 3 /V 8 C 7 @carbon@graphene cathode exhibits prominent rate performance (587.6 mAh g −1 at 5 C) and a long lifespan (1000 cycles, 0.017% decay per cycle). It can still deliver superior electrochemical performance even with a sulfur loading of 8.1 mg cm −2 . These heterostructures can be further applied in pouch cells and produce stable output at different folding angles (0−180°). More crucially, the cells could retain 4.3 mAh cm −2 even after 150 cycles, which is higher than that of commercial lithium-ion batteries (LIBs). This strategy for solving the shuttle effect under high sulfur loading provides a promising solution for the further development of high-performance Li−S batteries.

cm/GW, larger than that of conventional semiconductors by a factor of 10 3 . As a result of TPA, two-photon pumped frequency up-converted luminescence is observed directly in the monolayer MoS2. For the multilayer MoS2, the SA response is demonstrated with the ratio of the excited-state absorption cross section to ground-state cross section of ∼0.18. In addition, the laser damage threshold of the monolayer MoS2 is ∼ 97 GW/cm 2 , larger than that of the multilayer MoS2 of ∼78 GW/cm 2 .2

Enantioselective α-functionalizations of carbonyl compounds are fundamental transformations for the asymmetric synthesis of organic compounds. One of the more recent developments along this line is in aminocatalysis, which leads to the direct α-functionalization of simple aldehydes and ketones. However, most of the advances have been achieved with linear aldehydes and ketones as substrates. Effective aminocatalysis with α-branched carbonyls, particularly α-branched ketones, has remained elusive. The primary difficulty arises from the space-demanding α-substituent, which impedes iminium/enamine formation. In 2005, synthetic organic chemists revived catalysis using primary amines, which brought new attention to these challenges, because of the conformational flexibility of primary amines. On the basis of early biomimetic studies by Hine, in 2007 we developed the bioinspired chiral primary amine catalysts featuring primary-tertiary diamines. This type of catalyst involves enamine/iminium catalysis, and we could apply this chemistry to all of the major types of ketones and aldehydes. In this Account, we present research from our laboratory that significantly expands aminocatalysis to include α-branched ketones such as β-ketocarbonyls and α-substituted vinyl ketones. Our primary amine catalysis methodology, when used alone or in conjunction with metal catalysts, provides convenient access to both enantiopure α-tertiary and quaternary ketones, structures that are not available via other approaches. Our mechanistic studies showed that acidic additives play the critical role in facilitating catalytic turnover, most likely by shuttling protons during the enamine/iminium tautomerizations. These additives are also critical to induce the desired stereochemistry via ammonium N-H hydrogen bonding. Proton transfer by shuttling is also stereoselective, resulting in enantioselective enamine protonation as observed in the reactions of α-substituted vinyl ketones. In addition, we have carried out density functional theory studies that help to delineate the origins of the stereoselectivity in these reactions.

Cooperite, or platinum sulfide (PtS), is a rare mineral that generally exists as microscale, irregularly shaped crystallites. The presence of impurities, in both naturally occurring and synthesized samples, has hindered the study of its optical properties in the past. In this work, we prepare large-scale, uniform PtS films in bulk to two-dimensional form through the thermally assisted conversion method. An abnormal trend is observed in linear spectral studies whereby the optical bandgap narrows as the film thickness decreases. A model based on the continuous distribution of carriers in real space, which can be regarded as a quantum well normal to the plane, is used to describe the thickness-dependent carrier recombination phenomenon. In the nonlinear optical measurements, PtS exhibits ultrafast saturable absorption and self-defocusing properties in the visible region, which are dominated by the resonant electronic nonlinearities.

Selective H transfer by ABC: A new asymmetric binary acid catalyst was developed to promote 1,5-H transfer specifically and stereoselectively in tert-aminocyclization reactions with excellent activity, high enantioselectivity, and broad substrate scope. The H atom (in red) was proven to transfer through a stereospecific suprafacial pathway (see scheme).

Enamine protonation: A chiral diamine catalyzes an asymmetric Friedel–Crafts reaction through catalytic enantioselective protonation of an enamine. This process can be applied to a range of α‐substituted acroleins and indoles with high yields of products and high enantioselectivity (up to 94 % ee). An OH/π interaction between H2O and the indole ring was found to play an important role in the transition state (see scheme).

Enamines are electron-rich compounds bearing intriguing redox properties. Herein, a series of secondary enamines condensed from primary amine and β-ketocarbonyls were synthesized and their electrochemical oxidation properties were systematically studied by cyclic voltammetry. Furthermore, theoretical calculation of oxidation potentials of enamines, particularly those catalytic intermediates, was also conducted to further broaden the scope investigated. Possible structural factors on oxidation and the nature of the resulted radical cation intermediates were revealed and discussed. Correlation of redox potentials with molecular properties such as highest occupied molecular orbital energies and natural population analysis charge were explored, and there appears no simple linear correlation. On the other hand, a good correlation with Mayr's nucleophilicity parameter N was noted among a range of catalytically relevant enamines. Spin population analysis disclosed that enamine radical cations mainly exhibit the carbon-center free radical feature. Taking experimental and computation data together, a comprehensive picture about the redox property of enamines is presented, which would provide guidance in the development of oxidative enamine catalysis and transformations.

The energy performance of solid energetic materials (Al, Mg, etc.) is typically restricted by a natural passivation layer and the diffusion-limited kinetics between the oxidizer and the metal. In this work, we use polytetrafluoroethylene (PTFE) as the fluorine carrier and the shielding layer to construct a new type of nano-Al based fuels. The PTFE shell not only prevents nano-Al layers from oxidation, but also assists in enhancing the reaction kinetics, greatly improving the stability and reactivity of fuels. An in situ chemical vapor deposition combined with the electrical explosion of wires (EEW) method is used to fabricate core-shell nanostructures. Studies show that by controlling the stoichiometric ratio of the precursors, the morphology of the PTFE shell and the energy performance can be easily tuned. The resultant composites exhibit superior energy output characters than that of their physically mixed Al/PTFE counterparts. This synthetic strategy might provide a general approach to prepare other high-energy fuels (Mg, Si).