Computational Insights into Different Mechanisms for Ag-, Cu-, and Pd-Catalyzed Cyclopropanation of Alkenes and Sulfonyl Hydrazones

The [2+1] cycloaddition reaction of a metal carbene with an alkene can produce important cyclopropane products for synthetic intermediates, materials, and pharmaceutical applications. However, this reaction is often accompanied by side reactions, such as coupling and self-coupling, so that the yield of the cyclopropanation product of non-silver transition-metal carbenes and hindered alkenes is generally lower than 50 %. To solve this problem, the addition of a low concentration of diazo compound (decomposition of sulfonyl hydrazones) to alkenes catalyzed by either CuOAc or PdCl₂ was studied, but side reactions could still not be avoided. Interestingly, however, the yield of cyclopropanation products for such hindered alkenes were as high as 99 % with AgOTf as a catalyst. To explain this unexpected phenomenon, reaction pathways have been computed for four different catalysts by using DFT. By combining the results of these calculations with those obtained experimentally, it can be concluded that the efficiency of the silver catalyst is due to the barrierless concerted cycloaddition step and the kinetic inhibition of side reactions by a high concentration of alkene.     

A review of recent advances in selective catalytic NOx reduction reactor technologies

Research on NOx treatment is extensive in recent years due to growing environmental awareness. Selec- tive catalytic reduction （SCR） of NOx, as a proven technology, offers higher NOx control efficiency than many other NOx treatment methods. The present work reviews the recent development of SCR reactor technologies. Firstly, catalysts and mechanism of different SCRs were briefly summarized. Different SCR reactors, e.g. structured reactor, fluidized bed reactor and moving bed reactor, were then discussed. As a more advanced technology, multifunctional reactors were also developed for SCR process and could be divided into two categories： decoupled adsorption-reaction process and combined SCR system. The mechanism and properties of these processes were discussed in detail. Some recommendations were given for the future work in SCR reactor design. SCR reactor technology for emerging energy processes was also addressed, such as oxyfuel combustion and biofuel conversion processes, which put forward new requirements for SCR technologies and also open new opportunities for advanced design of SCR reactors.     

Atomic-Scale Dispersed Fe-Based Catalysts Confined on Nitrogen-Doped Graphene for Li-S Batteries: Polysulfides with Enhanced Conversion Efficiency

Lithium-sulfur batteries have been considered as potential electrochemical energy-storage devices owing to their satisfactory theoretical energy density. Nonetheless, the inferior conversion efficiency of polysulfides in essence leads to fast capacity decay during the discharge/charge cycle. In this work, it is successfully demonstrated that the conversion efficiency of lithium polysulfides is remarkably enhanced by employing a well-distributed atomic-scale Fe-based catalyst immobilized on nitrogen-doped graphene (Fe@NG) as a coating of separator in lithium-sulfur batteries. The quantitative electrocatalytic efficiency of the conversion of lithium polysulfides is determined through cyclic voltammetry. It is also proven that the Fe-N_X configuration with highly catalytic activity is quite beneficial for the conversion of lithium polysulfides. In addition, the adsorption and permeation experiments distinctly indicate that the strong anchoring effect, originated from the charge redistribution of N doping into the graphene matrix, inhibits the movement of lithium polysulfides. Thanks to these advantages, if the as-prepared Fe@NG catalyst is combined with polypropylene and applied as a separator (Fe@NG/PP) in Li-S batteries, a high initial capacity (1616 mA h g⁻¹ at 0.1 C), excellent capacity retention (93 % at 0.2 C, 70 % at 2 C), and superb rate performance (820 mA h g⁻¹ at 2 C) are achieved.     

A Tree-valued Markov Process Associated with an Admissible Family of Branching Mechanisms

Let E?R be an interval. By studying an admissible family of branching mechanisms{ψt,t ∈E} introduced in Li [Ann. Probab., 42, 41-79(2014)], we construct a decreasing Levy-CRT-valued process {Tt, t ∈ E} by pruning Lévy trees accordingly such that for each t ∈E, Tt is a ψt-Lévy tree. We also obtain an analogous process {Tt*,t ∈E} by pruning a critical Levy tree conditioned to be infinite. Under a regular condition on the admissible family of branching mechanisms, we show that the law of {Tt,t ∈E} at the ascension time A := inf{t ∈E;Tt is finite} can be represented by{Tt*,t∈E}.The results generalize those studied in Abraham and Delmas [Ann. Probab., 40, 1167-1211(2012)].     

Dodecahedral Au/Pt Nanobowls as Robust Plasmonic Electrocatalysts for Methanol Oxidation under Visible-Light Illumination

Plasmonic nanostructures with large absorption areas under resonant excitation have been utilized extensively in photon-assisted applications. In this work, dodecahedral Au nanobowls were first prepared by an easy and template-free method only through the introduction of H₂PtCl₆ and I⁻ during the growth procedure. The Au nanobowls show electron-field enhancement due to the high curvature of the bowl edge, the open region, and dodecahedral morphology. Au/Pt nanobowls, which couple plasmonic Au and catalytic Pt, were then constructed as plasmonic electrocatalysts for methanol oxidation. The mass activity reached 497.6 mA mg⁻¹ under visible-light illumination, which is 1.9 times that measured in the dark. Simultaneously, the electrocatalytic stability is also greatly improved under light excitation. The enhanced properties of the plasmonic Au/Pt electrocatalysts are ascribed to the synergistic effect of the plasmon-enhanced photothermal and hot-carrier effects on the basis of experimental investigations. This work thus offers an effective methodology to construct efficient plasmonic electrocatalysts for fuel cells.     

AuPt Bipyramid Nanoframes as Multifunctional Platforms for In Situ Monitoring of the Reduction of Nitrobenzene and Enhanced Electrocatalytic Methanol Oxidation

Multifunctional metal nanostructures with a hollow feature, especially for nanoframes, are highly attractive owing to their high surface-to-volume ratios. However, pre-grown metal nanocrystals are always involved during the preparation procedure, and a synthetic strategy without the use of a pre-grown template is still a challenge. In this article, a template-free strategy is reported for the preparation of novel AuPt alloy nanoframes through simply mixing HAuCl₄ and H₂PtCl₆ under mild conditions. The alloy nanostructures show a bipyramid-frame hollow architecture with the existence of only the ten ridges and absence of their side faces. This is the first report of bipyramid-like nanoframes and a template-free method under mild conditions. This configuration merges the plasmonic features of Au and highly active catalytic sites of Pt in a single nanostructure, making it an ideal multifunctional platform for catalyzing and monitoring the catalytic reaction in real time. The superior catalytic activity is demonstrated by using the reduction of nitrobenzene to the corresponding aminobenzene as a model reaction. More importantly, the AuPt nanoframes can track the reduction process on the basis of the SERS signals of the reactants, intermediates, and products, which helps to reveal the reaction mechanism. In addition, the AuPt nanoframes show much higher electrocatalytic properties toward the methanol oxidation reaction than commercial Pt/C electrocatalysts.     

PPh3/I2/HCOOH: An efficient CO source for the synthesis of phthalimides

A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh₃/I₂/HCOOH in the presence of a catalytic amount of Pd(OAc)₂. The reaction results demonstrate that PPh₃/I₂/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80?°C and furnishes the desired products in good to excellent yields.     

Temperature and pH dual‐sensitive polyaspartamide derivatives for antitumor drug delivery

The pH‐sensitive tertiary amino groups were introduced to synthesize temperature and pH dual‐sensitive degradable polyaspartamide derivatives (phe/DEAE‐g‐PHPA) containing pendant aromatic structures and ionizable tertiary amino groups. The thermo/pH‐responsive behavior of phe/DEAE‐g‐PHPA polymer can be tuned by adjusting the graft copolymer composition. Due to the pH sensitivity of the phe/DEAE‐g‐PHPA‐g‐mPEG polymer with hydrophilic long PEG chain, the micelles and the anticancer drug‐loaded micelles were prepared by a quick pH‐changing method without using toxic organic solvent. The obtained polymeric micelles, paclitaxel‐loaded micelles and doxorubicin‐loaded micelles were stable under physiological conditions. Both the drug‐loaded micelles showed much faster release at pH 5 than at pH 7.4. The doxorubicin‐loaded micelles showed obvious and better anticancer activity against both HepG2 and HeLa cells than free doxorubicin. Thus these nontoxic, dual thermo‐ and pH‐sensitive phe/DEAE‐g‐PHPA‐g‐mPEG micelles may be a promising anticancer drug delivery system. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 879–888     

Amorphous Manganese–Cobalt Nanosheets as Efficient Catalysts for Hydrogen Evolution Reaction (HER)

Catalysis Surveys from Asia - A facile and efficient electrocatalyst for hydrogen evolution reaction (HER) to produce hydrogen is very important for future energy. In this paper, amorphous...