Phase Modulating of Cu–Ni Nanowires Enables Active and Stable Electrocatalysts for the Methanol Oxidation Reaction

The design and development of non-noble metal alternatives with superior performance and promising long-term stability that is comparable or even better than those of noble-metal-based catalysts is a significant challenge. Here, we report the thermal-induced phase engineering of non-noble-metal-based nanowires with superior electrochemical activity and stability for the methanol oxidation reaction (MOR) under alkaline conditions. The optimized Cu–Ni nanowires deliver an unprecedented mass activity of 425 mA mg⁻¹, which is 4.3 times higher than that of the untreated one. Detailed catalytic investigations show that the enhanced performance is due to the large active area, the increased number of active sites (NiOOH), and fast methanol electrooxidation kinetics. In addition, the generated hollow feature in the nanowires provides a unique void space to release the volume expansion, where the activity can be maintained for 5 h without a distinct activity decay. The present work emphasizes the importance of precisely phase modulating of nanomaterials for the design of non-noble metal electrocatalysts towards the MOR, which opens up a new pathway for the design of cost-effective electrocatalysts with promising activity and long-term stability.     

Interfacial Synthesis of a Monolayered Fluorescent Two-Dimensional Polymer through Dynamic Imine Chemistry

A fluorescent monolayered two-dimensional polymer (2DP) containing both tetraphenylethylene (TPE) and imine linkages is synthesized at air-water interface using the Langmuir-Blodgett method. We designed TPE-based monomers with long distances between the TPE and the imine linkages to avoid the charge transfer and therefore keep the fluorescence. A monolayered 2DP provided with more than 104 μm² in domain size and around 0.8 nm thickness was obtained through a successive Schiff base reaction at air-water interface. The nanostructures and fluorescent property of 2DP films were characterized by optical microscopy, SEM, TEM, AFM and fluorescence spectrum. Most importantly, the tip-enhanced Raman spectroscopy (TERS) was utilized here to confirm the success of the polycondensation of monolayered 2DP.     

Effects of top confinement and diluents on morphology in crystallization of poly(l‐lactic acid) interacting with poly(ethylene oxide)

Effects of top confinement and diluent poly(ethylene oxide) (PEO) on poly(l ‐lactic acid) (PLLA) crystal morphology have been investigated. When crystallized at 120 °C, uncovered neat PLLA sample exhibits higher growth rate ringless spherulites; while the covered sample exhibits lower growth rate ring‐banded spherulites. As PEO is introduced into PLLA, the morphology also undergoes significant changes. For the same T_c,PLLA = 120 °C, the PEO/PLLA blend with PEO composition greater than 25% exhibits ring‐banded patterns even in uncovered sample. However, in much greater PEO composition (>80 wt %), uncovered samples exhibit ring bands diverging into dendritic patterns, while top covered samples tend to maintain the spiral ring‐band patterns. Both PEO inclusion in PLLA and top cover on films impose growth kinetic alterations. Additionally, the top glass cover tends to prevent the lower surface tension PLLA to be accumulated on the surface, resulting in the formation of ring‐band pattern. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1160–1170     

New Crown Ether of Mahonia fortunei

Chemistry of Natural Compounds - A new 24-crown 8-ether, namely mahoniafortunin (1) was isolated from the leaves of Mahonia fortunei (Lindl.) Fedde (Berberidaceae). The structure of the new crown...     

Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).