Nickel‐Promoted Highly Regioselective Carboxylation of Aryl Ynol Ether and Its Application to the Synthesis of Chiral β‐Aryloxypropionic Acid Derivatives

Nickel(0)‐promoted carboxylation of aryl ynol ether proceeded in a highly regioselective manner to produce α‐substituted‐β‐aryloxyacrylic acid derivatives. The α‐substituted‐β‐aryloxyacrylic acids were transformed into the corresponding β‐aryloxypropionic acid derivative as an optically active form via rhodium‐catalyzed asymmetric hydrogenation.     

Electrocatalytic Carbon Dioxide Reduction by Using Cationic Pentamethylcyclopentadienyl–Iridium Complexes with Unsymmetrically Substituted Bipyridine Ligands

Eight [Ir(bpy)Cp*Cl]⁺‐type complexes (bpy= bipyridine, Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) containing differently substituted bipyridine ligands were synthesized and characterized. Cyclic voltammetry (CV) of the complexes in Ar‐saturated acetonitrile solutions showed that the redox behavior of the complexes could be fine tuned by the electronic properties of the substituted bipyridine ligands. Further CV in CO₂‐saturated MeCN/H₂O (9:1, v/v) solutions showed catalytic currents for CO₂ reduction. In controlled potential electrolysis experiments (MeCN/MeOH (1:1, v/v), E_app=?1.80 V vs Ag/AgCl), all of the complexes showed moderate activity in the electrocatalytic reduction of CO₂ with good stability over at least 15 hours. This electrocatalytic process was selective toward formic acid, with only traces of dihydrogen or carbon monoxide and occasionally formaldehyde as byproducts. However, the turnover frequencies and current efficiencies were quite low. No direct correlation between the redox potentials of the complexes and their catalytic activity was observed.     

Porous carbon nanospheres with moderately oriented domains for EDLC electrode

Porous carbon nanospheres with moderately oriented microcrystalline structures were prepared via a relatively simple synthetic route in this article. CTAB acted as a structure‐directing agent to induce small sulfonated pitch (SP) pieces to assemble orderly. By this means, the formation of carbon nanospheres was simultaneous with the moderate orientation of carbon microcrystalline without additional process. Owing to the moderately oriented microcrystalline structures, the resultant sample CNS3 possessed a high e‐conductivity of 62.5 S/m. When used as an electrode material for EDLCs, it showed excellent electrochemical properties even without any conductive agent. In an organic electrolyte, the resultant sample CNS3 possessed a high specific capacitance of 155 F/g at 20 A/g and outstanding cycle life with 94.2% capacity retention after 10,000 cycles. This work puts forward a novel design for carbon nanospheres with moderately oriented domains by a simple and energy‐efficient means.     

Molecular-Based Design of Microporous Carbon Nanosheets

Microporous carbons afford high surface areas, large pore volumes, and good conductivity, and are fascinating over a wide range of applications. Traditionally synthesized microporous carbon materials usually suffer from some limitations, such as poor accessibility and slow mass transport of molecules due to the micrometer-scale diffusion pathways and space confinement imposed by small pore sizes. Two-dimensional microporous carbon materials, denoted as microporous carbon nanosheets (MCNs), possess nanoscale thickness, which allows fast mass and heat transport along the z axis; thus overcoming the drawbacks of their bulk counterparts. Herein, recent breakthroughs in the synthetic strategies for MCNs are summarized. Three typical methods are discussed in detail with several examples: pyrolysis of organic precursors with 2D units, a templating method that uses wet chemistry, and the molten salt method. Among them, molecular-based assembly of MCNs in the liquid phase shows more controllable morphology, thickness, and pore size distribution. Finally, challenges in this research area are discussed to inspire future explorations.     

Strongly localized states in a single carbon nanotube with polymer molecules

A single-walled carbon nanotube (SWCNT) with conjugated polymer molecules is analyzed via optical spectroscopy. The presence of strongly localized excitonic states in the SWCNT is confirmed using time-integrated photoluminescence (PL). The PL spectrum exhibits extremely narrow width (~0.8 meV) which is attributed to the strong confinement of the states by polymer molecules. In addition, I observed that the excited states are gradually filled as a function of the excitation power, which supports the localized excitonic behavior. Only the ground excitonic state is observed at low excitation powers, but three additional PL peaks appear as the excitation power is increased. Especially, the power-dependent PL spectrum shows a blueshift and increased width, which can be elucidated in terms of quantum confined stark effect and the screening of induced electric fields. Overall, I demonstrate that the presence of polymer molecules induces several localized states in a single SWCNT.     

浮升力和流动加速对超临界CO2管内流动传热影响

基于单相流体的概念,超临界流体的异常传热行为已经被研究很多年了,但是关于其流动传热机理仍没有统一的认识.本文通过理论分析和实验研究了超临界二氧化碳在竖直管内向上流动过程中,浮升力和流动加速效应对其流动结构和传热过程的影响.结果表明,没有确凿的实验证据表明超临界流体的异常传热行为是浮升力和流动加速直接导致的,存在的估计浮升力和流动加速效应准则均是在常物性流体的基础上,做了大量假设得出的,不同的研究者采用浮升力和流动加速准则分析超临界流体的传热恶化得出的结论不一致.最后,基于拟沸腾理论分析超临界流体的传热恶化过程,提出超临界沸腾数区分了超临界流体正常传热与恶化传热的转换边界,为超临界流体流动传热研究提供新思路,超临界沸腾数对建立用于不同技术的超临界流体动力循环的最佳运行条件具有重要意义.     

Facile sonochemical synthesis of rutile-type titanium dioxide microspheres decorated graphene oxide composite for efficient electrochemical sensor

In this reports the facile and green synthesis of rutile-type titanium dioxide nanoparticles decorated graphene oxide nanocomposite via the ultrasonication process (frequency: 50 kHz, Power: 100 W/cm² and Ultrasonic type: Ti-horn). Because, the sonochemical synthesis method is simple, non-explosive and harmless method than other conventional technique. Furthermore, the synthesized material was characterized by various analytical techniques including FESEM, EDX, XRD, EIS and electrochemical methods. Then, the synthesized TiO₂ MPs@GOS composite was applied for the electrocatalytic detection of theophylline (TPL) using CV and amperometric (current-time) techniques. Captivatingly, the modified sensor has excellent electrocatalytic performance with the wider linear range from 0.02 to 209.6 µM towards the determination of theophylline and the LOD and sensitivity of the modified sensor was calculated as 13.26 nM and 1.183 μA·µM⁻¹·cm⁻², respectively. In addition, a selectivity, reproducibility and stability of the TiO₂ MPs@GOS modified GCE were analyzed towards the determination of theophylline molecule. Finally, the real time application of TiO₂ MPs@GOS modified theophylline sensor was established in serum and drug samples.     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).