XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

甲烷-二氧化碳重整制合成气与现代分析技术应用于探究性化工专业实验的设计与探索

以甲烷-二氧化碳重整制合成气为实例，设计探究性实验，将合成气的制备和现代分析技术应用于化工专业实验的教学实践中以提高学生的创新和实践能力。实验包括催化剂的制备，催化剂的性能评价和催化剂的表征等3大部分。采用工业最常用的浸渍法制备含有不同助剂的Ni/X/γ-Al2O3（X为Co，Fe，MgO，CeO2）催化剂，以甲烷-二氧化碳重整反应评价其催化性能，并采用XRD、H2-TPR、BET和TG对催化剂的微观结构进行表征。结合催化剂的性能评价结果和表征结果，探讨不同助剂对镍基催化剂性能的改善效果及机制。通过开设该实验，可以让学生了解化工学科的前沿知识以及现代分析技术的基本原理和用途，掌握专业的实验操作、数据处理和谱图绘制方法，提高学生的专业素养和综合能力。     

Advanced Li-Ion Batteries with High Rate,Stability, and Mass Loading Based on Graphene Ribbon Hybrid Networks

To optimize the cycle life and rate performance of lithium-ion batteries (LIBs), ultra-fine Fe₂O₃ nanowires with a diameter of approximately 2 nm uniformly anchored on a cross-linked graphene ribbon network are fabricated. The unique three-dimensional structure can effectively improve the electrical conductivity and facilitate ion diffusion, especially cross-plane diffusion. Moreover, Fe₂O₃ nanowires on graphene ribbons (Fe₂O₃/GR) are easily accessible for lithium ions compared with the traditional graphene sheets (Fe₂O₃/GS). In addition, the well-developed elastic network can not only undergo the drastic volume expansion during repetitive cycling, but also protect the bulk electrode from further pulverization. As a result, the Fe₂O₃/GR hybrid exhibits high rate and long cycle life Li storage performance (632 mAh g⁻¹ at 5 A g⁻¹, and 471 mAh g⁻¹ capacity maintained even after 3000 cycles). Especially at high mass loading (≈4 mg cm⁻²), the Fe₂O₃/GR can still deliver higher reversible capacity (223 mAh g⁻¹ even at 2 A g⁻¹) compared with the Fe₂O₃/GS (37 mAh g⁻¹) for LIBs.     

Improvement of capacitance activity for Cu‐doped Ni‐based metal–organic frameworks by adding potassium hexacyanoferrate into KOH electrolyte

Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K₃[Fe(CN)₆] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni_2.6Cu_0.4 MOFs material shows the highest specific capacitance (1282 F g^?1 at 1 A g^?1 in mixed 2 M KOH and 0.1 M K₃[Fe(CN)₆]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production.     

Al2O3衬底无催化剂生长GaN纳米线及其光学性能

采用一种绿色的等离子增强化学气相沉积法,以Al2O3为衬底, Ga金属为镓源, N2为氮源,在不采用催化剂的情况下,成功制备获得了结晶质量良好的GaN纳米线.研究表明,生长温度可显著调控GaN纳米线的形貌,当反应温度为950℃时,生长出的GaN微米片为六边形;当反应温度为1000℃时,生长出了长度为10-20μm的超长GaN纳米线.随着反应时间增加, GaN纳米线的长度增加. GaN纳米线内部存在着压应力,应力大小为0.84 GPa.同时,也进一步讨论了GaN纳米线无催化剂生长机制. GaN纳米线光致发光结果显示, GaN纳米线缺陷较少,结晶质量良好,在360 nm处有一个较为尖锐的本征发光峰,可应用于紫外激光器等光电子器件.本研究结果将为新型光电器件低成本绿色制备提供一个可行的技术方案.     

Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Ni–Al composite hydroxides fabricated by cation–anion double hydrolysis method for high-performance supercapacitor

Chemical doping of nickel hydroxide with other cations(e.g. Al~(3+)) is an efficient way to enhance its electrochemical capacitive performances. Herein, a simple cation–anion(Ni~(2+)and AlO_2) double hydrolysis method was developed toward the synthesis of nickel–aluminum(Ni–Al) composite hydroxides. The obtained composite hydroxides possesses a porous structure, large surface area(121 m~2/g) and homogeneous element distribution. The electrochemical test shows that the obtained composite hydroxides exhibits a superior supercapacitive performances(specific capacitance of 1670F/g and rate capability of 87% from 0.5 A/g to 20 A/g) to doping-free nickel hydroxide(specific capacitance of 1227 F/g and rate capability of 47% from 0.5 A/g to 20 A/g). Moreover, the galvanostatic charge/discharge test displays that after 2000 cycles at large current density of 10 A/g, the composite hydroxides achieves a high capacitance retention of 98%, indicative of an excellent electrochemical cycleability.     

“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study

The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni⁰/Ni^II cycle is operative in this system.     

Click Chemistry Mediated Functionalization of Vertical Nanowires for Biological Applications

Semiconductor nanowires (NWs) are gaining significant importance in various biological applications, such as biosensing and drug delivery. Efficient and controlled immobilization of biomolecules on the NW surface is crucial for many of these applications. Here, we present for the first time the use of the Cu^I‐catalyzed alkyne–azide cycloaddition and its strain‐promoted variant for the covalent functionalization of vertical NWs with peptides and proteins. The potential of the approach was demonstrated in two complementary applications of measuring enzyme activity and protein binding, which is of general interest for biological studies. The attachment of a peptide substrate provided NW arrays for the detection of protease activity. In addition, green fluorescent protein was immobilized in a site‐specific manner and recognized by antibody binding to demonstrate the proof‐of‐concept for the use of covalently modified NWs for diagnostic purposes using minute amounts of material.