种晶表面粗糙度及边部形态对MPCVD法生长单晶金刚石的影响

针对种晶的表面粗糙度和边部形态对MPCVD法生长金刚石单晶的影响进行了研究。结果表明,当样品表面粗糙度Ra值达到0.0066μm时,单晶金刚石沉积层已经可以呈现出较高的结晶质量。当表面粗糙度Ra值达到0.0162μm后,种晶的中心区域受到的影响较小,但种晶边缘区域的沉积却受到了较明显的影响。研究边部形态的实验中,在同一种晶的不同区域抛磨出45°边棱和90°边棱,生长后分别对这两个区域进行了拉曼光谱测试,测试结果表明,90°边棱处1332 cm-1金刚石本征峰的半高宽较小,沉积层质量较好,初步推测90°是更适合的种晶边棱角度。     

Preparation and enhanced visible light photoelectrochemical activity of g-C3N4/ZnO nanotube arrays

Graphite-like carbon nitride particles were deposited onto ZnO nanotube arrays by thermal polycondenzation and the photoelectrochemical energy conversion property of the g-C₃N₄/ZnO photocathode was investigated. The photocurrent generated by the g-C₃N₄/ZnO composite photocathode is nearly five times as that of g-C₃N₄ and ten times as that of ZnO under visible light irradiation at applied potential of +0.40 V vs. Ag/AgCl electrode. The incident photon to electron conversion efficiency is also greatly enhanced after the modification of g-C₃N₄ nanoparticles onto the ZnO nanotube arrays. In addition, the g-C₃N₄/ZnO electrode exhibits excellent long-term stability. The matching conduction bands and valence bands of g-C₃N₄ and ZnO greatly enhanced the separation and transfer of the photogenerated electrons and holes in the composite, thus the photoelectrochemical performance of the g-C₃N₄/ZnO electrode is improved.     

Isocyanide‐Based Multicomponent Reactions: Concise Synthesis of Spirocyclic Oxindoles with Molecular Complexity by Using a [1,5]‐Hydrogen Shift as the Key Step

A concise multicomponent reaction of isocyanide, α‐substituted allenoate, and methyleneindolinone has been disclosed. This protocol provides a fast and straightforward approach to synthesize unusual tricyclic oxindoles in an efficient and atom‐economic manner. Mechanistically, the present cycloaddition may proceed through a cascade sequence involving double Michael addition, double cyclization, double [1,5]‐hydrogen shift, and group migration. The introduction of a special alkyl group to the allenoate is believed to play a key role in the cascade reaction. This method also features a broad substrate scope, which is particularly useful for the delivery of a large number of compounds.     

Visible‐Light‐Induced CS Bond Activation: Facile Access to 1,4‐Diketones from β‐Ketosulfones

A novel method for the synthesis of 1,4‐diketones from β‐ketosulfones was developed by means of a visible light‐induced C?S bond activation process. Symmetrical and unsymmetrical 1,4‐diketones can be easily prepared in moderate to good yields.     

A 3D 12‐Ring Zeolite with Ordered 4‐Ring Vacancies Occupied by (H2O)2 Dimers

A germanate zeolite, PKU‐14, with a three‐ dimensional large‐pore channel system was structurally characterized by a combination of high‐resolution powder X‐ray diffraction, rotation electron diffraction, NMR, and IR spectroscopy. Ordered Ge₄O₄ vacancies inside the [4⁶.6¹²] cages has been found in PKU‐14, in which a unique (H₂O)₂ dimer was located at the vacancies and played a structure‐directing role. It is the first time that water clusters are found to be templates for ordered framework vacancies.     

Facile Access to cis‐2,6‐Disubstituted Tetrahydropyrans by Palladium‐Catalyzed Decarboxylative Allylation: Total Syntheses of (±)‐Centrolobine and (+)‐Decytospolides A and B

cis‐2,6‐Tetrahydropyran is an important structural skeleton of bioactive natural products. A facile synthesis of cis‐2,6‐disubstituted‐3,6‐dihydropyrans as cis‐2,6‐tetrahydropyran precursors has been achieved in high regio‐ and stereoselectivity with high yields. This reaction involves a palladium‐catalyzed decarboxylative allylation of various 3,4‐dihydro‐2H‐pyran substrates. Extending this reaction to 1,2‐unsaturated carbohydrates allowed the achievement of challenging β‐C‐glycosylation. Based on this methodology, the total syntheses of (±)‐centrolobine and (+)‐decytospolides A and B were achieved in concise steps and overall high yields.     

Synthesis of Single‐Crystalline Spinel LiMn2O4 Nanorods for Lithium‐Ion Batteries with High Rate Capability and Long Cycle Life

The long‐standing challenge associated with capacity fading of spinel LiMn₂O₄ cathode material for lithium‐ion batteries is investigated. Single‐crystalline spinel LiMn₂O₄ nanorods were successfully synthesized by a template‐engaged method. Porous Mn₃O₄ nanorods were used as self‐sacrificial templates, into which LiOH was infiltrated by a vacuum‐assisted impregnation route. When used as cathode materials for lithium‐ion batteries, the spinel LiMn₂O₄ nanorods exhibited superior long cycle life owing to the one‐dimensional nanorod structure, single‐crystallinity, and Li‐rich effect. LiMn₂O₄ nanorods retained 95.6 % of the initial capacity after 1000 cycles at 3C rate. In particular, the nanorod morphology of the spinel LiMn₂O₄ was well‐preserved after a long‐term cycling, suggesting the ultrahigh structural stability of the single crystalline spinel LiMn₂O₄ nanorods. This result shows the promising applications of single‐crystalline spinel LiMn₂O₄ nanorods as cathode materials for lithium‐ion batteries with high rate capability and long cycle life.     

3,3′‐Bi(1,2,4‐oxadiazoles) Featuring the Fluorodinitromethyl and Trinitromethyl Groups

Here we report on the preparation of two hydrogen atom free 3,3′‐bi(1,2,4‐oxadiazole) derivatives. 5,5′‐Bis(fluorodinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole) was synthesised by fluorination of diammonium 5,5′‐bis(dinitromethanide)‐3,3′‐bi(1,2,4‐oxadiazole). For our previously reported analogue 5,5′‐bis(trinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole), a new synthetic route starting from new 3,3′‐bi(1,2,4‐oxadiazolyl)‐5,5′‐diacetic acid was developed. In this course also hitherto unknown 5,5′‐dimethyl‐3,3′‐bi(1,2,4‐oxadiazole) was isolated. The compounds were characterised by multinuclear NMR spectroscopy, IR and Raman spectroscopy, elemental analysis as well as mass spectrometry. X‐ray diffraction studies were performed and the crystal structures for the 5,5'‐dimethyl and 5,5'‐(fluorodinitromethyl) derivatives are reported. The energetic 5,5'‐(fluorodinitromethyl) and 5,5'‐(trinitromethyl) compounds do not contain any hydrogen atoms and show remarkable high densities. Furthermore, the thermal stabilities and sensitivities were determined by differential scanning calorimetry (DSC) and standardised impact and friction tests. The heats of formation were calculated by the atomisation method based on CBS‐4M enthalpies. With these values and the room‐temperature X‐ray densities, several detonation and propulsion parameters, such as the detonation velocity and pressure as well as the specific impulse of mixtures with aluminium, were computed using the EXPLO5 code.