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971.
Biao Xu Peilei He Huiling Liu Pengpeng Wang Prof. Dr. Gang Zhou Prof. Dr. Xun Wang 《Angewandte Chemie (International ed. in English)》2014,53(9):2339-2343
Multidimensional nano‐heterostructures (NHSs) that have unique dimensionality‐dependent integrative and synergic effects are intriguing but still underdeveloped. Here, we report the first helical 1D/2D epitaxial NHS between CdS and ZnIn2S4. Experimental and theoretical studies reveal that the mismatches in lattice and dangling bonds between 1D and 2D units govern the growth procedure. The resulting well‐defined interface induces the delocalized interface states, thus facilitate the charge transfer and enhance the performance in the photoelectrochemical cells. We foresee that the mechanistic insights gained and the electronic structures revealed would inspire the design of more complex 1D/2D NHSs with outstanding functionalities. 相似文献
972.
Pumping through Porous Hydrophobic/Oleophilic Materials: An Alternative Technology for Oil Spill Remediation 下载免费PDF全文
Jin Ge Yin‐Dong Ye Hong‐Bin Yao Xi Zhu Xu Wang Liang Wu Jin‐Long Wang Prof. Hang Ding Prof. Ni Yong Prof. Ling‐Hui He Prof. Dr. Shu‐Hong Yu 《Angewandte Chemie (International ed. in English)》2014,53(14):3612-3616
Recently, porous hydrophobic/oleophilic materials (PHOMs) have been shown to be the most promising candidates for cleaning up oil spills; however, due to their limited absorption capacity, a large quantity of PHOMs would be consumed in oil spill remediation, causing serious economic problems. In addition, the complicated and time‐consuming process of oil recovery from these sorbents is also an obstacle to their practical application. To solve the above problems, we apply external pumping on PHOMs to realize the continuous collection of oil spills in situ from the water surface with high speed and efficiency. Based on this novel design, oil/water separation and oil collection can be simultaneously achieved in the remediation of oil spills, and the oil sorption capacity is no longer limited to the volume and weight of the sorption material. This novel external pumping technique may bring PHOMs a step closer to practical application in oil spill remediation. 相似文献
973.
Alkyl Ammonium Cation Stabilized Biocidal Polyiodides with Adaptable High Density and Low Pressure 下载免费PDF全文
Dr. Chunlin He Dr. Damon A. Parrish Prof. Dr. Jean'ne M. Shreeve 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6699-6706
The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high‐temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine‐rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3?, I5?, which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm?3 that are low‐pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0–90.9 %. 相似文献
974.
975.
Yong‐Gang Zhang Xiang‐Lei Liu Zeng‐Yang He Xi‐Ming Li Hong‐Jian Kang Prof. Dr. Shi‐Kai Tian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2765-2769
An unprecedented oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed under aerobic conditions for the stereoselective synthesis of 1,2‐disubstituted alkenes. A range of aroyl hydrazides underwent palladium/copper‐catalyzed oxidative Mizoroki–Heck reaction with terminal alkenes open to air in a 1:1 mixture of dimethyl sulfoxide and acetonitrile to give structurally diverse 1,2‐disubstituted alkenes in moderate to excellent yields with excellent regio‐ and E‐selectivity. The reaction tolerated a wide variety of functional groups, such as alkoxy, hydroxy, amino, fluoro, chloro, bromo, cyano, nitro, ester, amide, imide, phosphine oxide, and sulfone groups, and, moreover, molecular oxygen and dimethyl sulfoxide were demonstrated to serve as terminal oxidants. This study provides a useful method for the stereoselective synthesis of 1,2‐disubstituted alkenes through direct transformation of the vinylic C?H bonds in terminal alkenes. 相似文献
976.
Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation 下载免费PDF全文
Li‐Hua Tian Jing‐Heng Meng Dr. Xiao‐Nan Wu Dr. Yan‐Xia Zhao Dr. Xun‐Lei Ding Prof. Dr. Sheng‐Gui He Dr. Tong‐Mei Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1167-1175
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation. 相似文献
977.
Cerium‐Based M4L4 Tetrahedra as Molecular Flasks for Selective Reaction Prompting and Luminescent Reaction Tracing 下载免费PDF全文
Yang Jiao Dr. Jian Wang Dr. Pengyan Wu Liang Zhao Dr. Cheng He Jing Zhang Prof. Chunying Duan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2224-2231
The application of metal–organic polyhedra as “molecular flasks” has precipitated a surge of interest in the reactivity and property of molecules within well‐defined spaces. Inspired by the structures of the natural enzymatic pockets, three metal–organic neutral molecular tetrahedral, Ce‐TTS, Ce‐TNS and Ce‐TBS (H6TTS: N′,N′′,N′′′‐nitrilotris‐4,4′,4′′‐(2‐hydroxybenzylidene)‐benzohydrazide; H6TNS: N′,N′′,N′′′‐nitrilotris‐6,6′,6′′‐(2‐hydroxybenzylidene)‐2‐naphthohydrazide; H6TBS: 1,3,5‐ phenyltris ‐4,4′,4′′‐(2‐hydroxybenzylidene)benzohydrazide), which exhibit different size of the edges and cavities, were achieved through self‐assembly by incorporating robust amide‐containing tridentate chelating sites into the fragments of the ligands. They acted as molecular flasks to prompt the cyanosilylation of aldehydes with excellent selectivity towards the substrates size. The amide groups worked as trigger sites and catalytic driven forces to achieve efficient guest interactions, enforcing the substrates proximity within the cavity. Experiments on catalysts with the different cavity radii and substrates with the different molecular size demonstrated that the catalytic performance exhibited enzymatical catalytic mechanism and occurred in the molecular flask. These amides were also able to amplify guest‐bonding events into the measurable outputs for the detection of concentration variations of the substrates, providing the possibility for metal–organic hosts to work as smart molecular flasks for the luminescent tracing of catalytic reactions. 相似文献
978.
Unravelling the Relationship between Raman Enhancement and Photocatalytic Activity on Single Anisotropic Au Microplates 下载免费PDF全文
Yudie Sun Dr. Honglin Liu Dr. Fei Zhou Liangbao Yang Dr. Shengnan He Bai Sun Jinhuai Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10414-10424
Anisotropic noble‐metal structures are attracting increasing attention because of interesting size‐ and shape‐dependent properties and have emerging applications in the fields of optics and catalysis. However, it remains a significant challenge to overcome chemical contributions and acquire molecular insight into the relationship between Raman enhancement and photocatalytic activity. This study gives visualized experimental evidence of the anisotropic spatial distribution of Raman signals and photocatalytic activity at the level of single nanometer‐thin Au microtriangles and microhexagons. Theoretical simulations indicate an anisotropic spatial distribution and sharpness‐dependent strength of the electric‐field enhancement. Analysis by using statistical surface‐enhanced Raman scattering (SERS) supports this view, that is, Raman enhancement is on the order of corner>edge>face for a single microplate, but SERS measurements at different depths of focus also imply a concentration‐dependent feature of SERS signals, especially at the corners and edges. Similarly, the SERS signals of product molecules in plasmonic photocatalysis also exhibit asymmetrical strengths at different corners of the same microplate. However, by examining the variations in the relative intensities of the SERS peaks, the difference in the photocatalytic activities at the corners, edges, and faces has been successfully calculated and is highly consistent with electric‐field simulations, thus indicating that an increased number of molecules adsorbed at specific sites does not necessarily lead to a higher conversion ratio in noble‐metal photocatalysis. Our strategy weakens the assumed impact of plasmonic local heating and, to a certain extent, excludes the influence of concentration effects and chemical contributions in noble‐metal photocatalysis, thus clearly profiling plasmon‐related characteristics. This study also promises a new research direction to understand the enhancement mechanism of SERS‐active structures. 相似文献
979.
Zi‐Yu Li Zhen Yuan Dr. Yan‐Xia Zhao Prof. Dr. Sheng‐Gui He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):4163-4169
Metal carbide species have been proposed as a new type of chemical entity to activate methane in both gas‐phase and condensed‐phase studies. Herein, methane activation by the diatomic cation MoC+ is presented. MoC+ ions have been prepared and mass‐selected by a quadrupole mass filter and then allowed to interact with methane in a hexapole reaction cell. The reactant and product ions have been detected by a reflectron time‐of‐flight mass spectrometer. Bare metal Mo+ and MoC2H2+ ions have been observed as products, suggesting the occurrence of ethylene elimination and dehydrogenation reactions. The branching ratio of the C2H4 elimination channel is much larger than that of the dehydrogenation channel. Density functional theory calculations have been performed to explore in detail the mechanism of the reaction of MoC+ with CH4. The computed results indicate that the ethylene elimination process involves the occurrence of spin conversions in the C?C coupling (doublet→quartet) and hydrogen atom transfer (quartet→sextet) steps. The carbon atom in MoC+ plays a key role in methane activation because it becomes sp3 hybridized in the initial stages of the ethylene elimination reaction, which leads to much lower energy barriers and more stable intermediates. This study provides insights into the C?H bond activation and C?C coupling involved in methane transformation over molybdenum carbide‐based catalysts. 相似文献
980.
α‐Fe2O3 Cubes with High Visible‐Light‐Activated Photoelectrochemical Activity towards Glucose: Hydrothermal Synthesis Assisted by a Hydrophobic Ionic Liquid 下载免费PDF全文
Dr. Li Xu Dr. Jiexiang Xia Prof. Leigang Wang Dr. Jing Qian Prof. Huaming Li Prof. Kun Wang Dr. Kaiyong Sun Prof. Minqiang He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2244-2253
A liquid/liquid interfacial reaction system was designed to fabricate α‐Fe2O3 cubes. The reaction system uses a hydrophobic ionic liquid containing iron ions ([(C8H17)2(CH3)2N]FeCl4) for manufacturing α‐Fe2O3 cubes by a novel and environmentally friendly hydrothermal method under low‐temperature conditions (140 °C). The iron‐containing ionic liquid is hydrophobic and can form a liquid/liquid interface with water, which is vital for fabrication of the α‐Fe2O3 cubes. Nanomaterials synthesized from hydrophobic iron‐containing ionic liquids show good crystallinity, well‐developed morphology, and uniform size. The effect of different ionic liquids on the morphology of α‐Fe2O3 was investigated in detail. [(C8H17)2(CH3)2N]FeCl4 is assumed to perform the triple role of forming a liquid/liquid interface with water and acting as reactant and template at the same time. The effect of the reaction temperature on the formation of the α‐Fe2O3 cubes was also studied. Temperatures lower or higher than 140 °C are not conducive to formation of the α‐Fe2O3 cubes. Their photoelectrochemical properties were tested by means of the transient photocurrent response of electrodes modified with as‐prepared α‐Fe2O3 cubes. The photocurrent response of an α‐Fe2O3 cubes/indium tin oxide electrode is high and stable, and it shows great promise as a photoelectrochemical glucose sensor with high sensitivity and fast response, which are beneficial to practical applications of nanosensors. 相似文献