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991.
Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity 下载免费PDF全文
Neng‐Fei Yu Dr. Na Tian Dr. Zhi‐You Zhou Long Huang Jing Xiao Yu‐Hua Wen Prof. Shi‐Gang Sun 《Angewandte Chemie (International ed. in English)》2014,53(20):5097-5101
Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO. 相似文献
992.
Synthesis of Chiral Exocyclic Amines by Asymmetric Hydrogenation of Aromatic Quinolin‐3‐amines 下载免费PDF全文
Xian‐Feng Cai Ran‐Ning Guo Mu‐Wang Chen Lei Shi Prof. Yong‐Gui Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7245-7248
Asymmetric hydrogenation of aromatic quinolin‐3‐amines was successfully developed with up to 94 % enantiomeric excess (ee). Introduction of the phthaloyl moiety to the amino group is crucial to eliminate the inhibition effect caused by the substrate and product, to activate the aromatic ring, and to improve the diastereoselectivity. This new methodology provides direct and facile access to chiral exocyclic amines. Notably, this report is the first on the highly enantioselective hydrogenation of aromatic amines. 相似文献
993.
Dr. Victor Malgras Dr. Priyanka Jood Dr. Ziqi Sun Prof. Shi Xue Dou Prof. Yusuke Yamauchi Prof. Jung Ho Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10451-10455
Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation. 相似文献
994.
Shujun Cai Zheming Xiao Yingbo Shi Prof. Dr. Shuanhu Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8677-8681
The reaction conditions and scope of the photo‐Nazarov reaction of aryl vinyl ketones were investigated. In contrast to the conventional acid‐catalyzed methods, this photolytic electrocyclization proceeds in the neutral or basic conditions. Irradiating substrates bearing various aromatic rings, acid‐sensitive groups, cyclohexenyl, cycloheptenyl, and unsaturated pyran with UV‐light (254 nm) smoothly yielded hexahydrofluorenones and related structures. This photo‐Nazarov reaction could also be applicable to the substrates carrying β‐alkyl groups on the enone, which gave corresponding polycyclic rings containing quaternary centers. These photo‐electrocyclized products may prove useful for synthesizing a variety of natural products and their derivatives. Further application of this mild photo‐Nazarov reaction in the synthesis of taiwaniaquinol B was achieved. 相似文献
995.
Tao Wang Shuai Shi Daniel Pflästerer Eva Rettenmeier Dr. Matthias Rudolph Dr. Frank Rominger Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):292-296
The conversion of simple, easily available urea‐substituted 3‐phenylpropargyl alcohols catalyzed by a simple IPr–gold(I) catalyst in a gold(I)‐catalyzed cascade reaction composing of a gold‐catalyzed nucleophilic addition and a subsequent gold‐catalyzed substitution reaction delivers 1H‐imidazo[1, 5?a]indol‐3(2 H)‐ones. Other gold(I) catalysts or silver catalysts gave lower yields and often gave other side products. Gold(III) and copper(II) catalysts decomposed the starting material. Twelve examples, including donor and acceptor substituents on the distal nitrogen of the urea substructure, are provided. An X‐ray crystal structure analysis confirmed the structural assignment. The mechanistic investigation including isolation and further conversion of intermediates and reactions with enantiopure starting materials indicated that after the nucleophilic‐addition step, the substrate undergoes an SN1‐type benzylic substitution reaction at the indolyl alcohol intermediate or an intramolecular hydroamination reaction of the 2‐vinylindole intermediate. 相似文献
996.
Gold‐Catalyzed Cycloisomerization of Yne‐Vinylidenecyclopropanes: A Three‐Carbon Synthon for [3+2] Cycloadditions 下载免费PDF全文
Wei Yuan Xiangying Tang Yin Wei Min Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(11):3198-3204
A novel type of yne‐vinylidenecyclopropanes (VDCPs) has been synthesized and applied in gold‐catalyzed cycloisomerization reactions. It was found that these compounds can undergo an intramolecular cycloisomerization and perform as a three‐carbon synthon for [3+2] cycloaddition under gold catalysis to give fused [4.3.0] and [5.3.0] bicyclic derivatives and VDCP rearranged products in moderated to good yields under mild conditions. The substrate scope of these novel transformations has been explored and plausible reaction mechanisms have been presented on the basis of deuterium labeling experiments and DFT calculations. 相似文献
997.
Effects of lignin and hemicellulose contents on dissolution of wood pulp in aqueous NaOH/urea solution 总被引:1,自引:0,他引:1
Zhuqun Shi Quanling Yang Jie Cai Shigenori Kuga Yuji Matsumoto 《Cellulose (London, England)》2014,21(3):1205-1215
Four species of delignified woodchips with about 1 % lignin content (Chlorite–Woodchips) and a series of softwood pulps with different lignin contents were prepared by sodium chlorite delignification. After mechanical defibration, some Chlorite–Woodchips were directly subjected to dissolution treatment in NaOH/urea solvent; the others were first treated with NaOH solution to remove the hemicellulose to obtain NaOH–Chlorite–Woodchips or oxidized with potassium permanganate (OPP) to remove lignin completely to obtain OPP–Chlorite–Woodchips, and then subjected to the dissolution in NaOH/urea solvent. The results showed that the dissolved proportion of the Chlorite–Woodchips ranged from 36 to 46 %, the dissolved proportion of glucan was within 12 %, and most of the hemicellulose was dissolved in NaOH/urea solvent. Compared with Chlorite–Woodchips, the dissolved proportion of NaOH–Chlorite–Woodchips was lower, but their dissolved proportion of glucan was higher. After further permanganate delignification, both the dissolved proportion of the OPP–Chlorite–Woodchips and the dissolved proportion of glucan of the OPP–Chlorite–Woodchips were higher than those of the Chlorite–Woodchips. However, the dissolved proportion of glucan was still limited to only 15–30 %. The effect of the lignin content of softwood pulps on their dissolution is complicated. With the decrease of the lignin content of softwood pulp from 6.9 to 2.8 %, the dissolved proportion of pulp increased from 14 to 26 %. However, further reduction of lignin content from 2.8 to 0.3 % led to a decrease in the dissolved proportion of pulp from 26 to 12 %. The dissolved proportion of glucan followed the same tendency. These results indicated that the dissolution of wood cellulose in NaOH/urea solvent is not simply controlled by the hemicellulose and lignin contents, but also by some other factors. 相似文献
998.
采用阳极氧化法和脉冲电沉积制备出β-PbO2改性TiO2纳米管(β-PbO2/TiO2-NTs)电极,通过扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等技术手段对制备的β-PbO2/TiO2-NTs电极的表面形貌和结构进行了表征。结果表明,该方法成功地将β-PbO2纳米颗粒分散在TiO2纳米管中,通过电催化降解苯酚评价了β-PbO2/TiO2-NTs电极的电催化活性,实验结果表明,在TiO2-NTs中电沉积β-PbO2提高了电极的电催化活性,对苯酚的降解达到83%。 相似文献
999.
建立了茶叶中氟虫腈残留量快速测定的气相色谱-电子轰击源质谱法。茶叶中的氟虫腈用正己烷-丙酮(7:3,V/V)混合液提取,经石墨化碳黑固相萃取小柱净化后,用正己烷-丙酮(9:1,V/V)混合液洗脱,浓缩定容后,用气相色谱-电子轰击源质谱法测定,外标法定量。结果表明,目标物质在0.001~0.040 mg/L范围内的线性关系良好;空白样品在0.002~0.010 mg/L范围三水平加标回收实验的平均回收率在96.6%~114.2%之间,相对标准偏差(n=6)为2.9%~4.4%;方法的定量限为0.001 mg/kg。该方法能满足茶叶中氟虫腈残留量0.002 mg/kg的检测要求。 相似文献
1000.