金催化-还原策略制备单原子层铂的Au@Pt核壳结构及电催化应用

在15 nm金纳米粒子(Au NPs)和4-(2-羟乙基)-哌嗪乙磺酸(HEPES)混合溶液中,Pt~(2+)在金催化作用下被HEPES还原为Pt原子并沉积于Au NPs表面,常温下制备了单原子层Pt包覆Au核的核壳纳米结构(Au@Pt NPs).通过紫外可见吸收光谱(UV-Vis)、高分辨透射电镜(HRTEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)以及电感耦合等离子体-原子发射光谱(ICP-AES)等对材料的晶体结构和形貌进行了表征.电化学测试表明,表面具有单原子层铂的Au@Pt NPs对氧气还原反应表现了良好的电催化性能,在碱性溶液中其电化学活性面积(ECSA,183.40 cm~2/mgPt)和质量活性(.0.075 V下为573.2 mA/mgPt)分别为商业Pt/C催化剂(102 cm2/mgPt和113.39 mA/mgPt)的1.72和5.06倍.     

铂-金交替修饰的铂核纳米颗粒的制备与表征

通过吸附在铂纳米颗粒表面的氢交替还原氯金酸和氯铂酸,得到了复合型纳米颗粒Pt@Au/Pt,用UV-Vis光谱、TEM和XRD对其进行了表征.     

吸汞载银活性炭纤维和吸汞活性炭纤维的热脱附特性研究

70℃下分别对载银活性炭纤维(载银量14.07%)和活性炭纤维的片状吸附体进行气态汞吸附实验,测定出载银活性炭纤维汞饱和吸附量为192.3 mg/g,活性炭纤维汞饱和吸附量为29.4 mg/g,分别为普通活性炭的48倍～192倍和7倍～29倍.采用热重分析法(TGA)研究了两种吸附剂汞饱和后的热脱附再生特性.结果表明,汞饱和载银活性炭纤维的汞脱附发生在100℃～650℃,在70 min内从50℃升温至650℃,才乏脱附率为94.73%;汞饱和活性炭纤维的汞脱附发生在100℃～230℃,在40 min内从50℃升温至350℃ ,汞脱附率为69.93%.扫描电镜分析发现,载银活性炭纤维因吸附汞而富集的银,经热脱附后变成均匀弥散于纤维表面的亚微米级和纳米级球状银颗粒;吸汞活性炭纤维经热脱附后物理吸附汞基本消失,而氧化汞颗粒反而变多,说明物理吸附的汞易于脱附,氧化汞难以脱附,同时在热脱附过程中存在金属汞向氧化汞的转化.     

通过柠檬酸改性提高载银活性炭的抗菌性能

通过负载柠檬酸对活性炭进行改性,用N2吸附法测定活性炭的比表面积,用AAS、SEM、XRD测试技术分析了银在活性炭上的吸附和分布,并研究了载银活性炭的抗菌性能。结果表明,负载柠檬酸使活性炭的比表面积下降约24%,但载银后活性炭的比表面积增大。柠檬酸改性为[Ag(NH3)2] 的还原吸附提供更多的活性点,使银的吸附速率加快,吸附量提高约25%,表面的银颗粒变得非常密集,粒径减小,且颗粒均匀,因此抗菌性能显著增强,其中对金黄色葡萄球菌的杀灭效果明显优于对大肠杆菌的,同时对于高分散Ag/C催化剂的制备及银的回收也具有重要的价值。     

活性炭表面含氧基团对苯酚吸附平衡及动力学的影响

煤基活性炭分别用烧失处理和HNO3氧化处理后得到不同表面性质的活性炭,采用X射线光电子能谱(XPS)、N2吸附、酸碱滴定及零电荷点(pHPZC)对活性炭表面性质及孔结构进行表征,研究了活性炭表面性质对苯酚吸附平衡和吸附动力学影响.经HNO3氧化后,活性炭表面含氧基团显著增加,烧失处理后,表面含氧基团尤其是羧基显著减少.苯酚最大平衡吸附量随活性炭表面含氧基团的增多而减少,吸附速率常数与碳表面含氧基团的量呈正相关,而吸附活化能与活性炭在一定吸附条件下表面所带电荷多少相关.随着活性炭表面含氧基团增多,吸附活化熵增大(负值减小),苯酚在活性炭表面排列的有序性减小.静态吸附与动态吸附实验结果都表明:在含氧基团较少而碱性更强的活性炭上,发生化学吸附的程度更大.     

水蒸气活化制备烟杆基颗粒活性炭的研究

以烟杆废弃物为原料,以木焦油为主的复合粘结剂,通过水蒸气活化制备了烟杆基颗粒活性炭.对影响颗粒活性炭吸附性能和收率的因素如活化温度、活化时间、水蒸气流量进行了系统研究,得到了最佳工艺条件:活化温度为900℃,活化时间为60 min,水蒸气流量为3.31 g/min.该工艺条件下,烟杆基颗粒活性炭对碘的吸附值为1028 mg/g,对亚甲基蓝的吸附值为285 mg/g,收率为24.39%.同时,测定了该活性炭氮吸附,通过BET计算了活性炭的比表面积,并通过密度函数理论(DFT)表征了活性炭的孔结构.结果表明,该活性炭为微孔型,BET比表面积为1073 m2/g,总孔容为0.8152 ml/g.     

通过氧化改性提高载银活性炭的抗菌性能

使用浓HNO3和浓H2O2对活性炭进行常温氧化改性,用FTIR和N2吸附法对活性炭进行表面分析,用AAS、SEM、XRD研究银在活性炭表面的吸附和分布特征,并研究了载银活性炭的抗茵性能.结果表明,活性炭经浓HNO3常温改性后,比表面积提高,而经浓H2O2常温改性后,比表面积略有下降,但都使活性炭表面含氧基团增加.改性后,活性炭表面增加的含氧基团为[Ag(NH3)2] 的还原吸附提供更多的活性点,使银的吸附量增大5倍多,银颗粒更加密集,大小更加均一.研究表明,载银活性炭具有明显的抗茵作用,其中对金黄色葡萄球菌的杀灭效果优于对大肠杆菌的杀灭效果,氧化改性使载银活性炭抗茵作用显著增强,其中硝酸改性现象更加明显.     

铂/酞菁/碳纳米管复合纳米催化剂的构建及其甲醇氧化性能

本文报道了一种方便地构建铂/酞菁/碳纳米管(Pt/Pc/CNTs)复合纳米催化剂的新方法：先通过简单的超声处理将酞菁分子(Pc)修饰至碳纳米管表面,随后采用乙二醇还原法将铂纳米粒子固载到酞菁修饰的碳纳米管表面,形成Pt/Pc/CNTs复合纳米催化剂。X射线衍射(XRD)和透射电镜(TEM)结果表明金属铂纳米颗粒均匀地分散在碳纳米管表面,尺寸约5 nm。采用UV-Vis、FTIR和Raman等手段研究了这种复合纳米催化剂的构建过程,结果表明酞菁分子与碳纳米管之间存在较强的π-π相互作用,使其能牢固地吸附于碳     

苯基键合高比表面积活性炭的制备及其对挥发性有机化合物的吸附性能研究

以核桃壳为原料,经过碳化、KOH活化, 制备了高比表面积活性炭,通过三甲基氧基苯基硅烷对活性炭表面进行改性,制得苯基键合高比表面积活性炭吸附材料.通过氮气吸附法测定了苯基键合活性炭的比表面积及孔径分布;采用红外光谱、X射线光电子能谱、X射线粉末衍射技术对苯基键合活性炭的有机官能团、表面元素的化学环境及晶体结构进行了表征.将该吸附材料制成采样管,吸附空气中的挥发性有机物,二硫化碳解吸后使用气相色谱进行分析.考察了苯基键合活性炭对乙醇、丙酮、正己烷、乙酸乙酯、四氢呋喃、1,2-二氯乙烷和苯共7种挥发性有机化合物(VOCs)的吸附性能,饱和吸附量在129~216 mg/g之间;在0.05~ 2.50 mg/mL范围内,7种组分的峰高与浓度呈良好的线性关系,检出限在0.92~3.60 mg/m3之间.     

K_2CO_3活化制备花椒籽废渣的活性炭及其对对硝基苯酚的吸附性能

采用花椒籽废渣(RPS)为原料,K_2CO_3为活化剂制备了花椒籽废渣活性炭(KAC),以期实现农业废弃物的再利用。采用傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)、热重分析仪(TGA)、能量散射光谱(EDS)、X射线衍射仪(XRD)和气体吸附法等技术手段对其进行表征。分析了浸渍比(m(K_2CO_3)∶m(RPS))、浸渍时间、活化温度和活化时间对制备花椒籽废渣活性炭的影响,并且测试了花椒籽废渣活性炭对对硝基苯酚的吸附行为。研究结果表明,在浸渍比为0.8,浸渍时间为12 h,活化温度为550℃,活化时间为60min的条件下,活性炭的产率为29.3%,比表面积为1210 m~2/g,碘值为1002 mg/g,对亚甲基蓝的平衡吸附容量为362 mg/g,灰分为2.2%,水分为6.6%。对对硝基苯酚的吸附性能研究表明,293 K,pH=8.0,吸附180min后可达到吸附平衡,对硝基苯酚的吸附容量为406 mg/g,吸附可用Langmuir等温方程较好模拟,吸附为自发的放热过程。动力学研究表明该吸附符合准二级动力学模型。K_2CO_3活化法制备花椒籽废渣活性炭原料廉价,工艺简单,制得的活性炭吸附性能优异,具有较好的应用前景。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.