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过刊目录

    催化学报
    Chinese Journal of Catalysis

    2014, Vol. 35, No. 7
    Online: 2014-06-28

    封面介绍:

    赫荣安等总结了可见光响应铋基光催化剂的化学组成、制备方法、形貌调控、复合结构和性能增强等方面的研究现状和最新进展, 讨论了铋基可见光光催化剂存在的科学和技术问题、挑战和发展前景. 见本期第 989–1007 页.

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    目录
    第35卷第7期目次
    2014, 35 (7):  0-0. 
    摘要 ( 132 )   PDF(1963KB) ( 644 )  
    亮点
    视角
    Organolead halide perovskite:A rising player in high-efficiency solar cells
    Zhou Yang, Wen-Hua Zhang
    2014, 35 (7):  983-988.  DOI: 10.1016/S1872-2067(14)60162-5
    摘要 ( 351 )   [Full Text(HTML)] () PDF(421KB) ( 1688 )  
    综述
    可见光铋系光催化剂的研究进展
    赫荣安, 曹少文, 周鹏, 余家国
    2014, 35 (7):  989-1007.  DOI: 10.1016/S1872-2067(14)60075-9
    摘要 ( 352 )   [Full Text(HTML)] () PDF(1660KB) ( 1904 )  

    当前工业发展导致了严重的能源和环境危机,光催化为这一难题提供了有效的解决方案.然而在实际应用中,传统氧化物光催化剂宽的带隙限制了它的可见光吸收,于是窄带隙光催化剂成为了研究的热点.其中铋系光催化剂以其高的可见光光催化活性引起了人们的广泛关注.因此本文介绍了铋系光催化剂的种类、制备、形貌、复合、性能等方面的研究现状,并展望了含铋可见光催化剂发展前景.

    快讯
    一种新型双亲性有机小分子催化剂在水相体系中催化环己酮与硝基烯烃直接不对称Michael加成反应
    魏建伟, 郭文岗, 张博宇, 刘?, 杜欣, 李灿
    2014, 35 (7):  1008-1011.  DOI: 10.1016/S1872-2067(14)60080-2
    摘要 ( 270 )   [Full Text(HTML)] () PDF(488KB) ( 496 )  

    设计合成了一系列基于脯氨酸巯基咪唑衍生物的新型双亲性有机小分子催化剂,在水相中加入酸作为助催化剂,可以高效高选择性的催化环己酮与硝基烯烃的不对称Michael加成反应,非对映选择性和对映选择性分别高达99:1和96%.

    铑(III)催化的醛的氧化胺化:一种有效的构建N-吡啶酰胺及酰亚胺的合成方法
    代伟, 刘玉臣, 童涛, 李兴伟, 罗芳
    2014, 35 (7):  1012-1016.  DOI: 10.1016/S1872-2067(14)60141-8
    摘要 ( 371 )   [Full Text(HTML)] () PDF(481KB) ( 628 )  

    描述了一种采用三价铑催化的醛的氧化胺化反应,利用Ag2CO3作为氧化剂.通过该方法可以以良好的收率合成各种类型的N-吡啶酰胺及酰亚胺.

    论文
    Poly(4-vinylpyridinium) perchlorate as an efficient and recyclable catalyst for the synthesis of biscoumarins and bisindoles
    Farhad Shirini, Saeed Esmaeeli-Ranjbar, Mohadeseh Seddighi
    2014, 35 (7):  1017-1023.  DOI: 10.1016/S1872-2067(14)60061-9
    摘要 ( 233 )   [Full Text(HTML)] () PDF(558KB) ( 653 )  

    Poly(4-vinylpyridinium) perchlorate has been used as an efficient solid acid catalyst for the synthesis of 3,3'-(arylmethylene)bis(4-hydroxycoumarins) and bis(indolyl)methanes, with the products being formed in excellent yields over very short reaction times under mild and environmentally friendly conditions. This catalyst can be reused several times without any appreciable loss in its activity.

    One-pot synthesis of 1-amidoalkyl-2-naphthols catalyzed by melamine-Br3 under solvent-free conditions
    Arash Ghorbani-Choghamarani, Shima Rashidimoghadam
    2014, 35 (7):  1024-1029.  DOI: 10.1016/S1872-2067(14)60029-2
    摘要 ( 221 )   [Full Text(HTML)] () PDF(355KB) ( 606 )  

    A facile and efficient method has been developed for the synthesis of 1-amidoalkyl-2-naphthols via the one-pot multi-component condensation of 2-naphthol with aromatic aldehydes and acetamide or thioacetamide in the presence of melamine-Br3 under solvent-free conditions. There are several advantages to this reaction, including high yields, short reaction time, and high catalytic efficiency.

    Cu-ETS-10催化NH3选择性还原NOx性能
    宋丽云, 展宗城, 刘晓军, 何洪, 邱文革, 訾学红
    2014, 35 (7):  1030-1035.  DOI: 10.1016/S1872-2067(14)60035-8
    摘要 ( 337 )   [Full Text(HTML)] () PDF(567KB) ( 569 )  

    采用离子交换法制备了Cu-ETS-10钛硅分子筛催化剂,该催化剂对于NH3选择性催化还原(SCR)NOx反应具有较高的催化活性、N2选择性和抗SO2性能.结果表明,Cu-ETS-10钛硅分子筛具有丰富的微孔结构和较高的比表面积(288-380m2/g);原子发射光谱、程序升温还原技术和原位红外漫反射等表征结果表明,Cu在Cu-ETS-10钛硅分子筛中具有多种存在形态,其中Cu2+物种为Cu-ETS-10的活性中心,其含量随Cu含量的增加而先增后降,与催化活性的变化趋势一致.

    Four-component one-pot synthesis of unsymmetrical polyhydroquinoline derivatives using 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate as a catalyst
    Nader Ghaffari Khaligh
    2014, 35 (7):  1036-1042.  DOI: 10.1016/S1872-2067(14)60038-3
    摘要 ( 195 )   [Full Text(HTML)] () PDF(379KB) ( 525 )  

    3-Methyl-1-sulfonic acid imidazolium hydrogen sulfate has been used as an efficient, halogen-free, and reusable Brönsted acidic ionic liquid catalyst for the synthesis of ethyl-4-aryl/heteryl-hexahydro-trimehtyl-5-oxoquinoline-3-carboxylates via the one-pot condensation of dimedone with aryl/heteryl aldehydes, ethyl acetoacetate, and ammonium acetate under solvent-free conditions. This method has the advantage of being clean and simple, as well as providing the desired product in high yield over a short reaction time. Furthermore, the catalyst could be recycled and reused four times without any discernible reduction in activity.

    热扩散法制备MoO3/SiO2催化草酸二甲酯和苯酚酯交换反应
    张付宝, 余晓鹏, 马飞, 杨先贵, 胡静, 邓志勇, 王公应
    2014, 35 (7):  1043-1053.  DOI: 10.1016/S1872-2067(14)60042-5
    摘要 ( 271 )   [Full Text(HTML)] () PDF(811KB) ( 644 )  

    采用热扩散法(TS)和等体积浸渍法制备了MoO3/SiO2催化剂用于草酸二甲酯和苯酚酯交换反应.结果表明,热扩散法制备的10%MoO3/SiO2-TS催化剂较等体积浸渍法制备的10%MoO3/SiO2-C催化剂具有更好的催化性能.运用X射线衍射、Raman光谱、X射线光电子能谱分析、吡啶吸附红外光谱、NH3程序升温脱附等手段对催化剂进行了表征,发现虽然两种方法制备的催化剂都只有弱Lewis酸中心,钼均以氧化钼单体形式存在,未形成解离和聚合,但是10%MoO3/SiO2-TS催化剂较10%MoO3/SiO2-C催化剂表面钼含量更高且MoO3分散得更好.在苯酚用量为0.2mol,10%MoO3/SiO2-TS催化剂用量为1.2g,反应温度为180℃,草酸二甲酯与苯酚的摩尔比为2,反应时间为4h的优化条件下,苯酚转化率可达70.9%,甲基苯基草酸酯和草酸二苯酯的收率分别达63.1%和7.7%.

    Cerium (IV) sulfate:A highly efficient reusable heterogeneous catalyst for the one-pot synthesis of 2,3-dihydroquinazolin-4(1H)-ones under solvent-free conditions
    Abolghasem Davoodnia, Maryam Khashi, Niloofar Tavakoli-Hoseini
    2014, 35 (7):  1054-1058.  DOI: 10.1016/S1872-2067(14)60041-3
    摘要 ( 241 )   [Full Text(HTML)] () PDF(392KB) ( 510 )  

    Cerium (IV) sulfate tetrahydrate, Ce(SO4)2·4H2O, is a novel inorganic solid acidic catalyst that efficiently catalyzes the synthesis of 2,3-dihydroquinazolin-4(1H)-ones via the one-pot three-component reaction of isatoic anhydride, aromatic aldehydes, and a nitrogen source (ammonium acetate, ammonium carbonate, ammonium chloride, or methylamine) under solvent-free conditions. The desired products are obtained in short reaction time with high yields. The catalyst is inexpensive and readily available and can be recovered conveniently and reused such that considerable catalytic activity can still be achieved after the fifth run. Easy work-up and avoiding the use of harmful organic solvents are other advantages of this simple procedure.

    含有酯基二茂铁亚胺环钯化合物催化Suzuki和Heck反应
    王炯, 穆兵, 付志华, 汪丽, 李铁生, 吴养洁
    2014, 35 (7):  1059-1067.  DOI: 10.1016/S1872-2067(14)60045-0
    摘要 ( 206 )   [Full Text(HTML)] () PDF(514KB) ( 530 )  

    合成并表征了系列含有酯基二茂铁亚胺环钯化合物.结果表明,该系列环钯催化剂在纯水或有机溶剂中均能高效催化Heck和Suzuki偶联反应.

    太阳光下高光催化活性Pr-N-P三元掺杂锐钛矿TiO2纳米片
    姜洪泉, 王巧凤, 李世洋, 李井申, 王庆元
    2014, 35 (7):  1068-1077.  DOI: 10.1016/S1872-2067(14)60047-4
    摘要 ( 268 )   [Full Text(HTML)] () PDF(904KB) ( 720 )  

    利用溶胶-凝胶和溶剂热联合技术制备了Pr-N-P三元掺杂锐钛矿TiO2(PrNPTO)纳米片,并采用X射线衍射、透射电镜、N2吸附、X射线光电子能谱、UV-vis吸收谱和光致荧光光谱分析技术对其进行了表征.当Pr掺杂量为1.75wt%,焙烧温度为550℃时,制得的PrNPTO在可见和紫外光下光催化降解亚甲基蓝(MB)活性最佳.在模拟太阳光照射下,PrNPTO也表现出优越的光催化降解4-氯酚性能(kapp=3.90×10-2min-1),优于未掺杂、单掺杂和双掺杂TiO2样品,其光活性是P25TiO2的3.33倍(kapp=1.17×10-2min-1).PrNPTO光活性的提高归因于Pr-N-P三元掺杂增强了紫外和可见光吸收,降低了光生载流子复合,增加了表面羟基以及改善了表面织构特性.在模拟太阳光照射下,PrNPTO光催化效率高且光催化性能稳定,适合于环境净化领域的实际应用.

    掺氮介孔炭作为双功能材料用于氧还原与超级电容器
    梁群英, 苏红, 闫晶, 梁俊杰, 曹水良, 袁定胜
    2014, 35 (7):  1078-1083.  DOI: 10.1016/S1872-2067(14)60044-9
    摘要 ( 265 )   [Full Text(HTML)] () PDF(867KB) ( 766 )  

    以壳聚糖为含氮碳源,正硅酸乙酯为软模板,硝酸镍为催化剂,通过简单的低温水热法及后续炭化,成功合成出掺氮介孔炭材料(NMC-1).NMC-1含有多孔结构以及氮氧等杂原子,能提高其电催化性能、双电层电容与赝电容.由于NMC-1在碱液中表现出显著的催化氧还原反应活性和具有较高的超级电容器比电容(在0.2A/g时为252F/g)及好的循环稳定性,因此,它有可能作为一种可再生、环保的双功能材料同时应用于燃料电池与超级电容器领域.

    Aspects of stability of K/Al2O3 catalysts for the transesterification of rapeseed oil in batch and fixed-bed reactors
    Petr Kutálek, Libor Čapek, Lucie Smoláková, David Kubička, Martin Hájek
    2014, 35 (7):  1084-1090.  DOI: 10.1016/S1872-2067(14)60054-1
    摘要 ( 165 )   [Full Text(HTML)] () PDF(422KB) ( 548 )  

    Catalytically active, stable, and mechanically durable solid K/Al2O3 catalysts for the transesterification of rapeseed oil with methanol was studied. In a batch reactor, high catalytic activity was accompanied by leaching of K species, caused by glycerol, and mechanical destruction of the solid catalyst as a result of contact with the stirrer. In a fixed-bed reactor, some leaching of K species into the liquid phases was also observed, but approached 0 during 30 h of time-on-stream; the activity of the K/Al2O3 catalyst (~83% ester yield) was stable for 100 h of time-on-stream and no mechanical destruction of the catalyst was observed. The populations of K2O and K-O-Al species for fresh and used K/Al2O3 catalysts were compared using Fourier transform infrared spectroscopy. It was found that some K2O species leached into the liquid phases at the beginning of the reaction.

    气体扩散电极参数对阴离子交换膜燃料电池性能的影响
    杨冬蕾, 俞红梅, 李光福, 宋微, 刘艳喜, 邵志刚
    2014, 35 (7):  1091-1097.  DOI: 10.1016/S1872-2067(14)60050-4
    摘要 ( 340 )   [Full Text(HTML)] () PDF(792KB) ( 720 )  

    优化了碱性阴离子交换膜燃料电池(AAEMFC)使用的气体扩散电极(GDE),发现催化层中PTFE含量与催化剂担载量对电池性能与其电化学动力学特征影响很大.采用i-V曲线,开路电压,电池内阻与在线的电化学阻抗谱与动力学分析,评估了所制GDE的电化学性能.在所研究的AAEMFC电极催化层中,PTFE的最佳含量是20%,Pt载量对膜电极三相界面、催化层导电性与催化剂利用率的影响极大.当制备的GDE催化层中Pt/C的Pt载量为1.0mg/cm2,PTFE含量为20%时,AAEMFC的峰电流密度在50oC达到了213mW/cm2.兼顾Pt催化剂的利用率与成本,在没有明显影响电池性能的情况下,Pt的担载量可降至0.5mg/cm2.

    Electrosynthesized polytyramine-copper oxalate nanocomposite on copper electrode for electrocatalytic oxidation of methanol in alkaline medium
    Robab Abbasi, Khalil Farhadi, Sepideh Banisaeid, Nader Nowroozi Pesyan, Arezu Jamali, Fatemeh Rahmani
    2014, 35 (7):  1098-1104.  DOI: 10.1016/S1872-2067(14)60049-8
    摘要 ( 242 )   [Full Text(HTML)] () PDF(702KB) ( 609 )  

    A polytyramine-copper oxalate nanocomposite modified copper (PTCOxNMC) electrode prepared by electropolymerization was examined for electrocatalytic activity towards the oxidation of methanol in alkaline solution using cyclic voltammetry and impedance spectroscopy. The prepared PTCOxNMC electrode showed a significantly high response for adsorbed methanol oxidation. The effects of various parameters such as potential scan rate and methanol concentration on the electrocatalytic oxidation at the surface of the PTCOxNMC electrode were investigated. Spectrometry techniques such as Fourier transform infrared spectroscopy and scanning electron microscopy were used to determine the surface physical characteristics of the modified electrode and revealed that the polytyramine-copper oxalate nanocomposite particles were highly dispersed on the surface of the copper electrode with a narrow size up to 40 nm. The very high current density obtained for the catalytic oxidation may have resulted from the high electrode surface area caused by modification with the poly-tyramine-copper oxalate nanocomposite.

    Pure and Ni-substituted Co3O4 spinel catalysts for direct N2O decomposition
    Bahaa M. Abu-Zied, Soliman A. Soliman, Sarah E. Abdellah
    2014, 35 (7):  1105-1112.  DOI: 10.1016/S1872-2067(14)60058-9
    摘要 ( 166 )   [Full Text(HTML)] () PDF(454KB) ( 768 )  

    A series of NixCo1-xCo2O4 (0 ≤ x ≤ 1) spinel catalysts were prepared by the co-precipitation method and used for direct N2O decomposition. The decomposition pathway of the parent precipitates was characterized by thermal analysis. The catalysts were calcined at 500℃ for 3 h and characterized by powder X-ray diffraction, Fourier transform infrared, and N2 adsorption-desorption. Nickel cobaltite spinel was formed in the solid state reaction between NiO and Co3O4. The N2O decomposition measurement revealed significant increase in the activity of Co3O4 spinel oxide catalyst with the partial replacement of Co2+ by Ni2+. The activity of this series of catalysts was controlled by the degree of Co2+ substitution by Ni2+, spinel crystallite size, catalyst surface area, presence of residual K+, and calcination temperature.

    ZnO纳米柱状阵列表面AgX等离子基元修饰及其可见光光催化活性
    芦佳, 王辉虎, 董一帆, 王凡强, 董仕节
    2014, 35 (7):  1113-1125.  DOI: 10.1016/S1872-2067(14)60055-3
    摘要 ( 400 )   [Full Text(HTML)] () PDF(1019KB) ( 649 )  

    采用浸渍法制备了表面AgX(X=I,Br)等离子基元修饰的ZnO纳米柱状阵列,研究了浸渍浓度和时间以及紫外光光照预处理对ZnO纳米柱状阵列可见光光催化活性的影响.采用场发射扫描电子显微镜、X射线衍射仪、紫外可见漫反射吸收光谱以及X射线光电子能谱仪等手段对ZnO纳米柱状阵列的形貌、相组成、禁带宽度及其表面特性进行了表征.结果显示,AgBr颗粒分布于ZnO纳米柱状阵列的顶端及顶端侧面,同时AgBr颗粒之间相互接触而形成网状结构.通过紫外光光照预处理,AgBr表面出现细小颗粒,形成Ag/AgBr/ZnO纳米复合结构.可见光光催化降解甲基橙结果表明,在相同工艺条件下所制AgBr/ZnO的可见光光催化活性明显优于AgI/ZnO,且与浸渍浓度及时间有关.由于ZnO纳米柱状阵列的比表面积大,AgBr的可见光响应特性以及Ag/AgBr纳米结构的表面等离子效应,经过紫外光光照预处理形成的Ag/AgBr/ZnO纳米复合结构表现出最好的可见光光催化活性.

    N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate as a novel, efficient, and reusable solid acid catalyst for acylation under solvent-free conditions
    Nader Ghaffari Khaligh, Parisa Ghods Ghasem-Abadi
    2014, 35 (7):  1126-1135.  DOI: 10.1016/S1872-2067(14)60052-8
    摘要 ( 174 )   [Full Text(HTML)] () PDF(511KB) ( 442 )  

    N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate has been developed as a recyclable solid acid catalyst for the acetylation of alcohols, phenols, thiols, and amines, as well as the 1,1-diacetylation of aldehydes under solvent-free conditions at room temperature. The acetylated products were formed in good to excellent yields over short reaction times, and the catalyst could be readily recovered by filtration and used several times without any discernible loss in activity. The hydrogen sulfate anion of the catalytic system was found to play a critical role in enhancing the reaction time and yield of the acetylation reaction.

    Zirconium phosphate nanoparticles as a remarkable solid acid catalyst for selective solvent-free alkylation of phenol
    Abdol R. Hajipour, Hirbod Karimi
    2014, 35 (7):  1136-1147.  DOI: 10.1016/S1872-2067(14)60060-7
    摘要 ( 282 )   [Full Text(HTML)] () PDF(641KB) ( 834 )  

    A facile synthesis of α-zirconium phosphate (ZP) nanoparticles as an effective, eco-friendly, and recyclable solid acid catalyst is reported. Polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) were used as organic matrix as dispersing agents and served as a template for the nanoparticles. Hydrogen bonds between ZP and PVA or PVP, along the polymer chains, appear to play an important role for improving the dispersion of in situ formed ZP. Following calcination of PVA/ZP or PVP/ZP, pure hexagonal ZP nanoparticles were obtained. The catalysts were characterized by nitrogen sorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, and transmission electron microscopy. Pyridine-FTIR and temperature-programmed desorption of NH3 suggest the presence of Brönsted acid sites. The acidic properties of the catalyst were studied in Friedel-Crafts alkylation of phenol by tert-butanol, producing 2-tert-butylphenol, 4-tert-butylphenol, and 2,4-di-tert-butylphenol. The alkylation reaction was performed in the presence of catalysts P2O5/Al2O3, P2O5/SiO2, α-ZrP (prepared in the absence of the polymers), and various ionic liquids. The use of the hexagonal ZP nanoparticle catalyst afforded an excellent phenol conversion (86%) and selectivity towards 4-tert-butylphenol (83%) under optimized reaction conditions. The catalyst was easily recovered from the reaction mixture, regenerated, and reused at least four times without significant loss in the catalytic activity.

    磷酸锆催化甘油气相脱水制备丙烯醛
    干慧媚, 赵秀阁, 宋宝宁, 郭立, 张然, 陈晨, 陈吉忠, 朱闻闻, 侯震山
    2014, 35 (7):  1148-1156.  DOI: 10.1016/S1872-2067(14)60057-7
    摘要 ( 302 )   [Full Text(HTML)] () PDF(646KB) ( 1242 )  

    以沉淀法、水热合成法和浸渍法制备了磷酸锆催化剂,通过X射线衍射、热重分析、氮气物理吸附、红外光谱和Hammett指示剂法对催化剂进行了表征,并将该催化剂用于甘油气相脱水反应.研究表明,由沉淀法得到的磷酸锆经过400℃焙烧后能达到最佳催化活性,在温和条件下,甘油可完全转化,丙烯醛选择性为81%,反应24h内催化剂失活不明显.不同方法制备的磷酸锆其结构和表面酸性显著不同,催化剂表面酸性对催化剂活性、丙烯醛选择性和催化剂的寿命均有较大影响.

    ZnO添加量对Pd/Zr0.5Al0.5O1.75催化剂净化稀燃天然气汽车尾气性能的影响
    王云, 尚鸿燕, 徐海迪, 龚茂初, 陈耀强
    2014, 35 (7):  1157-1165.  DOI: 10.1016/S1872-2067(14)60062-0
    摘要 ( 287 )   [Full Text(HTML)] () PDF(683KB) ( 608 )  

    以掺杂不同含量ZnO的Zr0.5Al0.5O1.75为载体,制备了系列1.5%Pd催化剂.在模拟稀燃天然气汽车尾气条件下,测试了催化剂的活性和抗水性,并用N2吸附-脱附、X射线衍射、H2程序升温还原和X射线光电子能谱等手段对催化剂进行了系统表征.研究结果表明,ZnO的添加及添加量对催化剂的活性和抗H2O性有明显影响,其中以ZnO添加量为15%时制备的复合氧化物为载体的催化剂活性最佳.当模拟尾气中不含H2O时,该催化剂对甲烷的起燃温度(T50)和完全转化温度(T90)分别为278和314℃;在含H2O时,该催化剂的T50T90分别为342和371℃.

    Application of 3,4-dihydroxycinnamic acid as a suitable mediator and multiwall carbon nanotubes as a sensor for the electrocatalytic determination of L-cysteine
    Mohsen Keyvanfard, Rasoul Salmani-mobarakeh, Hassan Karimi-Maleh, Khadijeh Alizad
    2014, 35 (7):  1166-1172.  DOI: 10.1016/S1872-2067(14)60065-6
    摘要 ( 201 )   [Full Text(HTML)] () PDF(734KB) ( 471 )  

    A highly sensitive electrochemical sensor was prepared for the determination of L-cysteine using a modified multiwall carbon nanotubes paste electrode in the presence of 3,4-dihydroxycinnamic acid (3,4-DHCA) as a mediator, based on an electrocatalytic process. The results indicate that the electrode is electrocatalytically efficient for the oxidation of L-cysteine in the presence of 3,4-DHCA. The interaction between the mediator and L-cysteine can be used for its sensitive and selective determination. Using chronoamperometry, the catalytic reaction rate constant was calculated to be 2.37×102 mol-1 L s-1. The catalytic peak current was linearly dependent on the L-cysteine concentration in the range of 0.4-115 μmol/L. The detection limit obtained by linear sweep voltammetry was 0.25 μmol/L. Finally, the modified electrode was examined as a selective, simple, and precise new electrochemical sensor for the determination of L-cysteine in real samples.

    改性炭黑-LaMnO3复合材料的制备及其共价复合效应对氧还原性能的影响
    刘景军, 金学民, 宋薇薇, 王峰, 王楠, 宋夜
    2014, 35 (7):  1173-1188.  DOI: 10.1016/S1872-2067(14)60066-8
    摘要 ( 265 )   [Full Text(HTML)] () PDF(3332KB) ( 688 )  

    以VulcanXC-72炭黑为载体,通过对炭载体石墨化处理和表面化学修饰,将其与化学沉淀法制备的纳米级LaMnO3颗粒共混,再经特定温度下煅烧,制备出改性炭黑-LaMnO3复合材料.X射线光电子能谱和热重分析表明,当煅烧温度在300℃时,炭载体与LaMnO3纳米颗粒之间形成了大量C-O-M(M=La,Mn)化学键.扫描电子显微镜和高分辨透射电子显微镜分析发现,纯相LaMnO3纳米颗粒主要呈现短棒、三支棒或竹节棒的形貌特征,炭载体则为具有完整石墨层的空心球结构,LaMnO3均匀分散在炭载体上.在25℃,1mol/LNaOH溶液中的电化学测试结果表明,成分比(LaMnO3:C)为2:3的复合材料具有很高的氧还原电催化活性,氧还原反应电子数为3.81,中间产物H2O2产率为9.5%,其活性接近商业Pt/C催化剂(E-TEK).高的氧还原电催化活性主要归因于LaMnO3纳米颗粒与炭载体之间形成了大量共价键.

    Aluminum sheet-based S-doped TiO2 for photocatalytic decomposition of toxic organic vapors
    Wan-Kuen Jo, Hyun-Jung Kang
    2014, 35 (7):  1189-1195.  DOI: 10.1016/S1872-2067(14)60076-0
    摘要 ( 169 )   [Full Text(HTML)] () PDF(516KB) ( 503 )  

    S-doped TiO2 (S-TiO2) films were immobilized on flexible low-cost aluminum sheets (S-TiO2-AS) using a sol-gel dipping process and low post-processing temperatures. The photocatalytic degradation of toxic organic vapors using the prepared films was evaluated using a continuous-flow glass tube under visible light exposure. The surface properties of the S-TiO2-AS and TiO2-AS films were examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and ultraviolet-visible spectroscopy. The photolysis of benzene, toluene, ethyl benzene, and xylene (BTEX) did not occur on the bare AS. In contrast, the photocatalytic degradation efficiencies of the target pollutants using S-TiO2-AS were higher than those obtained using reference TiO2-AS photocatalyst. In particular, the average photocatalytic degradation efficiencies of BTEX using S-TiO2-0.8-AS (S/Ti ratio=0.8) over a 3-h process were 34%, 78%, 91%, and 94%, respectively, whereas those of TiO2-AS were 2%, 11%, 21%, and 36%, respectively. The photocatalytic decomposition efficiencies of BTEX under visible irradiation using S-TiO2-AS increased with increasing S/Ti ratios from 0.2 to 0.8, but decreased when the ratio further increased to 1.6. Thus, S-TiO2-AS can be prepared using optimal S/Ti ratios. The degradation of BTEX over S-TiO2-AS depended on the air flow rates and initial concentrations of the target chemical. Overall, under optimal conditions, S-TiO2-AS can be effectively applied for the purification of toxic organic vapors.

    La1-xSrxFeO3钙钛矿型氧化物中的晶格氧用于甲烷部分氧化制合成气
    赵坤, 何方, 黄振, 郑安庆, 李海滨, 赵增立
    2014, 35 (7):  1196-1205.  DOI: 10.1016/S1872-2067(14)60084-X
    摘要 ( 272 )   [Full Text(HTML)] () PDF(1094KB) ( 879 )  

    采用燃烧法制备了Sr掺杂钙钛矿型氧化物La1-xSrxFeO3x=0,0.3,0.5,0.9)载氧体,对载氧体分别进行X射线衍射、扫描电镜和H2程序升温还原反应表征,在热重循环装置和固定床反应装置上考察甲烷与载氧体晶格氧的部分氧化反应.结果表明,La1-xSrxFeO3氧化物中的晶格氧适用于甲烷部分氧化制合成气,晶格氧的得失是一个可逆过程,Sr的掺杂提高了载氧体的供氧能力,5次循环后载氧体得失晶格氧的能力没有明显的衰减.从甲烷转化率、n(H2)/n(CO)比以及H2和CO的选择性等方面来考虑,x=0.3-0.5比较理想,甲烷转化率维持在70%左右,气体产物中n(H2)/n(CO)约为2,CH4没有发生明显的裂解.

    In(OTf)3 as a powerful and recyclable catalyst for Pechmann condensation without solvent
    Bahador Karami, Mahtab Kiani, Mohsen Ahmad Hoseini
    2014, 35 (7):  1206-1211.  DOI: 10.1016/S1872-2067(14)60090-5
    摘要 ( 178 )   [Full Text(HTML)] () PDF(363KB) ( 624 )  

    In(OTf)3 plays the role of a Lewis acid catalyst in the Pechmann condensation of phenols with β-ketoesters under solvent-free conditions to give coumarin derivatives. This novel and inexpensive method has advantages such as short reaction time, excellent product yields, and avoids the use of organic solvents in agreement with green chemistry principles. Catalyst loadings can be as low as 1 mol% to give high yields of the corresponding coumarins at 80℃. The catalyst can be recovered after the reaction, and reused with only a slight decrease in the yield.

    M/Al2O3-CeO2(M=Pt-Ru,Ru,Pt)催化剂在甲胺催化湿式氧化中的活性与选择性
    宋爱英, 吕功煊
    2014, 35 (7):  1212-1223.  DOI: 10.1016/S1872-2067(14)60091-7
    摘要 ( 242 )   [Full Text(HTML)] () PDF(1034KB) ( 768 )  

    采用浸渍法制备了M/Al2O3-CeO2(M=Pt-Ru,Ru,Pt)催化剂,并将其用于甲胺的催化湿式氧化反应(CWAO).结果表明,Pt-Ru/Al2O3-CeO2具有最佳活性和选择性.运用程序升温还原、X射线光电子能谱、X射线衍射、透射电子显微镜、N2吸附和CO化学吸附等技术对催化剂的物化性质进行了表征.Pt组分的引入可有效提高双金属催化剂活性组分的分散度,从而明显提高了其催化性能.升降温过程中总有机碳(TOC)转化率与N2选择性迟滞效应表明,甲胺CWAO遵循化学吸附-脱附机理.

    (TEAH)nH3-nPW12O40催化苯甲醇选择氧化及其反应机理
    苏浩, 杨春
    2014, 35 (7):  1224-1234.  DOI: 10.1016/S1872-2067(14)60097-8
    摘要 ( 258 )   [Full Text(HTML)] () PDF(671KB) ( 524 )  

    以Keggin结构的磷钨酸和三乙胺(TEA)为原料,通过简单的酸碱反应合成了磷钨酸的TEA盐.并以它们为催化剂,考察了以H2O2为氧化剂、以水为溶剂的体系中苯甲醇选择氧化制备苯甲醛的反应性能.结果表明,(TEAH)nH3-nPW12O40n=1,2,3)系列催化剂对苯甲醇的选择氧化反应有很高的活性和选择性,且可被分离和循环使用.在适宜的反应条件下,最佳催化剂(TEAH)H2PW12O40上,苯甲醇的转化率可达99.6%,苯甲醛的选择性为100%.还采用IR,31PNMR谱和元素分析技术,对催化剂和反应过程中催化剂物种的转化和分布进行了考察,进而导出了反应机理.在这个水--油两相反应中,(PW12O403-首先在H2O2的作用下,氧化降解为溶于水的小分子过氧物种(PO4(WO(O2243-和自由W物种.(PO4(WO(O2243-是真正的活性物种,可将部份溶于水层的苯甲醇氧化为苯甲醛,自身转变为失去活性氧的反应后物种(SAR).而SAR又可与自由W物种一起聚合为前驱体状态的(PW12O403-,完成催化循环.