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过刊目录

    催化学报
    Chinese Journal of Catalysis

    2014, Vol. 35, No. 9
    Online: 2014-08-19

    封面介绍:

    贺泓及研究团队基于实验室对 V2O5-WO3/TiO2 催化剂配方及涂覆成型技术的大量研究, 在中国重汽集团建成了一条 NH3-SCR 催化剂生产线, 产品满足国产重型柴油车国 IV 排放标准要求. 见本期第1438-1445 页.

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    目录
    第35卷第9期目次
    2014, 35 (9):  0-0. 
    摘要 ( 175 )   PDF(1993KB) ( 600 )  
    亮点
    Recent progress on photocatalysts with wide visible light range absorption for heterogeneous water splitting
    Shanshan Chen, Fuxiang Zhang
    2014, 35 (9):  1431-1432.  DOI: 10.1016/S1872-2067(14)60183-2
    摘要 ( 273 )   [Full Text(HTML)] () PDF(422KB) ( 679 )  
    快讯
    分子氧为氧化剂磷钒酸盐为催化剂超深度氧化脱除柴油中的二苯并噻吩
    唐南方, 赵小平, 蒋宗轩, 李灿
    2014, 35 (9):  1433-1437.  DOI: 10.1016/S1872-2067(14)60194-7
    摘要 ( 315 )   [Full Text(HTML)] () PDF(623KB) ( 664 )  

    一种“双帽Keggin型”磷钒酸盐在温和的反应条件下以分子氧为氧化剂氧化二苯并噻吩至二苯并噻吩砜的反应中表现出很高的催化活性. 用溶剂萃取或者选择吸附等方法可轻易地将反应产生的二苯并噻吩砜从油品中除去. 这提供了一种新型的分子氧为氧化剂的超深度氧化脱硫方法.

    论文
    NH3选择性还原NOx技术在重型柴油车尾气净化中的应用
    刘福东, 单文坡, 潘大伟, 李腾英, 贺泓
    2014, 35 (9):  1438-1445.  DOI: 10.1016/S1872-2067(14)60048-6
    摘要 ( 388 )   [Full Text(HTML)] () PDF(724KB) ( 720 )  

    基于实验室对柴油车用V2O5-WO3/TiO2催化剂配方以及涂覆成型技术的大量研究,设计了一条产量为6000只/月的NH3选择性催化还原NOx (NH3-SCR)催化剂中试生产线,并对生产的催化剂产品进行了发动机台架测试. 结果表明,实验室制备的V2O5-WO3/TiO2粉体催化剂和生产线产品,在空速为50000 h-1和200-450 ℃条件下NOx转化率均可达80%以上;采用大尺寸堇青石载体涂覆后制备的V2O5-WO3/TiO2整体催化剂经实验室小样测试,在空速为10000-30000 h-1和250-450 ℃条件下NOx转化率也为80%以上. 发动机台架测试结果表明,该催化剂产品可使重型柴油机NOx排放达到国IV标准中欧洲稳态循环(ESC)和欧洲瞬态循环(ETC)排放限值的要求. 该生产线经适当调整后也可用于生产非钒基NH3-SCR整体催化剂,以满足未来钒基NH3-SCR催化剂更新换代的需求.

    可调苯氧基修饰的聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆固载手性Mn(Salen)高效催化烯烃环氧化
    邹晓川, 石开云, 王存
    2014, 35 (9):  1446-1455.  DOI: 10.1016/S1872-2067(14)60064-4
    摘要 ( 389 )   [Full Text(HTML)] () PDF(719KB) ( 609 )  

    使用不同空间位阻的苯氧链接手臂修饰的聚(苯乙烯基-苯乙烯膦酸)-磷酸氢锆轴向固载手性Mn(Salen)催化剂(Cat1-Cat3),随后在间氯过氧苯甲酸(m-CPBA)为氧化剂的体系中考察了固载催化剂的催化性能. 同时,在相同氧化体系下测试了一系列均相催化剂类似物(Cat4-Cat6). 结果表明,在非均相条件下,可调变苯氧链接手臂的邻位取代基对催化剂活性起着重要作用,环氧化产物的对映选择性随着取代基位阻的增加而增大,但产物转化率有一定程度下降. 此外,非均相催化剂即使在没有轴向助剂的参与下(通常需要添加,为了增大催化活性)仍然表现出非常高的催化活性,尤其对α-甲基苯乙烯反应,其对映选择性从6.8%增加到76.8%,转化率从19.8%上升到90.7%. 制备的非均相催化剂11次的循环使用实验表明,在前5次使用后催化剂活性与对映选择性没有明显变化.

    编织芳基网络聚合物负载Rh催化剂上高碳烯烃氢甲酰化反应性能
    姜淼, 丁云杰, 严丽, 宋宪根, 林荣和
    2014, 35 (9):  1456-1464.  DOI: 10.1016/S1872-2067(14)60068-1
    摘要 ( 302 )   [Full Text(HTML)] () PDF(908KB) ( 740 )  

    考察了编织芳基网络聚合物(KAPs)负载的Rh催化剂(Rh/KAPs)在高碳烯烃氢甲酰化反应中的催化性能. 结果表明,三苯基膦-苯基底KAPs负载Rh催化剂(Rh/KAPs-1)具有优异的高碳烯烃氢甲酰化反应活性,产物醛收率显著高于Rh/SiO2催化剂. 傅里叶变换红外光谱、热重、氮气吸附-脱附、X射线衍射、透射电子显微镜、13C核磁共振和31P核磁共振结果显示,Rh/KAPs-1催化剂具有优异的热稳定性及大的比表面积和多级孔道结构,Rh颗粒处于高度分散状态,并可在反应过程中形成均相催化活性物种.

    AgMn/HZSM-5催化剂上室温O3氧化脱除空气中的苯:Mn含量和水含量的影响
    刘阳, 李小松, 刘景林, 石川, 朱爱民
    2014, 35 (9):  1465-1474.  DOI: 10.1016/S1872-2067(14)60070-X
    摘要 ( 364 )   [Full Text(HTML)] () PDF(731KB) ( 607 )  

    考察了Mn含量和水含量对AgMn/HZSM-5(AgMn/HZ)催化剂上室温O3氧化(OZCO)脱除空气中苯的影响. 研究发现,Mn含量为2.4 wt%的AgMn/HZ催化剂(AgMn/HZ(2.4))具有大的比表面积和高的MnOx分散度,OZCO活性和稳定性最高. 反应后的程序升温脱附结果表明,2.4 wt%的Mn含量能有效抑制苯和甲酸在催化剂上的残留. 当Mn含量≤ 2.4 wt%时,催化剂分解O3的活性在苯氧化过程中占主导;当Mn含量 > 2.4 wt%时,苯的活化起主要作用. 基于AgMn/HZ(2.4)催化剂优越的反应活性和稳定性,进一步研究了湿气流中该催化剂上苯的氧化. 与干气流相比,水汽的加入能显著提高催化剂的反应活性和稳定性,且以0.1-0.2 vol%水含量时最优.

    纳米片聚结Co3O4微球催化甲苯燃烧
    王芳, 戴洪兴, 邓积光, 谢少华, 杨黄根, 韩文
    2014, 35 (9):  1475-1481.  DOI: 10.1016/S1872-2067(14)60072-3
    摘要 ( 302 )   [Full Text(HTML)] () PDF(1205KB) ( 565 )  

    采用乙二胺辅助的水热法制备了纳米片聚结的Co3O4微球. 利用多种分析技术表征了其物化性质,并评价了其对甲苯燃烧的催化活性. 结果表明,由添加1.0 ml乙二胺经140 ℃水热处理12 h后制得的Co3O4样品呈纳米片聚结的微球状表面形貌. Co3O4微球样品的比表面积约为66 m2 g-1. 与体相Co3O4样品相比,Co3O4微球样品具有较高的氧吸附物种浓度和较好的低温还原性. 当空速为20000 ml g-1 h-1时,在Co3O4微球样品上甲苯转化率达到50%和90%时的反应温度分别为230和254 ℃. 这与该样品具有较大的比表面积、较高的氧吸附物种浓度和较好的低温还原性相关.

    一个新的满足未来排放标准的摩托车尾气净化催化剂
    王苏宁, 崔亚娟, 兰丽, 史忠华, 赵明, 龚茂初, 方瑞梅, 陈思洁, 陈耀强
    2014, 35 (9):  1482-1491.  DOI: 10.1016/S1872-2067(14)60092-9
    摘要 ( 318 )   [Full Text(HTML)] () PDF(692KB) ( 866 )  

    采用共沉淀法制备CeO2-ZrO2-La2O3-PrO2-Al2O3复合氧化物载体材料,以浸渍法制备了Pd-Rh,Pt-Rh和Pt-Pd-Rh型整体式催化剂. 用N2吸附-脱附、程序升温还原、储氧量和X射线衍射对其进行了表征,并考察了老化前后催化剂的空燃比特性、空速特性和温度特性. 结果表明,在三种催化剂中,Pt-Pd-Rh型催化剂表现出更优异的性能. 在40000 h-1空速下,新鲜Pt-Pd-Rh型催化剂对C3H8,CO和NO的起燃温度T50分别为239,187和191 ℃,ΔTT90 - T50)分别为21,3和3 ℃. 老化后,C3H8,CO和NO的T50分别为298,203和223 ℃,ΔT分别为22,5和13 ℃,且老化前后空燃比窗口较宽,适合于未来排放标准的摩托车尾气净化.

    Synthesis of novel hierarchical ZSM-5 monoliths and their application in trichloroethylene removal
    João Pires, Ana C. Fernandes, Divakar Duraiswami
    2014, 35 (9):  1492-1496.  DOI: 10.1016/S1872-2067(14)60085-1
    摘要 ( 251 )   [Full Text(HTML)] () PDF(614KB) ( 789 )  

    A self-supporting ZSM-5 monolith with a hierarchical porosity was prepared using polyurethane foam (PUF) as a structural template and a hydrothermal synthesis procedure. The synthesized monolith was characterized and investigated towards the adsorption and catalytic oxidation of trichloroethylene (TCE). Adsorption of TCE was studied gravimetrically and oxidation of TCE was studied using a vapor-phase down-flow reactor. Monolithic ZSM-5 displayed good sorption properties and completely oxidized TCE. Conversion levels of 50% and 90% were achieved at reduced temperatures (by ~50 ℃) when compared with the conversion temperatures obtained from the powder counterparts. Besides the activity of the monolith towards TCE adsorption and oxidation, it was stable and enhanced diffusion, thereby reducing pressure drops to a great extent owing to its hierarchical porous nature.

    One-pot multicomponent synthesis of unsymmetrical polyhydroquinoline derivatives with 1,1’-butylenebispyridinium hydrogen sulfate as an efficient, halogen-free and reusable Brönsted ionic liquid catalyst
    Nader Ghaffari Khaligh
    2014, 35 (9):  1497-1503.  DOI: 10.1016/S1872-2067(14)60087-5
    摘要 ( 283 )   [Full Text(HTML)] () PDF(675KB) ( 608 )  

    1,1'-Butylenebispyridinium hydrogen sulfate is an efficient, halogen-free and reusable Brönsted ionic liquid catalyst for the synthesis of ethyl-4-aryl/heteryl-hexahydro-trimehtyl-5- oxoquinoline-3-carboxylates by the one-pot condensation of dimedone, aryl/heteryl aldehydes, ethyl acetoacetate, and ammonium acetate under solvent-free conditions. This method has the advantages of high yield, clean reaction, simple methodology, and short reaction time. The ionic liquid can be recycled five times without significant loss of the catalytic activity.

    硫中毒对Co3O4/CeO2复合氧化物上炭黑催化燃烧的影响
    石晓燕, 余运波, 薛莉, 贺泓
    2014, 35 (9):  1504-1510.  DOI: 10.1016/S1872-2067(14)60088-7
    摘要 ( 289 )   [Full Text(HTML)] () PDF(677KB) ( 736 )  

    采用共沉淀法制备了CeO2,Co3O4和一系列Co3O4/CeO2复合氧化物催化剂,在400 ℃下含SO2的氧化气氛中对催化剂进行了硫中毒处理,通过原位红外光谱、X射线衍射、程序升温脱附和X射线光电子能谱对新鲜和硫中毒的样品进行了表征. 结果表明,所有测试的硫中毒样品上均形成了硫酸盐,CeO2上累积的硫酸盐明显比Co3O4上的多,Co3O4/CeO2复合氧化物在硫中毒过程中形成了硫酸钴和硫酸铈. 对新鲜和硫化样品在NO/O2气氛下进行了催化炭黑燃烧实验,发现Co3O4/CeO2复合氧化物的活性和抗硫性能优于CeO2,但抗硫性能低于Co3O4.

    具有高可见光催化活性的Ti3+和碳共掺杂改性的TiO2光催化剂
    刘允昌, 邢明阳, 张金龙
    2014, 35 (9):  1511-1519.  DOI: 10.1016/S1872-2067(14)60093-0
    摘要 ( 352 )   [Full Text(HTML)] () PDF(952KB) ( 962 )  

    以乙醇为碳源,采用操作简单的真空活化法一步实现对TiO2的Ti3+与C的共掺杂改性,TiO2用X衍线衍射、紫外-可见光谱、顺磁共振、X射线光电子能谱和红外光谱等手段表征了催化剂的结构、组成、光学性质. 结果表明, 经Ti3+与C共掺杂改性后的催化剂表现出高的可见光降解甲基橙活性. 复合在催化剂表面的石墨可以增强催化剂对可见光的响应范围,而Ti3+与氧缺陷形成的掺杂能级则可以提高光生电子的迁移效率. 实验表明,两者之间的协同作用促进了其可见光催化活性的提高.

    Nd, Ce和La改性对Ni/SBA-15催化剂在CH4/CO2重整反应中性能的影响
    刘会敏, 李宇明, 吴昊, 杨维维, 贺德华
    2014, 35 (9):  1520-1528.  DOI: 10.1016/S1872-2067(14)60095-4
    摘要 ( 343 )   [Full Text(HTML)] () PDF(732KB) ( 749 )  

    以稀土金属Nd,Ce或La的氧化物为助剂,采用β-环糊精浸渍法对Ni/SBA-15催化剂进行了改性,并运用X射线衍射、N2吸附-脱附、程序升温还原和热重等手段考察了改性的催化剂在CO2重整CH4制合成气反应中的催化性能. 结果表明,Nd等稀土金属氧化物的添加对催化剂孔结构和晶相结构等性质影响不大,但可影响NiO的还原; Nd的添加使NiO与载体之间以Ni-Nd-O形式相互作用,促进了活性组分NiO的还原. 其中,Nd的添加量为5-10 wt%时所制备的催化剂在重整反应中的催化活性最高,且具有很强的抗积碳性能. La和Ce氧化物促进的Ni催化剂也表现出类似的性质和催化性能.

    Selective oxidation of alcohols over copper zirconium phosphate
    Abdol R. Hajipour, Hirbod Karimi
    2014, 35 (9):  1529-1533.  DOI: 10.1016/S1872-2067(14)60096-6
    摘要 ( 358 )   [Full Text(HTML)] () PDF(727KB) ( 743 )  

    The catalytic activity of copper zirconium phosphate (ZPCu) in the selective oxidation of alcohols to their corresponding ketones or aldehydes, using H2O2 as an oxidizing agent, was studied. The oxidation reaction was performed without any organic solvent, phase-transfer catalyst, or additive. Steric factors associated with the substrates influenced the reaction. The catalyst was characterized using X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. It was shown that the interlayer distance increased from 0.74 to 0.80 nm and the crystallinity was reduced after Cu2+ intercalation into the layers. This catalyst can be recovered and reused three times without significant loss of activity and selectivity.

    哈茨木霉CGMCC 2979生物转化栀子中的京尼平苷制备京尼平
    董悦生, 刘乐平, 包永明, 郝爱鱼, 秦莹, 温祖佳, 修志龙
    2014, 35 (9):  1534-1546.  DOI: 10.1016/S1872-2067(14)60134-0
    摘要 ( 278 )   [Full Text(HTML)] () PDF(924KB) ( 816 )  

    采用微生物直接转化药材的方法,将栀子中的京尼平苷转化为京尼平,无需糖苷酶和京尼平苷的制备. 在培养温度为30 ℃,pH 6.1以及栀子载量为80 g/L的条件下,48 h京尼平苷的转化率为97.8%. 转化后的京尼平通过XAD-16N大孔树脂偶联硅胶层析的方法,制备得到纯度大于95%的京尼平,收率为62.3%. 在催化、转化机制研究中,从哈茨木霉CGMCC2979的发酵液中分离得到了分子量为74.4 kDa的京尼平苷β-葡萄糖苷酶,该酶最优催化条件为50 ℃和pH 4.0-5.0. KmVmax分别为3.6 mmol/L和775 μmol/h/mg蛋白. 本文提供了一种简便、高效制备京尼平的新方法.

    Immobilized Pd nanoparticles on Tris-modified SiO2:Synthesis, characterization, and catalytic activity in Heck cross-coupling reactions
    Abdol R. Hajipour, Ghobad Azizi
    2014, 35 (9):  1547-1554.  DOI: 10.1016/S1872-2067(14)60109-1
    摘要 ( 214 )   [Full Text(HTML)] () PDF(948KB) ( 629 )  

    The preparation of supported Pd nanoparticles on Tris (tris(hydroxymethyl)aminomethane)- modified SiO2 gel and their catalytic application in Heck coupling are investigated. The catalyst was characterized using a combination of X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. The supported Pd nanoparticles were found to be a highly active and reusable catalyst for the Heck reaction at a low Pd loading (0.02 mol%) because of stabilization by the Tris moieties. Several reaction parameters, including the type and amount of solvent, base, and temperature, were evaluated. The heterogeneity of the catalytic system was investigated using different approaches, and showed that slight Pd leaching into the reaction solution occurred under the reaction conditions. Despite this metal leaching, the catalyst can be reused seven times without significant loss of its activity.

    Covalent immobilization of Candida antarctica lipase B on nanopolystyrene and its application to microwave-assisted esterification
    Attaullah Bukhari, Ani Idris, Madiha Atta, Teo Chee Loong
    2014, 35 (9):  1555-1564.  DOI: 10.1016/S1872-2067(14)60111-X
    摘要 ( 313 )   [Full Text(HTML)] () PDF(602KB) ( 674 )  

    Nanopolystyrene was used as a solid support for the covalent immobilization of Candida antarctica lipase B (CalB) using the photoreactive reagent 1-fluoro-2-nitro-4-azido benzene (FNAB) as a coupling reagent. The obtained derivative was then used as a biocatalyst in a microwave assisted esterification experiment. Factors such as contact time, pH, and enzyme concentration were investigated during immobilization. The hydrolytic activity, thermal, and operational stability of immobilized-CalB were determined. The maximum immobilized yield (218 μg/mg support) obtained at pH 6.8 exhibited optimum hydrolytic activity (4.42 × 103 mU p-nitrophenol/min). The thermal stability of CalB improved significantly when it was immobilized at pH 10, however, the immobilized yield was very low (93.6 μg/mg support). The immobilized-CalB prepared at pH 6.8 and pH 10 retained 50% of its initial activity after incubation periods of 14 and 16 h, respectively, at 60 ℃. The operational stability was investigated for the microwave assisted esterification of oleic acid with methanol. Immobilized-CalB retained 50% of its initial activity after 15 batch cycles in the microwave-assisted esterification. The esterification time was notably reduced under microwave irradiation. The combined use of a biocatalyst and microwave heating is thus an alternative total green synthesis process.

    Silver nanoparticle decorated poly(2-aminodiphenylamine) modified carbon paste electrode as a simple and efficient electrocatalyst for oxidation of formaldehyde
    Reza Ojani, Saeid Safshekan, Jahan-Bakhsh Raoof
    2014, 35 (9):  1565-1570.  DOI: 10.1016/S1872-2067(14)60115-7
    摘要 ( 311 )   [Full Text(HTML)] () PDF(557KB) ( 576 )  

    This work describes the promising activity of silver nanoparticles on the surface of a poly(2-amino diphenylamine) modified carbon paste electrode (CPE) towards formaldehyde oxidation. Electrodeposition of the conducting polymer film on the CPE was carried out using consecutive cyclic voltammetry in an aqueous solution of 2-aminodiphenylamine and HCl. Nitrogen groups in the polymer backbone had a Ag ion accumulating effect, allowing Ag nanoparticles to be electrochemically deposited on the surface of the electrode. The electrochemical and morphological characteristics of the modified electrode were investigated. The electro-oxidation of formaldehyde on the surface of electrode was studied using cyclic voltammetry and chronoamperometry in aqueous solution of 0.1 mol/L NaOH. The electro-oxidation onset potential was found to be around -0.4 V, which is unique in the literature. The effect of different concentrations of formaldehyde on the electrocatalytic activity of the modified electrode was investigated. Finally, the diffusion coefficient of formaldehyde in alkaline media was calculated to be 0.47 × 10-6 cm2/s using chronoamperometry.

    Kinetics and efficiency displayed by supported and suspended TiO2 catalysts applied to the disinfection of Escherichia coli
    Majdi Kacem, Gael Plantard, Nathalie Wery, Vincent Goetz
    2014, 35 (9):  1571-1577.  DOI: 10.1016/S1872-2067(14)60125-X
    摘要 ( 213 )   [Full Text(HTML)] () PDF(628KB) ( 437 )  

    TiO2-mediated photocatalysis is widely used in a variety of applications and products in the environmental and energy fields, including photoelectrochemical conversion, self-cleaning surfaces, and especially water purification systems. The dimensionality of the structure of a TiO2 material can affect its properties, functions, and more specifically, its photocatalytic performance. In this work, the photocatalytic inactivation of Gram-negative Escherichia coli using three photocatalysts, differing in their structure and other characteristics, was studied in a batch reactor under UVA light. The aim was to establish the disinfection efficiency of solid TiO2 compared with that of suspended catalysts, widely considered as reference cases for photocatalytic water disinfection. The bacterial inactivation profiles obtained showed that: (1) the photoinactivation was exclusively related to the quantity of photons retained per unit of treated volume, irrespective of the characteristics of the photocatalyst and the emitted light flux densities; (2) across the whole UV light range studied, each of the photocatalytic solids was able to achieve more than 2 log bacterial inactivation with less than 2 h UV irradiation; (3) none of the used catalysts achieved a total bacterial disinfection during the treatment time. For each of the catalysts the quantum yield has been assessed in terms of disinfection efficiency, the 2D material showed almost the same performance as those of suspended catalysts. This catalyst is promising for supported photocatalysis applications.

    铋掺杂二氧化钛纳米颗粒的制备及其可见光催化性能
    李海燕, 刘金凤, 钱俊杰, 李秋叶, 杨建军
    2014, 35 (9):  1578-1589.  DOI: 10.1016/S1872-2067(14)60124-8
    摘要 ( 495 )   [Full Text(HTML)] () PDF(1154KB) ( 799 )  

    采用水热法,以纳米管钛酸为前驱物制备了Bi掺杂的TiO2,并利用X射线衍射、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱等手段对样品进行了表征. 以甲基橙的光催化降解为模型反应评价了样品的可见光催化性能. 结果表明,Bi离子并没有进入TiO2的晶格中,而是以BiOCl的形式存在. 所制得的BiOCl/TiO2复合物对甲基橙降解表现出较优越的可见光催化活性;当Bi/Ti摩尔比为1%,水热温度为130℃时,所制催化剂的光催化性能最佳,并对光催化活性提高的机理进行了讨论. 同时,该催化剂对4-氯苯酚降解也表现出较高的光催化性能.