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过刊目录

    催化学报
    Chinese Journal of Catalysis

    2015, Vol. 36, No. 4
    Online: 2015-03-23

    封面介绍:

    Kannan 教授及其合作者分析了用于质子交换膜燃料电池和碱性膜燃料电池纳米催化剂的研究现状, 介绍了几种贵金属和非贵金属催化剂的合成方法, 并讨论了用于原位和非原位表征这些催化材料的各种方法. 见本期第 458–472 页.

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    目录
    第36卷第4期目次
    2015, 36 (4):  0-0. 
    摘要 ( 114 )   PDF(2546KB) ( 494 )  
    燃料电池电催化专栏
    Preface to Special Column on Electrocatalysis for Fuel Cells
    Panagiotis Tsiakaras, Shuqin Song
    2015, 36 (4):  457-457.  DOI: 10.1016/S1872-2067(15)60832-4
    摘要 ( 251 )   [Full Text(HTML)] () PDF(241KB) ( 476 )  
    Nano-electrocatalyst materials for low temperature fuel cells: A review
    K. Vignarooban, J. Lin, A. Arvay, S. Kolli, I. Kruusenberg, K. Tammeveski, L. Munukutla, A. M. Kannan
    2015, 36 (4):  458-472.  DOI: 10.1016/S1872-2067(14)60175-3
    摘要 ( 310 )   [Full Text(HTML)] () PDF(3549KB) ( 1070 )  

    Low temperature fuel cells are an attractive technology for transportation and residential applications due to their quick start up and shut down capabilities. This review analyzed the current status of nanocatalysts for proton exchange membrane fuel cells and alkaline membrane fuel cells. The preparation process influences the performance of the nanocatalyst. Several synthesis methods are covered for noble and non-noble metal catalysts on various catalyst supports including carbon nanotubes, carbon nanofibers, nanowires, and graphenes. Ex situ and in situ characterization methods like scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and fuel cell testing of the nanocatalysts on various supports for both proton exchange and alkaline membrane fuel cells are discussed. The accelerated durability estimate of the nanocatalysts, predicted by measuring changes in the electrochemically active surface area using a voltage cycling method, is considered one of the most reliable and valuable method for establishing durability.

    A review of the development of high temperature proton exchange membrane fuel cells
    Suthida Authayanun, Karittha Im-orb, Amornchai Arpornwichanop
    2015, 36 (4):  473-483.  DOI: 10.1016/S1872-2067(14)60272-2
    摘要 ( 326 )   [Full Text(HTML)] () PDF(529KB) ( 1394 )  

    Due to the need for clean energy, the development of an efficient fuel cell technology for electricity generation has received considerable attention. Much of the current research efforts have investigated the materials for and process development of fuel cells, including the optimization and simplification of the fuel cell components, and the modeling of the fuel cell systems to reduce their cost and improve their performance, durability and reliability to enable them to compete with the conventional combustion engine. A high temperature proton exchange membrane fuel cell (HT-PEMFC) is an interesting alternative to conventional PEMFCs as it is able to mitigate CO poisoning and water management problems. Although the HT-PEMFC has many attractive features, it also possesses many limitations and presents several challenges to its widespread commercialization. In this review, the trends of HT-PEMFC research and development with respect to electrochemistry, membrane, modeling, fuel options, and system design were presented.

    Facile synthesis of Zr- and Ta-based catalysts for the oxygen reduction reaction
    David Sebastián, Vincenzo Baglio, Shuhui Sun, Ana C. Tavares, Antonino S. Aricò
    2015, 36 (4):  484-489.  DOI: 10.1016/S1872-2067(14)60253-9
    摘要 ( 211 )   [Full Text(HTML)] () PDF(792KB) ( 560 )  

    Cathode catalysts for direct alcohol fuel cells (DAFCs) must have high catalytic activity for the oxygen reduction reaction (ORR), low cost, and high tolerance to the presence of methanol or ethanol. Pt is the benchmark catalyst for this application owing to its excellent electrocatalytic activity, but its high cost and low tolerance to the organic fuel permeating through the membrane have hindered the commercialization of DAFCs. Herein we present a facile synthesis route to obtain organic fuel-tolerant Zr- and Ta-based catalysts supported on carbon. This method consists of a simple precipitation of metal precursors followed by a heat treatment. X-ray diffraction analyses confirmed that the obtained samples were crystalline ZrO2-x and Na2Ta8O21-x having crystallite sizes of 26 and 32 nm, respectively. The thermal treatment effectively increased the activity of the catalysts towards the ORR, although further optimization is necessary. Both catalysts exhibited a high tolerance to the presence of methanol with only a moderate reduction in ORR activity even at high methanol concentration (0.5 mol/L).

    应用于氧还原反应的石墨烯-无定形碳核壳结构复合材料载铂催化剂
    吴惠, 彭焘, 寇宗魁, 张建, 程坤, 何大平, 潘牧, 木士春
    2015, 36 (4):  490-495.  DOI: 10.1016/S1872-2067(14)60211-4
    摘要 ( 384 )   [Full Text(HTML)] () PDF(1122KB) ( 737 )  

    采用氯化法制备石墨烯-无定型碳复合材料(GNS@a-C), 并用作质子交换膜燃料电池(PEMFC)氧还原反应Pt催化剂的载体. 结果显示, 所制Pt/GNS@a-C催化剂与传统商业催化剂Pt/C相比, 有较好的活性和较高的稳定性: 质量活性(0.121 A/mg)几乎是Pt/C (0.064 A/mg)的两倍. 更重要的是, 该新型催化剂加速4000圈后其电化学活性面积保留了最初的51%,与Pt/C的33%相比, 前者有更好的电化学稳定性, 显示它在PEMFC中将具有较好的应用潜力.

    Improving the efficiency of a direct ethanol fuel cell by a periodic load change
    Andrzej Jablonski, Adam Lewera
    2015, 36 (4):  496-501.  DOI: 10.1016/S1872-2067(14)60226-6
    摘要 ( 272 )   [Full Text(HTML)] () PDF(675KB) ( 680 )  

    We present a simple method to increase the efficiency of a direct ethanol fuel cell by a periodic modulation of the load (pulsed mode). The fuel cell was periodically short circuited with a resistor (1 Ω) for a few seconds (high load period) followed by a low load period of up to 100 s when the resistor was disconnected. The open circuit voltage (OCV) values before and after the short circuit of the cell showed an increase of up to 70 mV. The higher OCV was due to the oxidation and removal of strongly adsorbed CO during the electric short circuit when the electric potential of the anode was increased to be close to the cathode potential. The depoisoned anode surface was much more active directly after the short circuit. The slow decrease of the OCV observed after the short circuit was caused by the subsequent poisoning of the anode surface, which can be neutralized by another short circuit. In general, a stable increase in cell performance was obtained by repetition of the electric short circuit. The data showed that the pulse mode gave an increase in the power generated by the direct ethanol fuel cell by up to 51% and was 6% on average. It is anticipated that this mode of operation can be used also in different types of polymer electrolyte membrane fuel cells where CO poisoning is a problem, and after optimization of the parameters, a much higher gain in efficiency can be obtained.

    TiO2修饰La0.6Sr0.4Co0.2Fe0.8O3-δ用于中温固体氧化物燃料电池的阴极
    刘伟星, 赵哲, 涂宝峰, 崔大安, 区定容, 程谟杰
    2015, 36 (4):  502-508.  DOI: 10.1016/S1872-2067(14)60235-7
    摘要 ( 390 )   [Full Text(HTML)] () PDF(901KB) ( 723 )  

    纳米TiO2修饰的La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF)阴极被直接应用于YSZ电解质电池上. TiO2可阻止LSCF和YSZ间的化学反应, 抑制SrZrO3的形成. LSCF-0.25 wt% TiO2阴极电池在0.7 V和600 ℃下的电流密度是LSCF阴极电池的1.6倍. 电化学阻抗谱结果表明, TiO2修饰显著加快了氧离子注入电解质的过程, 这可能与TiO2抑制了阴极/电解质界面处高电阻SrZrO3层的形成有关. 本文为在ZrO2基电解质上使用高性能的(La,Sr)(Co,Fe)O3阴极材料提供了一种简单有效的方法.

    Carbon to electricity in a solid oxide fuel cell combined with an internal catalytic gasification process
    M. Konsolakis, G. E. Marnellos, A. Al-Musa, N. Kaklidis, I. Garagounis, V. Kyriakou
    2015, 36 (4):  509-516.  DOI: 10.1016/S1872-2067(14)60262-X
    摘要 ( 257 )   [Full Text(HTML)] () PDF(867KB) ( 809 )  

    This study explores strategies to develop highly efficient direct carbon fuel cells (DCFCs) by combining a solid-oxide fuel cell (SOFC) with a catalyst-aided carbon-gasification process. This system employs Cu/CeO2 composites as both anodic electrodes and carbon additives in a cell of the type: carbon|Cu-CeO2/YSZ/Ag|air. The study investigates the impact on in situ carbon-gasification and DCFC performance characteristics of catalyst addition and variation in the carrier gas used (inert He versus reactive CO2). The results indicate that cell performance is significantly improved by infusing the catalyst into the carbon feedstock and by employing CO2 as the carrier gas. At 800 ℃, the maximum power output is enhanced by approximately 40% and 230% for carbon/CO2 and carbon/catalyst/CO2 systems, respectively, compared with that of the carbon/He configuration. The increase observed when employing the catalyst and CO2 as the carrier gas can be primarily attributed to the pronounced effect of the catalyst on carbon-gasification through the reverse-Boudouard reaction, and the subsequent in situ electro-oxidation of CO at the anode three-phase boundary.

    亮点
    Catalysis on a metal surface with a graphitic cover
    Qiang Fu, Xinhe Bao
    2015, 36 (4):  517-519.  DOI: 10.1016/S1872-2067(15)60828-2
    摘要 ( 299 )   [Full Text(HTML)] () PDF(495KB) ( 792 )  
    综述
    Silica supported Brönsted acids as catalyst in organic transformations: A comprehensive review
    Manpreet Kaur, Sahil Sharma, Preet M. S. Bedi
    2015, 36 (4):  520-549.  DOI: 10.1016/S1872-2067(14)60299-0
    摘要 ( 331 )   [Full Text(HTML)] () PDF(1040KB) ( 2124 )  

    Brönsted acid catalysts have been used in a number of organic transformations. To overcome limitations, such as toxicity, volatility, high price and hazardous nature of the conventional methods, the catalysts are adsorbed on silica gel to give the benefits and advantages of ready availability, simple work-up procedure, long catalytic life, environment-friendliness, good to excellent yields and recyclability. The uses of such catalysts have gained importance worldwide. This article describes some of the important silicated catalysts, namely, heteropolyacids, polyphosphoric acid, perchloric acid, fluoroboric acid, and silicated sulphuric acid. These catalysts have been used in a number of organic reactions to yield compounds that are important in the chemical and pharmaceutical industries. We summarize the beneficial effects of these catalysts and the reports that have been published on them in the past several years. In the present review, the description of the catalysts are introduced followed by a recent research history, and a comparison between the silica supported catalysts and other (polymer) supported catalysts. The article ends up giving the advantages of these catalytic systems over the conventional catalyst.

    论文
    TiN0.3/CeO2光阳极材料的构筑及其光电催化性能
    崔华楠, 李登, 刘冠涛, 梁振兴, 石建英
    2015, 36 (4):  550-554.  DOI: 10.1016/S1872-2067(14)60295-3
    摘要 ( 324 )   [Full Text(HTML)] () PDF(716KB) ( 662 )  

    采用高温氮化法在Ti片基底上生长一层TiN0.3薄膜, 进一步利用电化学沉积法在TiN0.3薄膜上生长CeO2, 制备了TiN0.3/CeO2复合材料. 分别用X射线衍射和扫描电镜研究了复合材料的晶体和形貌结构, 用紫外-可见光谱探究了材料的光学吸收性能. 结果表明, 球状CeO2颗粒均匀地分布在TiN0.3表面; 该复合光阳极除了TiN0.3对可见光的吸收外, 外层的CeO2同时实现了对紫外光的吸收. 光电催化性能研究发现, TiN0.3/CeO2复合光阳极能够显著提高TiN0.3或CeO2的光电流密度, 同时增加光电流的稳定性. TiN0.3/CeO2独特的双层结构是其光电催化性能提高的主要原因. 在TiN0.3与CeO2界面处异质结构的驱动下, CeO2层中的光生电子迁移至TiN0.3层, 而相应的光生空穴在界面处被Ce3+所消耗, 从而提高了CeO2层中电子和空穴的分离效率, 光电流密度也随之提高; 同时, 位于CeO2与电解液界面处的Ce3+作为水分子的吸附中心和反应活性中心, 加快了界面处水的氧化反应, 从而进一步促进了稳定光电流的产生. 鉴于TiN0.3/CeO2光阳极材料优良的光电催化性能, 其在太阳能光电催化领域具有潜在的应用, 对于新型高效光电转化材料的设计与合成具有借鉴作用.

    Pd-isatin Schiff base complex immobilized on γ-Fe2O3 as a magnetically recyclable catalyst for the Heck and Suzuki cross-coupling reactions
    Sara Sobhani, Farzaneh Zarifi
    2015, 36 (4):  555-563.  DOI: 10.1016/S1872-2067(14)60291-6
    摘要 ( 254 )   [Full Text(HTML)] () PDF(600KB) ( 646 )  

    A Pd-isatin Schiff base complex immobilized on γ-Fe2O3 (Pd-isatin Schiff base-γ-Fe2O3) was synthesized and characterized by Fourier transform infrared, scanning electron microscopy, high resolution transmission electron microscopy, X-ray diffraction, thermogravimetric gravimetric analysis, inductively-coupled plasma, X-ray photoelectron spectroscopy, and elemental analysis. It was used as a magnetically reusable Pd catalyst for the Heck and Suzuki cross-coupling reactions.

    高效稳定的AgxS的制备及其光催化性能
    常平静, 程海洋, 林伟伟, 李小汝, 赵凤玉
    2015, 36 (4):  564-571.  DOI: 10.1016/S1872-2067(14)60288-6
    摘要 ( 251 )   [Full Text(HTML)] () PDF(790KB) ( 573 )  

    分别采用水热法(AgxS-H)和原位离子交换法(AgxS-IE)制备了AgxS. 采用扫描电镜(SEM)、X射线衍射光谱、紫外可见近红外吸收光谱、N2吸附-脱附、X射线光电子能谱和表面光电压测试对催化剂进行了表征. 以光(λ ≥ 420 nm)降解亚甲基蓝为模型反应, 考察了AgxS的光催化性能. 与AgxS-IE相比, AgxS-H具有较小的粒径、较大的禁带宽度、较低光生电荷复合率, 因此具有较高的光催化活性. 此外, AgxS-H还表现了较好的稳定性, 循环使用五次仍能够保持较高的光催化活性. 结果表明, AgxS光催化降解亚甲基蓝主要以羟基自由基氧化为主, 光生空穴氧化为辅的光催化氧化过程. AgxS-H作为一种有效的光催化剂, 在降解有机染料污水方面具有潜在的应用价值.

    Fe3O4@MCM-48-SO3H: An efficient magnetically separable nanocatalyst for the synthesis of benzo[f]chromeno[2, 3-d]pyrimidinones
    Hassan Kefayati, Mostafa Golshekan, Shahab Shariati, Mahsa Bagheri
    2015, 36 (4):  572-578.  DOI: 10.1016/S1872-2067(14)60286-2
    摘要 ( 276 )   [Full Text(HTML)] () PDF(663KB) ( 1040 )  

    Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM-48. The sulfonic acid-functionalized nanoparticles were evaluated as catalysts for the synthesis of 5-aryl-1H-benzo[f]chromeno[2,3-d]pyrimidine- 2,4(3H,5H)-dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1-methylimidazolium hydrogen sulfate ([HMIm][HSO4]). The activity of Fe3O4@MCM-48-SO3H was comparable to those of the other heterogeneous and homogeneous catalysts.

    Catalytic abatement of CO and volatile organic compounds in waste gases by gold catalysts supported on ceria-modified mesoporous titania and zirconia
    Vasko Idakiev, Dimitar Dimitrov, Tatyana Tabakova, Krasimir Ivanov, Zhong-Yong Yuan, Bao-Lian Su
    2015, 36 (4):  579-587.  DOI: 10.1016/S1872-2067(14)60283-7
    摘要 ( 192 )   [Full Text(HTML)] () PDF(683KB) ( 734 )  

    Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6-Zr(OC3H7)4 assembly pathway, and ceria-modified TiO2 and ZrO2, prepared by a deposition-precipitation (DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the catalytic abatement of air pollutants, i.e., CO, CH3OH, and (CH3)2O. The gold was supported on the mesoporous oxides by a DP method. The supports and catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N2 adsorption-desorption analysis, and temperature-programmed reduction technique. A high degree of synergistic interaction between ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction between the gold nanoparticles and ceria-mesoporous oxide supports. The gold catalysts supported on ceria-modified mesoporous ZrO2 displayed superior catalytic activity (~100% conversion of CO at 10 ℃ and CH3OH at 60 ℃). The high catalytic activity can be attributed to the ability of the support to assist oxygen vacancies formation. The studies indicate that the ceria-modified mesoporous oxide supports have potential as supports for gold-based catalysts.

    MOCVD法制备Pd@ZIF-8催化剂及其催化Suzuki反应性能
    张明明, 高雅, 李闯, 梁长海
    2015, 36 (4):  588-594.  DOI: 10.1016/S1872-2067(14)60292-8
    摘要 ( 353 )   [Full Text(HTML)] () PDF(1028KB) ( 868 )  

    以金属有机骨架化合物ZIF-8为载体, Pd(C3H5)(C5H5)为金属有机前体, 采用金属有机气相沉积方法在室温下制备了Pd@ZIF-8催化剂. Pd纳米粒子在ZIF-8载体上均匀分布, 粒子尺寸约为1.5-3.5 nm. Pd@ZIF-8在温和条件下对多种卤代芳烃和苯硼酸的偶联反应均具有良好的活性. ZIF-8优异的化学稳定性不仅保证了其在制备过程中结构的完整, 而且赋予了催化剂优异的循环使用性能. 反应后Pd@ZIF-8材料的晶体结构、孔结构以及粒子分布均未发生明显的变化.

    Acetylation of alcohols and phenols under solvent-free conditions using iron zirconium phosphate
    Abdol R. Hajipour, Hirbod Karimi, Amir Masti
    2015, 36 (4):  595-602.  DOI: 10.1016/S1872-2067(14)60280-1
    摘要 ( 305 )   [Full Text(HTML)] () PDF(762KB) ( 797 )  

    Iron zirconium phosphate (ZPFe) nanoparticles were found to function as an efficient catalyst for the acetylation of a wide range of alcohols and phenols using acetic anhydride, generating good to excellent yields under solvent-free conditions. The steric and electronic properties of various substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively coupled plasma-optical emission spectrometry, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. These analyses revealed that the interlayer distance in the catalyst increased from 7.5 to 9.3 Å when Fe3+ was intercalated between the layers, whereas the crystallinity of the material was reduced. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity. This new method for the acetylation of alcohols and phenols has several important advantages, including mild and environmentally friendly reaction conditions, as well as good to excellent yields and a facile work-up.

    Modified hydrothermal synthesis and characterization of reduced graphene oxide-silver selenide nanocomposites with enhanced reactive oxygen species generation
    Lei Zhu, Shu Ye, Asghar Ali, Kefayat Ulla, Kwang Youn Cho, Won-Chun Oh
    2015, 36 (4):  603-611.  DOI: 10.1016/S1872-2067(14)60275-8
    摘要 ( 189 )   [Full Text(HTML)] () PDF(1433KB) ( 1042 )  

    A visible-light photocatalyst containing Ag2Se and reduced graphene oxide (RGO) was synthesized by a facile sonochemical-assisted hydrothermal method. X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analysis, and ultraviolet-visible diffuse reflectance spectroscopy results indicated that the RGO-Ag2Se nanocomposite contained small crystalline Ag2Se nanoparticles dispersed over graphene nanosheets and absorbed visible light. The high crystallinity of the nanoparticles increased photocatalytic activity by facilitating charge transport. N2 adsorption-desorption measurements revealed that the RGO-Ag2Se nanocomposite contained numerous pores with an average diameter of 9 nm, which should allow reactant molecules to readily access the Ag2Se nanoparticles. The RGO-Ag2Se nanocomposite exhibited higher photocatalytic activity than bulk Ag2Se nanoparticles to degrade organic pollutant rhodamine B and industrial dye Texbrite BA-L under visible-light irradiation (λ > 420 nm). The generation of reactive oxygen species in RGO-Ag2Se was evaluated through its ability to oxidize 1,5-diphenylcarbazide to 1,5-diphenylcarbazone. The small size of the Ag2Se nanoparticles in RGO-Ag2Se was related to the use of ultrasonication during their formation, revealing that this approach is attractive to form porous RGO-Ag2Se materials with high photocatalytic activity under visible light.

    掺氮纳米炭球担载高分散钯纳米催化剂的制备及其苯甲醇氧化性能
    郝燕, 王帅, 孙蔷, 石磊, 陆安慧
    2015, 36 (4):  612-619.  DOI: 10.1016/S1872-2067(14)60274-6
    摘要 ( 275 )   [Full Text(HTML)] () PDF(833KB) ( 812 )  

    负载型贵金属纳米催化剂中的金属纳米粒子易发生团聚或流失, 因此提高金属活性组分的分散性和稳定性很重要。我们报道了一种制备高分散钯纳米催化剂的方法, 通过浸泡法将氯钯酸前驱体负载到苯并噁嗪聚合物上, 再经过惰性气氛一步热解得到纳米炭球担载钯催化剂. 催化剂性能通过温和条件下苯甲醇氧化反应进行评价. 经过500 ℃热处理制备的催化剂, 从TEM图可以看出Pd纳米粒子均匀分散在载体上, 尺寸大小约为3 nm, 这是由于载体和钯活性组分的配位作用有利于提高钯纳米粒子的分散性和稳定性. 通过调控金属负载量及负载时间, 尽可能地实现活性组分分布在载体外表面, 制备的催化剂上最高TOF为690 h-1. 此催化剂同时具有较好的循环稳定性, 失活后的催化剂经过200 ℃焙烧即可实现再生.

    Nano-sized silica supported FeCl3 as an efficient heterogeneous catalyst for the synthesis of 1, 2, 4-triazine derivatives
    Davood Habibi, Somayyeh Vakili
    2015, 36 (4):  620-625.  DOI: 10.1016/S1872-2067(15)60829-4
    摘要 ( 207 )   [Full Text(HTML)] () PDF(648KB) ( 735 )  

    The one-pot synthesis of a series of 1,2,4-triazines from the reactions of semicarbazide or thiosemicarbazide with various α,β-dicarbonyl compounds under reflux conditions in a EtOH-H2O (9:1) mixture as solvent and catalyzed by nano-sized silica supported FeCl3 (FeCl3@SiO2) was investigated. The FeCl3 content of the catalyst was measured by atomic absorption to get the adsorption capacity. The reactions gave high yields of the product and the catalyst was easily separated and reused for successive reaction runs without significant loss of activity.

    Tin sulfide nanoparticles supported on activated carbon as an efficient and reusable Lewis acid catalyst for three-component one-pot synthesis of 4H-pyrano[2, 3-c]pyrazole derivatives
    Nasir Iravani, Mosadegh Keshavarz, Hossein Ali Shojaeian Kish, Rasool Parandvar
    2015, 36 (4):  626-633.  DOI: 10.1016/S1872-2067(14)60284-9
    摘要 ( 251 )   [Full Text(HTML)] () PDF(664KB) ( 677 )  

    Tin sulfide nanoparticles (SnS-NPs) were prepared in aqueous solution at room temperature on the surface of activated carbon (AC) and were investigated using field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction, reflective ultraviolet-visible spectrophotometry, and spectrofluorimetry. Calculations based on the SEM and TEM images showed that the sizes of the SnS-NPs immobilized on the AC were 30-70 nm. The prepared nanocomposite was used as a heterogeneous Lewis acid catalyst for the three-components one-pot synthesis of 4H-pyrano[2,3-c]pyrazole derivatives in ethanol at 80 ℃. The reactions were efficiently performed in the presence of the prepared catalyst in short reaction times, and gave the desired products in high yields. This catalyst can be easily recovered by simple filtration and recycled up to eight consecutive times without significant loss of its efficiency.

    High enantioselectivity in the asymmetric hydrogenation of ketones by a supported Pt nanocatalyst on a mesoporous modified MCM-41 support
    Susmit Basu
    2015, 36 (4):  634-638.  DOI: 10.1016/S1872-2067(14)60279-5
    摘要 ( 169 )   [Full Text(HTML)] () PDF(654KB) ( 567 )  

    Catalysts containing metal nanotubes were prepared by the adsorption of platinum metal nanotubes onto functionalized and modified silica surfaces (MCM-41 and fumed silica). (3- Chloropropyl)trimethoxysilane and cinchonidine were used for functionalization and modification, respectively. Potassium chloroplatinate was used as the metal precursor to impregnate platinum metal nanotubes on the pretreated functionalized and modified silica surfaces. The solid catalysts were characterized by ESEM, TEM, EDAX, and XPS. The MCM-41 supported platinum nanotube catalyst showed >98% to ~100% enantioselectivity towards the hydrogenation of a range of pharmaceutically important chemicals such as methyl pyruvate, ethyl pyruvate, and acetophenone with nearly full conversion.

    钯前驱体对汽车尾气处理Pd/Ce0.67Zr0.33O2催化剂催化性能的影响
    林嗣煜, 杨林颜, 阳雪, 周仁贤
    2015, 36 (4):  639-648.  DOI: 10.1016/S1872-2067(14)60264-3
    摘要 ( 286 )   [Full Text(HTML)] () PDF(1136KB) ( 705 )  

    分别以Pd(NO3)2, Pd(NH3)4(NO3)2和H2PdCl4为钯前驱体制备了Pd/Ce0.67Zr0.33O2 (CZ)催化剂. 以硝酸钯为钯前驱体制得的Pd/CZ(NO)催化剂具有较高的储氧量, 存在较多的小的钯簇, 其钯与载体间相互作用较强, 因此在三种新鲜催化剂中对HC和CO的消除表现出了最好的催化活性. 以硝酸四氨钯为钯前驱体制得的Pd/CZ(NH)催化剂具有较高的钯分散度, 存在较多的大的钯簇, 同时存在金属态和氧化态的钯, 从而对NO和NO2的消除表现出了较好的催化活性. 以氯钯酸为钯前驱体制得的Pd/CZ(Cl)催化剂由于钯分散度较小, 钯与载体间作用较弱, 存在的CeOCl抑制了氧空穴的生成, 因此对各种反应物的催化活性都较低. 但Pd/CZ(Cl)催化剂表现出了较好的热稳定性, 这是由于老化处理消除了残余的氯物种并且促进了钯与载体间的作用.

    NH3-SCR反应中Fe-ZSM-5的Fe物种分布和酸性位对其水热稳定性及抗硫和抗碳氢性能的影响
    石晓燕, 贺泓, 谢利娟
    2015, 36 (4):  649-656.  DOI: 10.1016/S1872-2067(14)60268-0
    摘要 ( 283 )   [Full Text(HTML)] () PDF(654KB) ( 906 )  

    以Na+型和H+型ZSM-5为载体制备了Fe-ZSM-5催化剂并用于氨选择性催化还原(NH3-SCR)氮氧化物. Fe-H-ZSM-5在新鲜时和750 oC含10%水的空气中老化后, 其SCR活性均优于Fe-Na-ZSM-5. 表征结果显示, Fe-H-ZSM-5和Fe-Na-ZSM-5的Fe物种分布和酸性位有所不同. 高温水热老化后Fe-H-ZSM-5分子筛骨架的脱铝较Fe-Na-ZSM-5严重. 水和硫的存在对Fe-H-ZSM-5和Fe-Na-ZSM-5的SCR活性的影响相似, 即降低了低温活性, 略提高了高温活性. Fe-Na-ZSM-5表现出比Fe-H-ZSM-5更好的抗碳氢中毒性能. 这两种催化剂的SO2和碳氢中毒是可逆的.

    水杨醛亚胺钒(Ⅲ)化合物催化乙烯聚合反应机理
    王永霞, 左明辉, 李悦生
    2015, 36 (4):  657-666.  DOI: 10.1016/S1872-2067(14)60271-0
    摘要 ( 349 )   [Full Text(HTML)] () PDF(1073KB) ( 747 )  

    钒系烯烃聚合催化剂在工业上有着不可替代的位置, 它可用于制备高活性窄分布的聚合物、乙烯与α-烯烃共聚物和间规聚丙烯等. 但由于实验手段难以确定钒催化剂活性物种的结构, 进一步对催化机理的确认及催化剂结构的改进十分困难. 本文运用密度泛函方法对水杨醛亚胺钒配合物催化乙烯聚合的活性物种结构进行了理论研究. 对多种活性物种模型的比较研究结果表明, 对此催化反应最有利的活性物种为中性双金属物种a1, a1结构中包含两个连接铝原子与钒中心的氯桥结构. 研究同时表明, 助催化剂AlEt2Cl的存在不仅加速了钒配合物前体的烷基化反应, 同时其对活性物种a1结构中氯桥的形成至关重要. 最后还研究了该催化体系的链终止反应机理.

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