催化学报

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第34卷第4期目次

2013, 34 (4): 0-0.

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半导体/石墨烯复合光催化剂的制备及应用

陈建炜, 石建稳, 王旭, 崔浩杰, 付明来

2013, 34 (4): 621-640. DOI: 10.1016/S1872-2067(12)60530-0

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首先分析了石墨烯和半导体光催化剂的特点,以及二者复合后可能具有的优越性质,接着介绍了石墨烯和半导体复合光催化剂的制备方法,归纳了石墨烯增强半导体光催化的机理,然后阐述了复合光催化剂在降解有机污染物、光催化分解水产氢、光催化还原CO₂制有机燃料和光催化灭菌四个典型的应用,最后对半导体/石墨烯复合光催化剂未来的发展趋势提出了展望.

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HZSM-5上生物质催化裂解的近期研究进展

谭顺, 张志军, 孙剑平, 王清文

2013, 34 (4): 641-650. DOI: 10.1016/S1872-2067(12)60531-2

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概述了近期的HZSM-5对生物质和生物油催化裂解的研究进展，重点介绍了催化剂的应用、生物油提质的方法和反应机理.

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Ni基催化剂上木质素模型化合物苯基苯乙醚C-O键的加氢裂解

宋奇, 蔡嘉莹, 张俊杰, 于维强, 王峰, 徐杰

2013, 34 (4): 651-658. DOI: 10.1016/S1872-2067(12)60535-X

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研究了Ni基催化剂上木质素模型化合物苯基苯乙醚中C-O-C键加氢裂解性能.结果表明,Ni/C催化剂显示出优异的加氢裂解能力,苯基苯乙醚的转化率达到99%以上.Ni/C催化剂的还原方法对裂解选择性有重要影响;氢气还原制备的Ni/C-H催化剂上,C-O-C键裂解选择性为85%.Ru/C和Pd/C催化剂上裂解选择性分别为40%和69%.采用碳热还原方法制备的Ni/C-C催化剂,可以实现高选择性加氢和裂解,C-O-C键裂解选择性达到99%以上,其中芳烃化合物收率为44%.这可能与镍组分和载体碳之间的相互作用有关.

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乙醇辅助的化学沉积法制备硫化型Mo/γ-Al₂O₃加氢脱硫催化剂

石冈, 韩伟, 袁珮, 范煜, 鲍晓军

2013, 34 (4): 659-666. DOI: 10.1016/S1872-2067(11)60516-0

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以硫代乙酰胺为硫源,钼酸钠为钼源,乙醇为分散剂,采用化学沉积法制备了MoS₃/Al₂O₃催化剂前驱体,再用H₂高温处理得到高分散硫化型MoS₂/γ-Al₂O₃催化剂,运用N₂吸附-脱附、X射线光电子能谱以及高分辨透射电子显微镜等技术对MoS₂/γ-Al₂O₃催化剂进行了表征,并以二苯并噻吩作为模型化合物评价了催化剂的加氢脱硫(HDS)活性.结果表明,与浸渍法相比,所制催化剂具有更大的比表面积和孔体积、更高的活性金属分散度、更佳的Mo物种硫化度以及更短的MoS₂片层长度和更高的堆积度,因而在二苯并噻吩HDS反应中表现出远优于浸渍法所制催化剂的活性.乙醇可通过S?H-O氢键吸附至MoS₃纳米粒子表面,可有效防止其生长和团聚,起到分散剂的作用.

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一种具有低SO₂氧化活性并满足欧V排放标准的柴油车氧化型催化剂

陈永东, 王磊, 关小旭, 唐水花, 龚茂初, 陈耀强

2013, 34 (4): 667-673. DOI: 10.1016/S1872-2067(12)60545-2

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制备了具有高性能的稀土储氧材料Ce_0.75Zr_0.25O₂-Al₂O₃,Ti_0.9Zr_0.1O₂复合材料和Cr改性的β分子筛(Cr-β分子筛),并以此制备了单Pt型柴油车尾气净化氧化型催化剂.低温N₂吸附-脱附、储氧量测试结果表明,Ce_0.75Zr_0.25O₂-Al₂O₃样品具有较大的比表面积和优异的储氧性能,Ti_0.9Zr_0.1O₂复合材料也具有优越的织构性能.催化剂对HC和CO具有较高的催化活性,可使SOF在140℃开始转化,且具有较低的SO₂氧化活性.在YC4F国Ⅳ柴油机的测试结果表明,经该催化剂处理后的尾气排放能够满足欧Ⅴ排放标准对HC和CO排放要求.

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温控聚乙二醇两相体系中纳米钯催化肉桂醛选择性加氢反应

牛明铭, 王艳华, 李文江, 蒋景阳, 金子林

2013, 34 (4): 674-678. DOI: 10.1016/S1872-2067(12)60552-X

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将具有“高温混溶、室温分相”功能的聚乙二醇4000(PEG₄₀₀₀)与甲苯-正庚烷组成的两相体系用于纳米钯催化的肉桂醛选择性加氢反应中.在优化的反应条件下,肉桂醛转化率和氢化肉桂醛选择性分别为99%和98%.钯纳米催化剂经简单分相即可与产物分离,且循环使用8次,其活性和选择性基本保持不变.

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三价铑催化亚甲胺内盐与丙烯酰胺氧化合成三取代吡唑

甄文萃, 杜正银, 李兴伟

2013, 34 (4): 679-683. DOI: 10.1016/S1872-2067(12)60584-1

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将三价铑离子配合物用于催化甲亚胺内盐与取代的丙烯酰胺之间的氧化偶联反应,实现了三取代的吡唑化合物的合成.在这个过程中,取代的丙烯酰胺的烯烃发生了C-H键活化.此类反应和用丙烯酸酯时的反应具有不同的选择性.

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纳米Ru-Mn/ZrO₂催化剂上苯选择加氢制环己烯

孙海杰, 江厚兵, 李帅辉, 王红霞, 潘雅洁, 董英英, 刘寿长, 刘仲毅

2013, 34 (4): 684-694. DOI: 10.1016/S1872-2067(11)60489-0

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采用共沉淀法制备了一系列不同Mn含量的纳米Ru-Mn催化剂,考察了纳米ZrO₂作分散剂时它们催化苯选择加氢制环己烯的反应性能,并采用X射线衍射、透射电镜、N₂物理吸附、X射线荧光、原子吸收光谱和俄歇电子能谱等手段对催化剂进行了表征.结果表明,Ru-Mn催化剂上Mn以Mn₃O₄存在于Ru的表面上.在加氢过程中,Mn₃O₄可以与浆液中ZnSO₄发生化学反应生成一种难溶性的(Zn(OH)₂)₃(ZnSO₄)(H₂O)₃盐.该盐易化学吸附在Ru催化剂表面上,从而在提高Ru催化剂上环己烯选择性起关键作用.当催化剂中Mn含量为5.4%时,环己烯收率为61.3%,同时具有良好的稳定性和重复使用性能.

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A succinimide-N-sulfonic acid catalyst for acetylation reactions in absence of a solvent

Farhad SHIRINI, Nader Ghaffari KHALIGH

2013, 34 (4): 695-703. DOI: 10.1016/S1872-2067(11)60499-3

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A small amount of succinimide-N-sulfonic acid efficiently catalyzed the acetylation of a variety alcohols, phenols, thiols, amines and aldehydes with acetic anhydride at room temperature under solvent free conditions. This catalyst has the advantages of excellent yields and short reaction times and the reaction can be carried out on a large scale, which makes it potentially useful for industrial applications.

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Combustion-derived CuO nanoparticles: An effective and environmentally benign catalyst in the synthesis of aromatic nitriles from aromatic aldehydes

Belladamadu Siddappa ANANDAKUMAR, Muthukur Bhojegowd Madhusudana REDDY, Chikka Nagaiah THARAMANI, Mohamed Afzal PASHA, Gujjarahalli Thimmanna CHANDRAPPA

2013, 34 (4): 704-710. DOI: 10.1016/S1872-2067(11)60503-2

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CuO nanoparticles were synthesized using an energy-efficient and rapid solution combustion technique with malic acid employed as a fuel. The combustion-derived CuO nanoparticles were used as catalysts in a one-pot synthesis of aromatic nitriles from aromatic aldehydes and hydroxylamine hydrochloride. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, and Brunauer-Emmett-Teller surface area analysis. The catalytic activity of the CuO nanoparticles in the synthesis of aromatic nitriles from aromatic aldehydes was evaluated. The present protocol offers the advantages of a clean reaction, simple methodology, short reaction duration (1-2 min), and high yield (85%-98%). The catalytic activity of the CuO nanoparticles was found to be higher than that of bulk CuO powder under the same conditions. The catalyst can also be recovered and reused up to four times with no significant loss of catalytic activity. The present approach is inexpensive and is a convenient technique suitable for industrial production of CuO nanoparticles and nitriles.

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Preparation of CuS-graphene oxide/TiO₂ composites designed for high photonic effect and photocatalytic activity under visible light

PARK ChongYeon, GHOSH Trisha, MENG ZeDa, KEFAYAT Ullah, VIKRAM Nikam, OH WonChun

2013, 34 (4): 711-717. DOI: 10.1016/S1872-2067(11)60502-0

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CuS-graphene oxide/TiO₂ composites were prepared using a sol-gel method to improve the photocatalytic performance of the photocatalyst. The composites were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, and transmission electron microscopy. The photocatalytic activities were examined by the degradation of methylene blue (MB) under visible-light irradiation. The photodegradation of MB under visible-light irradiation reached 90.1% after 120 min. The kinetics of MB degradation was plotted alongside the values calculated from the Langmuir-Hinshelwood equation. The CuS-graphene oxide/TiO₂ sample prepared using 0.2 mol of TiO₂ showed the best photocatalytic activity. This was attributed to a cooperative reaction as a result of increased photoabsorption by graphene oxide and an increased photocatalytic effect by CuS.

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Silica-functionalized N-propylpiperazine for immobilization of palladium nanoparticles as efficient heterogeneous catalyst for cyanation reactions

Khodabakhsh NIKNAM, Abdollah DERIS, Farhad PANAHI

2013, 34 (4): 718-722. DOI: 10.1016/S1872-2067(12)60532-4

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An efficient heterogeneous Pd catalytic system has been developed, based on immobilization of Pd nanoparticles (PNPs) on a silica-bonded N-propylpiperazine (SBNPP) substrate. The SBNPP substrate effectively stabilizes the PNPs and improves their stability against aggregation. The catalytic activity of this catalyst was investigated in the cyanation of aryl halides with K₄[Fe(CN)₆] as the cyanide source. The catalyst could be recycled several times without appreciable loss of catalytic activity.

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单壁碳纳米管对C-C键水解酶BphD的固定化性能

沈娥, 曲媛媛, 周豪, 孔春雷, 马桥, 张旭旺, 周集体

2013, 34 (4): 723-733. DOI: 10.1016/S1872-2067(12)60564-6

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采用修饰与未修饰单壁碳纳米管固定C-C键水解酶BphD,并对固定化酶的相对活性、稳定性、重复使用性进行了考察.结果表明,未修饰单壁碳纳米管固定的BphD相对活性为游离态的52.5%,其热稳定性和在变性剂中的稳定性均有所提高,且重复使用10次仍可保持初始活力的90%.修饰单壁碳纳米管固定的BphD相对活性可达99.7%,但其稳定性没有明显提高.同源模建及分子对接分析结果显示,未修饰的单壁碳纳米管对BphD亚基之间的联系可能存在干扰作用,从而对其活性产生影响.

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金纳米粒子在TiO₂气凝胶基质上的行为: 光催化活性评价和结构研究

Zsolt PAP, Andreea RADU, Izabella Jolan HIDI, Georgian MELINTE, Lucian DIAMANDESCU, Traian POPESCU, Lucian BAIA, Virginia DANCIU, Monica BAIA

2013, 34 (4): 734-740. DOI: 10.1016/S1872-2067(11)60500-7

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TiO₂-Au aerogels containing different amounts of gold nanoparticles of different sizes (5 and 16 nm) were successfully synthesized using a sol-gel procedure, and were tested for salicylic acid photodegradation under UV irradiation. The structure and morphology of the obtained materials were investigated using X-ray diffraction, transmission electron microscopy, and N₂ adsorption-desorption measurements. UV-Vis spectroscopy was used to study the optical properties. The effects of the gold nanoparticles on the TiO₂ crystallization process were twofold, as follows: (i) the number of crystallized zones was strongly related to the concentration of the gold nanoparticles, and (ii) the smaller gold particles increased the time taken for the crystallization of the samples. It was found that the noble metal-doped samples exhibited higher degradation rates compared with bare titania. It was found that the most active photocatalyst in each studied system was the sample with the highest concentration of gold nanoparticles. Additionally, the highest degradation rate value was obtained with the smallest Au nanoparticles (46.4 × 10^-3 μmol/(L·s).

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脂质体为模板仿生硅化固定葡萄糖氧化酶

朱亚男, 姜艳军, 高静, 周丽亚, 贺莹, 贾霏

2013, 34 (4): 741-750. DOI: 10.1016/S1872-2067(11)60519-6

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将脂质体囊泡与仿生硅化技术相结合,模拟细胞纳微环境,实现以脂质体为模板仿生制备氧化硅固定葡萄糖氧化酶(GOx),建立性能稳定的固定化酶.扫描电镜分析显示,固定化GOx为球形纳米粒子,粒径分布在200nm左右,在优化反应条件下GOx回收率达到71.8%.由于载体的空间限制作用及其提供的较稳定微环境,固定化GOx表现出良好的热稳定性和pH稳定性,其对变性剂耐受性和操作稳定性等也得到明显提高.

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超声辅助合成铈锆铝氧化物及其负载Pd催化剂对乙醇汽油车尾气的净化性能

刘建英, 赵明, 徐成华, 刘盛余, 张雪乔, 陈耀强

2013, 34 (4): 751-757. DOI: 10.1016/S1872-2067(11)60488-9

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在共沉淀法的基础上辅助以超声制备了铈锆铝复合氧化物(CZA),采用比表面分析仪、X射线衍射、程序升温还原、储氧量和X射线光电子能谱对材料进行了表征.结果表明,超声振荡有助于小而均匀的孔生成,有利于Pd物种的分散;超声振荡还能提高CZA的储氧量,使材料的表面组成与体相组成趋于一致.催化活性测试表明,材料经过超声处理的Pd-CZA净化乙醇汽油车尾气时,可以将氧气的完全利用窗口从0~0.64%拓宽至0~1.16%;并且使乙醇、C₃H₈和CO起燃温度分别下降了30,28和24℃.此外,Pd物种与CZA-U的相互作用有利于NO与C₃H₈和C₂H₅OH的反应.

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Synthesis of polyhydroquinoline derivatives via a four-component Hantzsch condensation catalyzed by tin dioxide nanoparticles

Seyed Mohammad VAHDAT, Fereshteh CHEKIN, Mehdi HATAMI, Maryam KHAVARPOUR, Saeed BAGHERY, Ziba ROSHAN-KOUHI

2013, 34 (4): 758-763. DOI: 10.1016/S1872-2067(11)60518-4

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Tin dioxide (SnO₂) nanoparticles efficiently catalyzed unsymmetrical four-component Hantzsch condensations of various aldehydes, dimedone, ethyl acetoacetate, and ammonium acetate to form polyhydroquinoline derivatives in excellent yields. This novel method offers several advantages over the traditional method of synthesizing these compounds, including safety, mild conditions, short reaction times, high yields, and an easy workup.

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Stabilities of zeolite-supported Ni catalysts for dry reforming of methane

Anis H. FAKEEHA, Wasim U. KHAN, Ahmed S. AL-FATESH, Ahmed E. ABASAEED

2013, 34 (4): 764-768. DOI: 10.1016/S1872-2067(12)60554-3

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Ni/γ-Al₂O₃, Ni/Y-zeolite, and Ni/H-ZSM-5 catalysts were prepared using the incipient wetness impregnation method. Their catalytic performance in dry reforming of methane was studied. The fresh and used catalysts and deposited carbon were characterized using H₂ temperature-programmed reduction, temperature-programmed oxidation, N₂ adsorption-desorption, X-ray diffraction, and thermogravimetric analysis. The H-ZSM-5-supported Ni catalyst proved to be more stable than the other two catalysts, as it had the lowest carbon deposition.

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烷基咪唑离子液体对脂肪酶催化酯水解反应活性的影响

李娜, 杜伟燕, 黄卓楠, 赵炜, 王寿江

2013, 34 (4): 769-780. DOI: 10.1016/S1872-2067(11)60521-4

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考察了1-烷基-3-甲基咪唑类离子液体对柱状假丝酵母脂肪酶(CRL)催化橄榄油水解反应活性的影响,利用电导法确定了磷酸盐缓冲液中Br^-,Cl^-,[BF₄]^-系列咪唑离子液体的临界胶束浓度(CMC)和[PF₆]^-系列咪唑离子液体的溶解度.结果显示,离子液体的阴、阳离子对酶活性的影响规律与离子液体的Kosmotropicity性质无明显关联,但与离子液体在体系中的含量密切相关,在最适离子液体含量时,酶活性达到最高;阳离子[C_nMIM]⁺中的n越大,可促进酶活性的离子液体适宜含量越低;Br^-,[BF₄]^-系列离子液体的浓度超过CMC时则抑制酶活;阴离子对酶活性的最大促进作用顺序为Br^->Cl^->[BF₄]^->[PF₆]^-.离子液体对酶活性的影响随体系pH和温度的不同而改变,在最适离子液体浓度时的最适pH均为7.000.在pH 7.000,30^oC以及[C₈MIM]Br离子液体浓度为47.6 mmol/L的最佳条件下,最高相对酶活力和比活力分别达到1734%和54.4 U/mg protein.

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超细钴纳米粒子催化1-己烯低压氢甲酰化反应的原位红外光谱研究

王航, 蔡志鹏, 钟梦琦, 姚思宇, 寇元

2013, 34 (4): 781-788. DOI: 10.1016/S1872-2067(11)60504-4

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利用原位透射红外光谱研究了2.8 nm超细钴纳米粒子在2~3 MPa合成气(CO:H₂= 1:1)和100^oC条件下催化的1-己烯氢甲酰化反应. 结果表明, 在反应中出现与Co₂(CO)₈类似的红外吸收峰(2071, 2041和2022 cm^-1), 被证明是不同Co位点端式吸附CO. 首次观测到了位于2054 cm^-1处吸收峰处的物种, 可能归属为RCH₂CH₂COCo. 通过此中间物种，产物醛可以在钴催化剂表面经由结合一个氢原子脱除反应而获得.

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金属对钛硅分子筛TS-1催化丁二烯环氧化性能的影响

吴妹, 丑凌军, 宋焕玲

2013, 34 (4): 789-797. DOI: 10.1016/S1872-2067(11)60498-1

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制备了不同金属改性的钛硅分子筛样品M-TS-1 (M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, La, 负载量为1%), 并研究了其催化丁二烯环氧化反应的性能. 结果表明, V, Cr, Mn的加入导致H₂O₂无效分解, 因而在丁二烯环氧化反应中表现出较高的H₂O₂转化率和较低有效利用率; Fe, Co, Ni以及稀土金属La均在一定程度上促进了TS-1对H₂O₂的有效利用; Cu, Zn抑制了H₂O₂的转化, 使得H₂O₂转化率和有效利用率都较低; Cd有效提高了TS-1的催化活性, H₂O₂转化率和有效利用率均接近100%. 采用X射线衍射、N₂吸附-脱附、X射线光电子能谱、傅里叶变换红外光谱等手段表征了上述各金属的改性对TS-1骨架结构以及Ti活性中心周围电子环境的影响. 结果表明, 各M-TS-1样品的骨架结构都仍保持原有的MFI构型, 但是TS-1中Ti活性中心周围的电子环境受到来自各种金属的不同程度影响, 关联催化活性时没有特定的规律性.

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SAPO-35分子筛的合成及其甲醇制烯烃反应性能

李冰, 田鹏, 李金哲, 陈景润, 袁扬扬, 苏雄, 樊栋, 魏迎旭, 齐越, 刘中民

2013, 34 (4): 798-807. DOI: 10.1016/S1872-2067(12)60557-9

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以六亚甲基亚胺为模板剂,采用水热法合成了不同硅含量的磷酸硅铝分子筛SAPO-35,并利用X射线衍射、X射线荧光光谱、扫描电镜、固体核磁、X射线光电子能谱和N₂吸附-脱附等方法对样品进行了表征.研究了不同硅含量的SAPO-35分子筛在甲醇转化制烯烃反应中的催化行为,同时对比分析了具有相近硅含量的SAPO-35和SAPO-34分子筛在甲醇转化反应过程中积炭物种随反应时间的演变特征,尝试将分子筛结构和其积炭失活行为进行了关联.

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花状TiO₂分级结构的可控合成与其光催化性能

杜利霞, 吴志娇, 吴谦, 江潮, 朴玲钰

2013, 34 (4): 808-814. DOI: 10.3724/SP.J.1088.2013.21281

摘要 ( 913 ) [Full Text(HTML)] ()

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采用水热法可控合成了花状TiO₂分级结构材料,运用扫描电镜、透射电镜、X射线衍射、N₂物理吸附-脱附等手段,对其进行了表征,系统研究了NaOH用量、H₂O₂浓度、HNO₃浓度、反应温度及时间等因素对所得样品形貌的影响,并评价了它们的光催化性能.结果表明,花状TiO₂分级结构为锐钛矿相,颗粒大小均一;随制备条件的变化,构成花状TiO₂分级结构的基元结构分别为纳米线、纳米片,纳米线直径约25nm,纳米片厚度不足10nm;该样品具有较高的比表面积,表现出良好的单次光催化活性与重复使用性能.

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