催化学报

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第34卷第12期目次

2013, 34 (12): 0-0.

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2013 年总目次

2013, 34 (12): 1-1.

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2013年作者索引

2013, 34 (12): 2-2.

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用于Suzuki-Miyaura反应的阴离子交换树脂负载钯催化剂

张明明, 江曼曼, 梁长海

2013, 34 (12): 2161-2166. DOI: 10.1016/S1872-2067(12)60698-6

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以碱性阴离子交换树脂Amberlite IRA-900为载体，Pd(C₃H₅)(C₅H₅)为金属有机前体，采用金属有机气相沉积法在室温下制备了Pd@IRA-900多相催化材料. 紫外-可见光谱分析证明前体和树脂骨架之间的化学作用以及树脂本身的孔道结构使得Pd纳米粒子均匀分散在载体上. 透射电镜结果显示钯纳米粒子的平均尺寸为2.6 nm. 在较温和的条件下Pd@IRA-900对多种卤代芳烃和苯硼酸的Suzuki偶联都具有良好的催化活性, 并且催化剂重复使用5次之后依然具有很好的活性. 此外，对树脂载体进行碱性交换处理后可得到一种双功能催化材料Pd@IRA-900(OH)，该催化剂在不加入碱的条件下也可以催化碘苯和苯硼酸的Suzuki偶联反应.

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Aldol condensations of a variety of different aldehydes and ketones under ultrasonic irradiation using poly(N-vinylimidazole) as a new heterogeneous base catalyst under solvent-free conditions in a liquid-solid system

Nader Ghaffari Khaligh, Taraneh Mihankhah

2013, 34 (12): 2167-2173. DOI: 10.1016/S1872-2067(12)60658-5

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An ultrasound-assisted aldol condensation reaction has been developed for a range of ketones with a variety of aromatic aldehydes using poly(N-vinylimidazole) as a solid base catalyst in a liquid-solid system. The catalyst can be recovered by simple filtration and reused at least 10 times without any significant reduction in its activity. The reaction is also amenable to the large scale, making the procedure potentially useful for industrial applications.

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高选择性和稳定性的CsPW/Nb₂O₅催化剂用于甘油脱水制备丙烯醛

刘蓉, 王铁峰, 刘畅, 金涌

2013, 34 (12): 2174-2182. DOI: 10.1016/S1872-2067(12)60666-4

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以磷钨酸铯盐Cs_2.5H_0.5PW₁₂O₄₀(CsPW)为活性组分, 负载到Nb₂O₅载体上, 并用于甘油脱水制备丙烯醛的反应中. 通过调节焙烧温度(400–700 ℃)以及活性组分负载量(5-60 wt%), 对催化剂酸性进行调节. CsPW负载量为20 wt%, 500 ℃焙烧的CsPW/Nb₂O₅催化剂性能最佳, 甘油转化率为96%, 丙烯醛选择性为80%, 反应10 h内没有失活现象, 并且该催化剂具有良好的热稳定性, 可通过烧炭进行再生.

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Cr掺杂的丙烷选择氧化制丙烯酸高效催化剂

徐爱新, 王阳, 葛汉青, 陈淑, 李彦花, 陆维敏

2013, 34 (12): 2183-2191. DOI: 10.1016/S1872-2067(12)60671-8

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在丙烷选择氧化制丙烯酸催化剂MoVTeNbO_x的活性相M1基础上掺杂一定量的Cr, 当Cr/Nb摩尔比为0.002时, 催化剂具有很高的丙烯酸选择性(78.3%)和收率(50.7%); 并采用X射线衍射、X射线光电子能谱、程序升温还原、O₂程序升温脱附、NH₃程序升温脱附和异丙醇氧化等手段对催化剂的构效关系进行了探讨. 结果表明, 适量Cr的添加可调节催化剂表面Mo⁶⁺, V⁵⁺和Te⁴⁺等物种含量, 提高催化剂的氧化能力, 使丙烷转化率增加. 同时, 适量Cr的添加使得催化剂表面酸强度下降, 酸性位点数量减少, 从而抑制丙烯酸的深度氧化, 提高了丙烯酸选择性.

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SAPO-34上甲醇及二甲醚吸附等温线及吸附热测量与分析

Yasukazu Kobayashi, 李玉新, 王垚, 王德峥

2013, 34 (12): 2192-2199. DOI: 10.1016/S1872-2067(12)60676-7

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在25, 60和100 ℃下分别测定了甲醇及二甲醚在SAPO-34分子筛上的吸附等温线, 同时用微量热法测定了微分吸附热与覆盖率的关系曲线(量热线), 提出了吸附数据需要利用双吸附位Langmuir方程拟合, 并获取了相应的吸附参数. 对比测得的吸附等温线与量热线发现, 在一定压力下, 当甲醇及二甲醚在SAPO-34上达到一定吸附量后, 随着吸附质分压增加, 量热线快速下降, 而吸附等温线显示出吸附量仍然继续增加. 由此推断, 在SAPO-34分子筛上存在两种吸附位——常规吸附位及弱吸附位, 其中弱吸附位在高分压下继续吸附. 如缺乏量热数据提供的常规吸附位饱和吸附量数据, 对吸附等温线进行单吸附位拟合获取吸附参数极易导致错误结果,尤其是当吸附质分压较高时. 建议采用双吸附位Langmuir方程, 参照量热线提供的常规吸附位的饱和吸附量, 通过拟合可以获得两种吸附位的吸附参数.

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Rice husk ash supported FeCl₂·2H₂O：A mild and highly efficient heterogeneous catalyst for the synthesis of polysubstituted quinolines by Friedländer heteroannulation

Farhad Shirini, Somayeh Akbari-Dadamahaleh, Ali Mohammad-Khah

2013, 34 (12): 2200-2208. DOI: 10.1016/S1872-2067(12)60684-6

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Rice husk ash was used as a new, green, and cheap adsorbent for FeCl₃. Characterization of the obtained reagent showed that rice husk ash supported FeCl₂·2H₂O was formed. This reagent is efficient at catalyzing the synthesis of multisubstituted quinolines by the Friedländer heteroannulation of o-aminoaryl ketones with ketones or β-diketones under mild reaction conditions. This methodology allows for the synthesis of a broad range of substituted quinolines in high yields and with excellent regioselectivity in the absence of a solvent.

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Iron-impregnated titania composites for the decomposition of low-concentration aromatic organic pollutants under UV and visible light irradiation

Wan-Kuen Jo, Joon Yeob Lee

2013, 34 (12): 2209-2216. DOI: 10.1016/S1872-2067(12)60688-3

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Fe-TiO₂ photocatalysts with different ratios of Fe to Ti were prepared by a sol-gel process using tetra-n-butyl titanium and iron(Ⅲ) nitrate as Ti and Fe sources, respectively. The photocatalytic function of the prepared composites was examined for the decomposition of low-concentration (0.1 ppm) airborne benzene, toluene, ethyl benzene, and o-xylene (BTEX). The Fe-TiO₂ composites were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction, UV-visible spectroscopy, and Fourier transform infrared spectroscopy. The time-series ratios of outlet to inlet concentrations of toluene, ethyl benzene, and o-xylene target chemicals, as determined by the Fe-TiO₂ composites under visible light exposure, were lower than or similar to those of the reference TiO₂photocatalyst. Moreover, the time-series ratios of outlet to inlet concentrations of the three compounds, as determined for the Fe-TiO₂ composites, increased as the ratio of Fe to Ti increased from 0.001 to 0.010. In contrast, under UV exposure, the time-series ratios of outlet to inlet concentrations of BTEX, determined for the Fe-TiO₂ composites, were similar to or higher than those obtained from the reference TiO₂ photocatalyst. Fe-TiO₂ composites with an optimal Fe to Ti ratio could effectively be applied for the purification of low-concentration aromatic organic pollutants.

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Cu(Ⅱ) salen complex catalyzed synthesis of propargylamines by a three-component coupling reaction

Mahmood Tajbaksh, Maryam Farhang, Hamid Reza Mardani, Rahman Hosseinzadeh, Yaghoub Sarrafi

2013, 34 (12): 2217-2222. DOI: 10.1016/S1872-2067(12)60683-4

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A one pot three-component coupling reaction of phenylacetylene, aldehyde, and amine derivatives in the presence of Cu(Ⅱ) Salen complex as an efficient heterogeneous catalyst under solvent-free conditions is reported. The catalyst displayed high activity and afforded the corresponding propargylamines in good to excellent yields. This method provides a wide range of substrate applicability. The catalyst was reused several times without significant loss of its catalytic activity.

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甲苯和一氧化碳氧化用介孔LaFeO₃催化剂

高宝族, 邓积光, 刘雨溪, 赵振璇, 李欣尉, 王媛, 戴洪兴

2013, 34 (12): 2223-2229. DOI: 10.1016/S1872-2067(12)60689-5

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以KIT-6和二氧化硅纳米球为硬模板制备了比表面积分别为138和65 m²/g的正交相蠕虫状介孔LaFeO₃催化剂LFO-1和LFO-2. 在空速为20000 mL/(g·h)的条件下, LFO-1样品显示出最高的催化活性: 对于CO氧化反应, T_50%和T_90%分别为155和180 ℃; 对于甲苯氧化反应, T_50%和T_90%分别为200和253 ℃. 该样品优异的催化性能与它具有较大的比表面积、较高的氧吸附物种浓度、较好的低温还原性以及良好的蠕虫状介孔结构有关.

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Cu-MgO/USY催化甘油氢解制丙二醇

牛磊, 魏瑞平, 杨慧, 李想, 姜枫, 肖国民

2013, 34 (12): 2230-2235. DOI: 10.1016/S1872-2067(12)60695-0

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以USY为载体制备了一系列不同Cu和MgO负载量的酸碱双功能催化剂Cu-MgO/USY用于甘油氢解制丙二醇反应, 并采用X射线粉末衍射、透射电镜、傅里叶红外光谱、NH₃程序升温脱附等手段对该催化剂进行了表征. 结果表明, 负载后的USY载体其Y沸石特征峰保持完整, 且MgO的加入提高了Cu在载体表面的分散度. 在200℃, 3.5 MPa H₂ 下反应10 h以及6% 催化剂0.2Cu-MgO/USY (0.2 g Cu与1.0 g MgO负载于1.0 g USY上面)用量的条件下, 甘油转化率达到83.6%, 1,2-丙二醇及1,3-丙二醇的选择性分别为40%和19.4%.

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双核烷基咪唑过氧磷钨酸盐相转移催化剂合成及催化烯烃环氧化性能

吴江浩, 蒋平平, 冷炎, 叶媛园, 秦晓洁

2013, 34 (12): 2236-2244. DOI: 10.1016/S1872-2067(12)60697-4

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合成并表征了一类双核长链烷基咪唑阳离子修饰的过氧磷钨杂多酸盐催化剂[D_nmin]_1.5PW₄O₂₄, 考察了催化剂在过氧化氢为氧源的烯烃环氧化反应中的催化活性. 研究表明, 这类催化剂在反应过程中表现出相转移催化现象, 并具有较高的催化活性和选择性. 其中, 双核十二烷基咪唑杂多酸盐催化剂[D₁₂min]_1.5PW₄O₂₄的活性最佳, 其环己烯转化率和环氧环己烷选择性分别达到97.7%和96.3%. 催化剂在经过简单离心分离后可重复使用, 重复使用4次后环己烯转化率和环氧环己烷选择性仍可分别达到72.4%和97.2%. 催化剂[D₁₂min]_1.5PW₄O₂₄在其它几种烯烃的环氧化反应中均表现出相转移催化特性, 且具有较高的催化活性.

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Silica-bonded N-propylpiperazine sodium n-propionate as recyclable catalyst for synthesis of 4H-pyran derivatives

Khodabakhsh Niknam, Nassim Borazjani, Reza Rashidian, Abbas Jamali

2013, 34 (12): 2245-2254. DOI: 10.1016/S1872-2067(12)60693-7

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Silica-bonded N-propylpiperazine sodium n-propionate (SBPPSP) was found to act as an efficient solid base for the preparation of a series of 4H-benzo[b]pyran derivatives. SBPPSP was used as a recyclable heterogeneous solid base catalyst for the synthesis of 3,4-dihydropyrano[c]chromenes, 2-amino-4H-pyrans, 1,4-dihydropyrano[2,3-c]pyrazoles, and 2-amino-4H-benzo[e]-chromenes via the condensation reaction of dimedone, ethyl acetoacetate, 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, and α-naphthol, respectively, with aromatic aldehydes and malononitrile in refluxing aqueous ethanol. The heterogeneous solid base showed similar efficiency when reused in consecutive reactions.

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有机相中固定化脂肪酶催化合成植物甾醇酯

蒋振华, 于敏, 任立伟, 周华, 韦萍

2013, 34 (12): 2255-2262. DOI: 10.1016/S1872-2067(12)60700-1

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酶法合成植物甾醇酯具有反应条件温和、产物纯度和产量高等优点, 但非水相酶催化的活性和稳定性普遍较低. 本文以大孔树脂固定化脂肪酶为催化剂, 并在催化过程中添加乳糖的类似物, 构建了有机相高效合成植物甾醇酯的工艺过程. 以酯化率为考察指标, 对脂肪酶和反应溶剂进行筛选, 对酯化条件进行优化, 同时考察了糖的种类及添加量对酶催化性能的影响. 结果表明, 大孔树脂NKA吸附固定化的褶皱假丝酵母(Candida rugosa)脂肪酶(NKA-CRL)为最适宜的催化剂, 以正己烷为反应介质, 在酸醇摩尔比为2和添加酶蛋白质量7.5%的海藻糖的条件下, 40 ℃反应10 h, 酯化率达到96.6%. 连续6次催化后, 植物甾醇的酯化率仍维持在85.0%以上.

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不同氮源溶剂热合成N-TiO₂纳米颗粒及其光催化降解气相苯

何霏, 马芳, 李涛, 李光兴

2013, 34 (12): 2263-2270. DOI: 10.1016/S1872-2067(12)60722-0

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采用三种不同的氮源溶剂热合成了锐钛矿-板钛矿混晶的N-TiO₂催化剂. 采用X射线衍射、N₂吸附-脱附、X射线光电子能谱和透射电子显微镜等手段对催化剂进行了表征. 重点研究了不同氮源对催化剂的相组成、晶粒尺寸、微观结构以及比表面积的影响. 采用紫外光降解气相苯测试了合成材料的催化活性. 结果表明, 以水合肼为氮源合成的N-TiO₂表现出最优的光催化活性, 其活性明显高于P25, 且能够循环使用15次以上. 采用气相色谱-质谱技术分析了光降解过程的中间产物, 基于此提出了相应的降解机理.

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碳纳米管-氧化铝: 高抗硫及再生性能的Pt基催化剂载体及在NO_x还原反应中的应用

江莉龙, 王玉玲, 刘弦, 曹彦宁, 魏可镁

2013, 34 (12): 2271-2276. DOI: 10.1016/S1872-2067(12)60745-1

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通过乙炔在Al₂O₃上的分解制备碳纳米管-氧化铝(Al₂O₃-CNTs)载体. 采用浸渍法, 分别制备了Pt/Ba/Al₂O₃-CNTs和Pt/Ba/Al₂O₃催化剂. 利用XRD, SEM, TEM, 低温N₂物理吸附, XPS和in-situ DRIFTS等手段对催化剂的物化性质进行了表征. 结果表明, 在SO₂存在下的NO_x还原反应中, Pt/Ba/Al₂O₃-CNTs比Pt/Ba/Al₂O₃具有更高的抗SO₂性能和再生性能. In-situ DRIFTS表明SO₂的存在对NO_x储存还原的途径没有影响.

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