催化学报

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第35卷第3期目次

2014, 35 (3): 0-0.

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环己烷氧化反应：有机小分子的催化作用

张义成, 戴卫理, 武光军, 关乃佳, 李兰冬

2014, 35 (3): 279-285. DOI: 10.1016/S1872-2067(14)60024-3

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考察了酮、醛、酯、醇与胺等几类有机小分子在环己烷氧化反应中的催化作用. 结果表明，有机小分子催化剂的活性与其极性的强弱、与环己烷形成氢键的强弱、α氢的活性及清除自由基的能力有关. 因此，对于环己烷氧化反应，溶剂很可能存在催化作用. 三丙胺在环己烷氧化反应中表现出较高的催化活性，具有进一步开发应用的前景.

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Ni-Mo氮化物催化剂：合成及其丙烷氨氧化催化性能

范晓强, 张惠民, 李建梅, 赵震, 徐春明, 刘坚, 段爱军, 姜桂元, 韦岳长

2014, 35 (3): 286-293. DOI: 10.1016/S1872-2067(14)60015-2

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分别采用溶胶-凝胶法、旋转蒸发微波干燥法、共沉淀法、浸渍法和机械混合法制备Ni-Mo氧化物前驱体. 以H₂和N₂的混合气为氮化气体，采用程序升温氮化法合成了镍钼氮化物催化剂. 利用X射线衍射、总氮含量分析、X射线光电子能谱及H₂程序升温还原对Ni-Mo氧化物前体及氮化物催化剂进行了表征. 将上述Ni-Mo氮化物催化剂用于丙烷氨氧化反应中. 结果表明，Ni-Mo氧化物前驱体的制备方法影响其氮化物催化剂上丙烷氨氧化反应性能. Ni-Mo氮化物催化剂中氮物种的移动性及反应性对产物丙烯腈选择性的影响较大，共沉淀法制备的催化剂存在大量的活性氮物种，因而具有良好的催化丙烷氨氧化反应活性.

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原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选择性催化还原反应机理

陈婷, 管斌, 林赫, 朱霖

2014, 35 (3): 294-301. DOI: 10.1016/S1872-2067(12)60730-X

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采用自蔓延燃烧法制备了Ti_0.9Mn_0.05Fe_0.05O_2-δ催化剂，运用原位漫反射傅里叶变换红外光谱对该催化剂的NO和NH₃稳态吸附以及NO和NH₃瞬态反应进行了详细地分析与讨论. 结果表明，相比于Lewis酸性位，150℃时Brönsted酸性位吸附的NH₃更具有SCR活性；与双齿硝酸盐和桥式硝酸盐相比，NO吸附产生的单齿硝酸盐是主要的中间物种；该SCR反应遵循Eley-Rideal和Langmuir-Hinshelwood机理，但以后者为主. 另外，O₂的存在有利于NO的氧化和配位态NH₃的活化.

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Ni/SiO₂-ZrO₂催化剂焙烧温度对其催化愈创木酚加氢脱氧性能的影响

张兴华, 张琦, 陈伦刚, 徐莹, 王铁军, 马隆龙

2014, 35 (3): 302-309. DOI: 10.1016/S1872-2067(12)60733-5

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采用化学沉淀法合成了SiO₂-ZrO₂复合氧化物载体，并以浸渍法制备了Ni/SiO₂-ZrO₂双功能催化剂，考察了焙烧温度对催化剂结构及其催化愈创木酚加氢脱氧制环己烷性能的影响. 结果表明，经500℃焙烧催化剂的加氢脱氧活性最高，在Ni金属中心和SiO₂-ZrO₂载体材料的协同作用下，愈创木酚转化率为100%，环己烷选择性为96.8%. 对催化剂进行N₂物理吸附、H₂化学吸附、X射线衍射分析、H₂程序升温还原、NH₃程序升温脱附与Raman光谱等表征后发现，合成的SiO₂-ZrO₂为无定形的酸碱两性氧化物；经500℃焙烧的催化剂样品的有效比表面积和孔体积均明显增大，表面酸量最多，硝酸镍分解成小颗粒的NiO较易被H₂还原，这些特性是该催化剂样品具有高效加氢脱氧活性的原因.

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Mg-Al水滑石催化甘油与碳酸二甲酯的酯交换反应

郑丽萍, 夏水鑫, 侯召同, 张梦媛, 侯昭胤

2014, 35 (3): 310-318. DOI: 10.1016/S1872-2067(12)60738-4

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报道了温和条件下甘油和碳酸二甲酯在一系列不同Mg/Al比（0.5-6）的Mg-Al水滑石催化下合成碳酸甘油酯（GC）的反应. 发现，Mg-Al水滑石对该反应具有很高的GC选择性，其中Mg/Al=2经400℃处理所得水滑石催化效率最高：70 ℃反应3 h甘油转化率达66.9%时，GC选择性维持在97%以上. 表征结果表明，水滑石样品的比表面积、孔径、结晶度和表面碱性对其催化活性影响很大.

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铜催化异噁唑还原开环清洁高效合成1-氨基-2-乙酰基蒽醌

赵忠奎, 李仁志, 李宇

2014, 35 (3): 319-323. DOI: 10.1016/S1872-2067(12)60743-8

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以水为反应介质，水合肼为还原剂，研究了痕量铜催化3-甲基蒽醌-[1，2-c]-异噁唑还原开环反应以清洁高效合成1-氨基-2-乙酰基蒽醌，考察了不同种类过渡金属硝酸盐的催化性能，发现Cu（NO₃）₂性能最好. 加入 2.6% 的催化剂和1.3倍的水合肼，在室温反应 2 h，底物转化率和目标产物选择性分别可达到 97.2%和 95%，TON达到38. 产品结构经氢核磁谱和质谱得以确证，主要副产为羟基取代的1-氨基-2-乙酰基蒽醌. 此外，提出了铜催化 3-甲基蒽醌-[1，2-c]-异噁唑还原开环反应合成 1-氨基-2-乙酰基蒽醌的可能反应机理.

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Poly(vinyl chloride)-supported Pd(Ⅱ) complex as an efficient catalyst for Heck and Cu-free Sonogashira reactions under aerobic conditions

Mohammad Bakherad, Ali Keivanloo, Shahrzad Samangooei

2014, 35 (3): 324-328. DOI: 10.1016/S1872-2067(12)60746-3

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A novel poly(vinyl chloride)-supported Pd complex was found to be a highly active catalyst for the Heck and Sonogashira reactions of aryl halides under aerobic conditions. The complex is thermally stable, and can be easily recovered and reused. The catalyst was recycled for the Heck and Sonogashira reactions for five runs without appreciable loss of its catalytic activity, and with negligible metal leaching.

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Poly(4-vinylpyridinium) perchlorate as an efficient solid acid catalyst for the chemoselective preparation of 1,1-diacetates from aldehydes under solvent-free conditions

Nader Ghaffari Khaligh

2014, 35 (3): 329-334. DOI: 10.1016/S1872-2067(12)60750-5

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Poly(4-vinylpyridinium) perchlorate has been used as a supported, recyclable, environmentally-benign catalyst for the formation of acylals from aliphatic and aromatic aldehydes in good to excellent yields under solvent-free conditions. Notably, the reaction conditions were tolerant of ketones. This methodology offers several distinct advantages, including its operational simplicity and high product yield, as well as being green in terms of avoiding the use of toxic catalysts and solvents. Furthermore, the catalyst can be recovered and reused several times without any loss in its activity.

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锰负载量对活性炭载锰氧化物的结构及催化分解臭氧性能的影响

王鸣晓, 张彭义, 李金格, 姜传佳

2014, 35 (3): 335-341. DOI: 10.1016/S1872-2067(12)60756-6

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将高锰酸钾与活性炭（AC）原位氧化还原制备的活性炭载锰氧化物（MnO_x/AC）用作臭氧分解的催化剂. 采用扫描电镜、X射线光电子能谱、X射线衍射、电子自旋共振波谱、拉曼光谱以及程序升温还原研究了设计Mn负载量对负载锰氧化物性质（形貌、氧化态和晶体结构）的影响. 结果表明，Mn负载量由0.44%增至11%，负载锰氧化物在活性炭表面由疏松的地衣状变为堆叠的纳米球状体，负载层的厚度由~180 nm增加至~710 nm，结构由氧化态+2.9到+3.1的低结晶β-MnOOH生长为由氧化态+3.7到+3.8的δ-MnO₂结晶. MnO_x/AC室温催化分解低浓度臭氧的活性与负载锰氧化物的形貌及含量密切相关. Mn负载量为1.1%的MnO_x/AC具有疏松的地衣状形貌，催化分解臭氧的性能最高，Mn负载量为11%的MnO_x/AC具有紧密的堆积结构，因而表现出最低的催化臭氧分解活性.

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以钴羰基簇合物为前驱体制备的钴基催化剂上F-T反应性能

李雪芬, 白凤华, 苏海全

2014, 35 (3): 342-350. DOI: 10.1016/S1872-2067(12)60757-8

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以含羧酸配体的钴羰基簇合物Co₂（CO）₆HCCCOOH，Co₃（CO）₉CCH₂COOH，Co₄（CO）₁₀HCCCOOH 为前驱体，γ-Al₂O₃为载体，通过浸渍法制备了一系列催化剂；同时以Co（NO₃）₂作为前驱体制备了参比催化剂. 对制备的催化剂进行了费托反应性能评价，并用透射电子显微镜、氨程序升温脱附和傅里叶变换红外光谱等手段对催化剂进行了表征. 结果发现，不同前驱体制备的催化剂对载体上Co的分布具有明显影响，进而影响催化剂活性. 反应结果表明，不同前驱体制备的催化剂上CO转化率及C₅₊选择性顺序为Co₃（CO）₉CCH₂COOH > Co₂（CO）₆HCCCOOH > Co₄（CO）₁₀HCCCOOH > Co（NO₃）₂.

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Preparation and characterization of nano-CaO based on eggshell waste：Novel and green catalytic approach to highly efficient synthesis of pyrano[4,3-b]pyrans

Elaheh Mosaddegh, Asadollah Hassankhani

2014, 35 (3): 351-356. DOI: 10.1016/S1872-2067(12)60755-4

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Nano-CaO was prepared by calcination of ball-milled chicken eggshell waste. This novel, bioactive, heterogeneous catalyst, which had high catalytic activity and reusability, was used in the green synthesis of pyrano[4,3-b]pyrans via condensation of various aromatic aldehydes, malononitrile, and 4-hydroxy-6-methyl-2H-pyran-2-one at 120℃ under solvent-free conditions. The reaction proceeded to completion within 5-45 min in 93%-98% yield. The nano-CaO was fully characterized by scanning electron microscopy, X-ray powder diffraction, infrared spectroscopy, X-ray fluorescence spectroscopy, and thermal gravimetric, surface area, and elemental analyses.

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纯水中有氧条件下Pd/C催化的无配体Suzuki反应

饶小峰, 刘春, 张义霞, 高占明, 金子林

2014, 35 (3): 357-361. DOI: 10.1016/S1872-2067(12)60754-2

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报道一种在纯水中Pd/C催化的高效Suzuki反应体系，该体系无需除氧，且无外加配体和添加剂，底物普适性广泛，含有亲水或疏水基团的溴代芳烃都能被高效活化. 此外，对部分杂环芳烃与芳基硼酸的偶联反应也有较好的催化效果. 该催化剂可高效循环使用三次，且性能无明显下降.

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Boehmite nanoparticle catalyst for the one-pot multicomponent synthesis of 3,4-dihydropyrimidin-2-(1H)-ones and thiones under solvent-free conditions

Ali Keivanloo, Mahdi Mirzaee, Mohammad Bakherad, Atena Soozani

2014, 35 (3): 362-367. DOI: 10.1016/S1872-2067(12)60759-1

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A simple, green, and efficient synthesis protocol for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones using boehmite nanoparticles as catalyst was developed. It did not use any toxic metal catalysts or corrosive acidic reagents. The method gave good to excellent yields and has short reaction time, operational simplicity, and a recyclable catalyst.

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ZnAl₂O₄@SiO₂ nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions

Saeed Farhadi, Kosar Jahanara

2014, 35 (3): 368-375. DOI: 10.1016/S1872-2067(12)60758-X

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A ZnAl₂O₄@SiO₂ nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N₂ adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl₂O₄@SiO₂ nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH₂ group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl₂O₄@SiO₂ nanocomposite was higher than that of pure ZnAl₂O₄. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.

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Ferric hydrogen sulfate supported on silica-coated nickel ferrite nanoparticles as new and green magnetically separable catalyst for 1,8-dioxodecahydroacridine synthesis

Amir Khojastehnezhad, Mohammad Rahimizadeh, Hossein Eshghi, Farid Moeinpour, Mehdi Bakavoli

2014, 35 (3): 376-382. DOI: 10.1016/S1872-2067(14)60001-2

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A new magnetically separable catalyst consisting of ferric hydrogen sulfate supported on silica-coated nickel ferrite nanoparticles was prepared. The synthesized catalyst was characterized using vibrating sample magnetometry, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectroscopy. This new magnetic catalyst was shown to be an efficient heterogeneous catalyst for the synthesis of 1,8-dioxodecahydroacridines under solvent-free conditions. The catalyst is readily recovered by simple magnetic decantation and can be recycled several times with no significant loss of catalytic activity.

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An electrode with Ni(Ⅱ) loaded analcime zeolite catalyst for the electrooxidation of methanol

Seyed Naser Azizi, Shahram Ghasemi, Neda Salek Gilani

2014, 35 (3): 383-390. DOI: 10.1016/S1872-2067(14)60002-4

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There is a high overvoltage in the oxidation of methanol in fuel cells, and so modified electrodes are used to decrease it. A modified electrode that used Ni(Ⅱ) loaded analcime zeolite to catalyze the electrooxidation of methanol in alkaline solution was proposed. Analcime zeolite was synthesized by hydrothermal synthesis, and Ni(Ⅱ) ions were incorporated into the analcime structure, which was then mixed with carbon paste to prepare modified electrode. The electrocatalytic oxidation of methanol on the surface of the modified electrode in alkaline solution was investigated by cyclic voltammetry and chronoamperometry. The effects of the scan rate of the potential, concentration of methanol, and amount of zeolite were investigated. The rate constant for the catalytic reaction of methanol was 6×10³ cm³ mol^-1 s^-1 from measurements using chronoamperometry. The proposed electrode significantly improved the electron transfer rate and decreased the overpotential for methanol oxidation.

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An efficient one-pot three-component synthesis of tetrahydrobenzo[b]pyran and 3,4-dihydropyrano[c]chromene derivatives using starch solution as catalyst

Nourallah Hazeri, Malek Taher Maghsoodlou, Fatemeh Mir, Mehrnoosh Kangani, Hamideh Saravani, Ebrahim Molashahi

2014, 35 (3): 391-395. DOI: 10.1016/S1872-2067(14)60003-6

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Tetrahydrobenzo[b]pyran and 3,4-dihydropyrano[c]chromene derivatives were synthesized via a one-pot three-component condensation of aromatic aldehydes with malononitrile and dimedone or 4-hydroxycoumarin in excellent yields in the presence of starch solution as a highly efficient homogenous catalyst. The use of a nontoxic and biodegradable catalyst, simple work-up procedure, and short reaction time are advantages of this method.

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酸性离子液体催化油酸酯化合成生物柴油

李颖, 胡双岚, 程建华, 娄文勇

2014, 35 (3): 396-406. DOI: 10.1016/S1872-2067(14)60005-X

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酸性离子液体具有催化活性好、选择性高及易于回收等优点，是一种应用前景非常好的环境友好的酸性催化剂，在生物柴油合成反应中具有重大的理论意义和应用价值. 本文以油酸和甲醇为原料，探讨了7种不同酸性离子液体在生物柴油合成反应中的催化效应. 研究表明，离子液体酸性越强，催化酯化活性越高；引入磺酸基团可大大增强离子液体Brönsted酸性，使其在酯化反应中发挥溶剂/催化剂的双重作用，促进酯化反应向产物方向进行，达到高产率，因而1-丁基磺酸-3-甲基咪唑硫酸氢盐（[BHSO₃MIM]HSO₄）催化效果最好. 此外，系统研究了[BHSO₃MIM]HSO₄催化油酸与甲醇酯化反应，并采用响应面法优化了反应条件. 结果发现，该反应的最适醇酸摩尔比、催化剂用量、反应温度及反应时间分别为4：1，10%（基于油酸的质量），130 ℃和4 h；在此条件下，生物柴油产率为97.7%. [BHSO₃MIM]HSO₄连续使用10批次后，仍能保持初始催化活性的95.6%，表现出极好的操作稳定性. 另外，利用该离子液体催化游离脂肪酸含量为72%的废油脂生产生物柴油，反应6 h可获得产率94.9%. 可见，[BHSO₃MIM]HSO₄在酯化生产生物柴油方面具有巨大的应用潜力.

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Pt/Ce_0.6Zr_0.4O₂催化剂催化氧化碳烟过程中活性氧对NO-NO₂循环及表面含氧物种的分解作用

刘爽, 吴晓东, 林雨, 李敏, 翁端

2014, 35 (3): 407-415. DOI: 10.1016/S1872-2067(14)60004-8

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通过在Ce_0.6Zr_0.4O₂载体上浸渍Pt（NO₃）₂制得Pt/Ce_0.6Zr_0.4O₂催化剂，该催化剂在松散接触条件下，于NO+O₂或O₂气氛中均表现出比Pt/Al₂O₃更好的碳烟氧化性能. 进一步研究表明，Pt/Ce_0.6Zr_0.4O₂催化剂中的Pt 与Ce_0.6Zr_0.4O₂存在相互作用，使得催化剂在一定温度范围内对活性氧的利用率大为提高，从而促进了气氛中NO↔NO₂的循环，乃至碳烟与NO₂的反应和碳烟表面含氧中间物种的生成；更重要的是，这部分活性氧本身可加速含氧中间物种的分解. 因此，在NO + O₂的气氛中，Pt/Ce_0.6Zr_0.4O₂催化剂的碳烟起燃温度比Pt/Al₂O₃降低了34 ℃.

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水对甲醇在Rutile-TiO₂（110）-（1×1）表面光催化解离的影响

徐晨彪, 杨文绍, 郭庆, 戴东旭, 陈茂笃, 杨学明

2014, 35 (3): 416-422. DOI: 10.1016/S1872-2067(14)60006-1

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采用程序升温脱附方法研究了甲醇分子吸附在真空退火后的二氧化钛（110）表面的光催化过程，对比分析了单独吸附甲醇分子以及甲醇分子与水分子共吸附情况下的光催化解离过程. 结果表明，在二氧化钛（110）表面吸附的甲醇分子对共吸附水分子的光催化解离过程并没有直接的帮助作用. 共吸附状态下的水分子也同样没有影响到甲醇的光致解离过程，但是水分子的存在抑制了甲醇光解产物甲醛的光致脱附过程，同时促进了甲酸甲酯的形成.

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Simultaneous and sensitive detection of dopamine and uric acid using a poly(L-methionine)/gold nanoparticle-modified glassy carbon electrode

Reza Ojani, Jahan-Bakhsh Raoof, Ali Asghar Maleki, Saeid Safshekan

2014, 35 (3): 423-429. DOI: 10.1016/S1872-2067(14)60022-X

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A novel electrochemical sensor was fabricated by electrodeposition of gold nanoparticles on a poly(L-methionine) (PMT)-modified glassy carbon electrode (GCE) to form a nano-Au/PMT composite-modified GCE (nano-Au/PMT/GCE). Scanning electron microscopy and electrochemical techniques were used to characterize the composite electrode. The modified electrode exhibited considerable electrocatalytic activity towards the oxidation of dopamine (DA) and uric acid (UA) in phosphate buffer solution (pH = 7.00). Differential pulse voltammetry revealed that the electrocatalytic oxidation currents of DA and UA were linearly related to concentration over the range of 5.0×10^-8 to 10^-6 mol/L for DA and 7.0×10^-8 to 10^-6 mol/L for UA. The detection limits were 3.7×10^-8 mol/L for DA and 4.5×10^-8 mol/L for UA at a signal-to-noise ratio of 3. According to our experimental results, nano-Au/PMT/GCE can be used as a sensitive and selective sensor for simultaneous determination of DA and UA.

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混合气体中SAPO-34上单个物种的表面浓度

Ysukzu Koyshi, 李玉新, 王垚, 王德峥

2014, 35 (3): 430-436. DOI: 10.1016/S1872-2067(14)60007-3

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运用Langmuir等温线方程和理想吸附溶液理论（IAST）两种方法计算了SAPO-34在混合气体中的单个物种表面浓度，并对比了计算值与实验值的吻合程度. 考察了两个二元混合体系，分别为80 ℃的甲醇和二甲醚以及25 ℃的二甲醚和乙烯混合气，发现IAST计算值在实验压力范围内均与实验结果吻合；但是Langmuir理论计算值仅在酸性位覆盖率低于1/3时与实验值吻合较好，随着压力增加严重偏离实验值，而且Langmuir理论不能描述随压力增加低饱和吸附量物种覆盖率降低的现象. 因此，针对包含不同饱和吸附量组分的混合气，Langmuir理论仅适用于描述表面浓度低时的反应动力学，当表面浓度高时应该采用IAST方法.

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La（OH）₃和La₂O₂CO₃纳米棒的合成及其催化Claisen-Schmidt缩合反应性能

王非, 塔娜, 李勇, 申文杰

2014, 35 (3): 437-443. DOI: 10.1016/S1872-2067(14)60008-5

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通过调节溶液的pH值，在水热条件下合成出长径比为2-45的La（OH）₃纳米棒. 对水热合成过程中间体的结构演变分析，发现高碱度有利于小尺寸晶核的形成，La（OH）₃晶体结构的各向异性导致这些晶种沿着C轴方向生长，进而形成纳米棒结构. 将La（OH）₃纳米棒前驱体于773 K焙烧可以得到长径比为2-20的La₂O₂CO₃纳米棒. 随着长径比的增加，La₂O₂CO₃纳米棒暴露的（110）晶面逐渐增加，La³⁺-O^2-碱性位的数目也从0.08增加到0.24 mmol/g. 因此，在Claisen-Schmidt缩合反应中，La₂O₂CO₃纳米棒催化剂上的反应速率随着长径比的增加而逐渐增大.

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SiO₂-Cu₂O：An efficient and recyclable heterogeneous catalyst for N-benzylation of primary and secondary amines

Manjulla Gupta, Satya Paul, Rajive Gupta

2014, 35 (3): 444-450. DOI: 10.1016/S1872-2067(14)60009-7

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A mild, effective, and selective procedure is reported for the mono N-benzylation and N,N-dibenzylation of primary amines as well as mono N-benzylation of secondary amines using silica-supported copper(I) oxide in water. The silica-supported Cu₂O was generated in situ by the reaction of Fehling solution and glucose at 100 ℃ onto activated silica. The catalyst was filtered, washed with water, and oven-dried, and was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic absorption spectroscopy. The prepared Cu₂O-SiO₂ was found to be thermally stable up to 325 ℃. The copper was uniformly distributed onto the surface of the silica, and the mean particle diameter was 7 nm. The catalyst served as a selective heterogenous catalyst for the N-benzylation of primary and secondary amines. The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity. Various reaction solvents including water, acetonitrile, and toluene were screened for N-benzylation of amines, and the success of the aqueous system highlights the low environmental impact of the procedure.

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Author Index

2014, 35 (3): 451-451.

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