催化学报

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第36卷第7期目次

2015, 36 (7): 0-0.

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焦炉煤气二氧化碳重整制合成气中La_0.6Sr_0.4Ni_xCo_1-xO₃钙钛矿催化剂的合成、表征和催化性能研究

朱秋桦, 程红伟, 邹星礼, 鲁雄刚, 许茜, 周忠福

2015, 36 (7): 915-924. DOI: 10.1016/S1872-2067(14)60303-X

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采用溶胶凝胶法制备了La_0.6Sr_0.4Ni_xCo_1-xO₃ 钙钛矿催化剂, 并测试了该催化剂在焦炉煤气CO₂重整反应中的性能.通过X射线衍射、N₂吸附脱附、程序升温还原、扫描电镜、透射电镜和热重-微分扫描量热等方法对催化剂进行了表征. 结果表明, 溶胶凝胶法合成的La_0.6Sr_0.4Ni_xCo_1-xO₃催化剂形成了钙钛矿结构的固溶体. 着重考察了钙钛矿催化剂焙烧温度和A位Ni的掺杂含量对其催化性能和反应后积碳的影响. 结果表明: La_0.6Sr_0.4Ni_xCo_1-xO₃ 钙钛矿催化剂在反应中生成了活性金属Ni, Co颗粒和La₂O₂CO₃, 这些组分对催化剂的活性和稳定性起关键性的作用, 并且能够抑制积碳的形成; 焦炉煤气中的富氢气体具有抑制甲烷裂解反应发生的作用, 从而减少催化剂的积碳.

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三价铑催化硝酮与炔的碳氢活化偶联合成二氢吲哚

孔令恒, 谢芳, 于松杰, 戚自松, 李兴伟

2015, 36 (7): 925-932. DOI: 10.1016/S1872-2067(15)60866-X

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三价铑在氧化还原中性条件下催化硝酮与炔发生偶联, 经过氮芳环的碳氢键活化和氧转移可以高化学选择性、中等到良好非对映选择性的得到三取代二氢吲哚.

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Cr-free Co-Cu/SBA-15 catalysts for hydrogenation of biomass-derived α-, β-unsaturated aldehyde to alcohol

Sanjay Srivastava, Pravakar Mohanty, Jigisha K. Parikh, Ajay K. Dalai, S. S. Amritphale, Anup K. Khare

2015, 36 (7): 933-942. DOI: 10.1016/S1872-2067(15)60870-1

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Cr-free bi-metallic SBA-15-supported Co-Cu catalysts were examined in the conversion of biomass-derived α-, β-unsaturated aldehyde (furfural) to value-added chemical furfuryl alcohol (FOL). Co-Cu/SBA-15 catalysts with a fixed Cu loading of 10 wt% and varying Co loadings (2.5, 5, and 10 wt%) were prepared by the impregnation method. The catalysts were characterized by X-ray diffraction, N₂ sorption, H₂ temperature-programmed reduction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, CO chemisorption, and inductively coupled plasma mass spectrometry. The influence of different reaction parameters such as temperature, pressure, catalyst dosage, and furfural concentration on the catalyst performance was evaluated. Relative to catalysts supported on amorphous silica, the current SBA-15-supported Co-Cu catalysts displayed higher performance, attaining a furfural conversion of 99% and furfuryl alcohol selectivity of 80%. The catalytic reactions were conducted in a 100-mL autoclave at 170 ℃ and 2 MPa H₂ pressure for 4 h.

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聚苯胺对钯催化甲酸电氧化反应的促进作用

马先斌, 冯媛媛, 李扬, 韩运石, 鹿国萍, 杨海芳, 孔德生

2015, 36 (7): 943-951. DOI: 10.1016/S1872-2067(15)60863-4

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钯基纳米材料是甲酸电氧化反应的优良催化剂. 本工作制备了两个系列钯基催化剂, 并考察了聚苯胺对钯上甲酸电氧化反应的助催化作用. 一种是以聚苯胺为基底, 在其表面电沉积钯纳米粒子, 制得nPANI/Pd催化剂(n表示聚合苯胺的循环数); 另一种是直接在商业Pd/C催化剂表面电聚合苯胺, 制得Pd/C/nPANI催化剂. 结果显示, 聚苯胺单独存在时对甲酸电氧化反应没有催化活性, 但其可对钯上甲酸电氧化反应呈现明显的促进作用, 且促进作用与聚苯胺的厚度(聚合循环数)密切相关. 在两个系列催化剂中, 15PANI/Pd和Pd/C/20PANI显示出最高的催化性能. 15PANI/Pd中钯的质量比催化活性是纯钯催化剂的7.5倍; Pd/C/20PANI中钯的质量比催化活性和本征催化活性分别是商业Pd/C催化剂的2.3和3.3倍. 钯催化性能的提升与聚苯胺和钯纳米粒子间的电子效应有关.

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催化湿式共氧化法同时去除硝基苯和苯酚

付冬梅, 章飞芳, 王联芝, 杨帆, 梁鑫淼

2015, 36 (7): 952-956. DOI: 10.1016/S1872-2067(15)60835-X

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在150-210 ℃, 1.0 MPa氧分压条件下, 对催化湿式共氧化法同时去除硝基苯和苯酚进行了研究. 与无催化剂共氧化降解苯酚和硝基苯相比, 均相催化剂的加入极大提高了苯酚和硝基苯的去除. 在所研究的过渡金属催化剂中, Cu²⁺, Co²⁺和Ni²⁺是有效的催化剂, 其中Cu²⁺的催化活性最好. 引发剂苯酚的连续加入模式对硝基苯的去除有很大的促进作用, 分批加入苯酚的促进作用更明显. 在200 ℃, 以Cu²⁺为催化剂, 苯酚分两次加入, 反应1 h, 硝基苯去除率达到95%. 这种催化共氧化体系以及分批进样引发剂的反应模式对有效去除环境中其它有机污染物提供了一种方法.

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Hydrogenation of coumarin to octahydrocoumarin over a Ru/Ccatalyst

Dana Bílková, Petr Jansa, Iva Paterová, Libor Červený

2015, 36 (7): 957-960. DOI: 10.1016/S1872-2067(15)60860-9

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The production of octahydrocoumarin, which can serve as a replacement for toxic coumarin, was investigated using 5% Ru on active carbon (Ru/C) as the catalyst for the hydrogenation of coumarin. The hydrogenation was studied by optimizing the reaction conditions (pressure, solvent and coumarin concentration). The activity and selectivity of the Ru/C catalyst were compared for different solvents. The mechanism of coumarin hydrogenation was deduced. The formation of side products was explained. The optimal hydrogenation reaction conditions were: 130 ℃, 10 MPa, 60 wt% coumarin in methanol, and 0.5 wt% (based on coumarin) of Ru/C catalyst. At the complete conversion of coumarin, the selectivity to the desired product was 90%.

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超顺磁性氧化石墨烯复合材料固定辣根过氧化物酶催化去除氯酚

常青, 江国栋, 唐和清, 李娜, 黄佳, 吴来燕

2015, 36 (7): 961-968. DOI: 10.1016/S1872-2067(15)60856-7

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采用超声辅助共沉淀法成功地将磁性Fe₃O₄纳米颗粒沉积在氧化石墨烯表面, 利用透射电镜、磁滞回归曲线和X射线光电子能谱对材料进行了表征. 将该材料作为载体固定辣根过氧化物酶, 考察了固定化酶催化2-氯酚、4-氯酚和2,4-二氯酚降解反应, 研究了溶液pH值、反应温度、反应时间、H₂O₂和氯酚浓度以及固定化酶用量对酚类物质去除率的影响. 基于取代基数量和位置不同, 去除率排序为2-氯酚 < 4-氯酚 < 2,4-二氯酚. 另外, 采用GC-MS研究了降解过程中的氧化产物. 固定化酶的生化性质研究表明, 固定化酶比游离酶具有更好的储存稳定性、pH稳定性和热稳定性. 经过4次循环利用, 固定化酶仍保留66%的活性, 说明磁性纳米材料可以分离回收并重复利用, 在污水处理领域具有应用前景.

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Bi掺杂NaTaO₃中Bi的化学价态对其光催化性能的影响

崔华楠, 石建英, 刘鸿

2015, 36 (7): 969-974. DOI: 10.1016/S1872-2067(15)60858-0

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分别采用NaBiO₃和Bi(NO₃)₃为Bi源制备了Bi掺杂NaTaO₃光催化剂, 研究了Bi离子的价态对NaTaO₃光催化分解水制氢性能的影响. 采用X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)和紫外-可见吸收光谱研究了催化剂的晶体结构、Bi离子的化学状态和催化剂的光学吸收性能. 以光催化分解水制氢反应研究了Bi离子掺杂NaTaO₃的催化性能. XRD结果表明, 对于两个不同Bi源掺杂的NaTaO₃样品, Bi离子的掺杂没有改变催化剂的单斜相结构, 但拉曼光谱证实Bi离子的掺杂致使Ta-O-Ta键角偏离了180°. XPS结果表明, 以Bi(NO₃)₃为Bi源时, Bi离子以Bi³⁺掺杂于NaTaO₃的A位; 当以NaBiO₃为原料时, Bi³⁺和Bi⁵⁺共掺杂于NaTaO₃的A位. 两种不同Bi源掺杂得到的样品在紫外-可见吸收光谱中给出了相似的光学吸收, 但Bi³⁺的掺杂对NaTaO₃光催化性能影响不大, 而Bi³⁺和Bi⁵⁺共掺杂大大提高了NaTaO₃的光解水制氢性能. Bi离子取代Na离子在A位的掺杂, 在NaTaO₃结构中引入了能够促进载流子分离的空位和缺陷; 与此同时, Bi的掺杂导致Ta-O-Ta键角偏离180^o而不利于载流子迁移. 对于Bi³⁺掺杂的NaTaO₃样品, 这两种作用相互抵消, 使得其催化性能与NaTaO₃相比没有变化; 而Bi³⁺和Bi⁵⁺的共掺杂和高价态Bi⁵⁺的掺杂引入了更多的空位和缺陷, 提高了光生电子-空穴的分离效率, 从而提高了光催化产氢性能. 研究表明, 光催化过程中载流子的迁移是影响催化性能的重要因素, 而在ABO₃钙钛矿结构的A位引入高价态离子是促进光生载流子分离的有效途径.

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Ti/α-PbO₂/β-PbO₂电极电化学降解2-氯酚

张钱丽, 郭新艳, 曹晓丹, 王东田, 魏杰

2015, 36 (7): 975-981. DOI: 10.1016/S1872-2067(15)60851-8

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采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO₂/β-PbO₂, 扫描电镜结果表明电极呈现由β-PbO₂小晶体组成的菜花状微观形貌. 所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命. 用正交实验优化了电化学降解2-氯酚的实验条件. 在最优的实验条件(2-氯酚初始浓度50 mg/L, 电解质0.1 mol/L Na₂SO₄, 温度35 ℃, 阳极电流密度20 mA/cm²)下电化学降解180 min后, 2-氯酚的去除率达100%. 动力学结果表明, Ti/α-PbO₂/β-PbO₂电极上2-氯酚的电化学氧化符合准一级动力学过程.

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双子型Brönsted酸性离子液体催化高级脂肪酸与醇反应合成生物柴油

常涛, 何乐芹, 张晓婧, 袁明霞, 秦身钧, 赵继全

2015, 36 (7): 982-986. DOI: 10.1016/S1872-2067(15)60852-X

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合成了一系列双子型酸性离子液体, 该类型离子液体以乙二铵为连接链, 由碳链长度可调的双子型阳离子与不同的阴离子组成. 因此, 具有相分离催化剂的性质, 并应用于高级脂肪酸与醇的酯化反应, 以合成生物柴油. 详细考察了各参数的影响. 结果表明, [C₁₂Sb][p-CH₃C₆H₄SO₃]表现出高催化活性及可重复使用性能.

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异质结构AgCl/Bi₂WO₆微米球制备、表征及其光催化性能

李家德, 余长林, 方稳, 朱丽华, 周晚琴, 樊启哲

2015, 36 (7): 987-993. DOI: 10.1016/S1872-2067(15)60849-X

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首先利用水热法制备了由纳米片组装的粒径为1.5-2 μm的Bi₂WO₆微球, 然后在微球表面沉积了不同含量的AgCl (5 wt%, 10 wt%, 20 wt%, 30 wt%), 制备了异质结构AgCl/Bi₂WO₆微球光催化剂. 利用X射线粉末衍射、扫描电镜、透射电镜、红外光谱、紫外-可见漫反射吸收等手段对所制的光催化剂进行表征, 并以紫外光和可见光分别为光源, 罗丹明B为降解对象测试了其光催化活性, 考察复合不同含量的AgCl对Bi₂WO₆光催化剂的性能影响. 结果表明, 沉积AgCl对Bi₂WO₆的晶体结构、表面性能和光吸收性能没有产生明显影响, 但大幅度提高了Bi₂WO₆的紫外和可见光催化活性. 当复合20 wt%AgCl时, AgCl/Bi₂WO₆光催化活性最佳, 紫外光下比纯Bi₂WO₆提高了2.2倍, 可见光下提高了1倍. 这主要是由于形成的AgCl/Bi₂WO₆异质结能有效抑制光生电子和空穴的复合, 从而提了其光催化性能.

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Ni对Pd/Al₂O₃密偶催化剂催化性能的影响

方瑞梅, 崔亚娟, 史忠华, 龚茂初, 陈耀强

2015, 36 (7): 994-1000. DOI: 10.1016/S1872-2067(15)60850-6

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考察了助剂Ni对以改性氧化铝为载体的单Pd密偶催化剂的影响. 结果表明, 掺杂Ni可以明显改善对C₃H₈的催化性能, 尤其对老化催化剂效果显著. 此外, Ni的添加使老化催化剂Pd/Al₂O₃的起燃温度(T₅₀)和完全转化温度(T₉₀)分别降低31和30 ℃. 单反应测试结果表明, 添加Ni能明显提高对C₃H₈ + NO反应的催化性能. 采用H₂程序升温还原、CO吸附、高倍透射电镜和X射线光电子能谱等手段对新鲜和老化催化剂进行了表征. 结果表明, 掺杂Ni不仅可以抑制活性组分PdO_x的烧结, 减少金属态Pd⁰的产生, 而且可以提高PdO_x物种的可还原能力和有效比表面积.

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Al³⁺离子介入提升(NH₄)₂SiF₆对SBA-15介孔材料的水热稳定化作用

邹成龙, 沙观宇, 黄曜, 牛国兴, 赵东元

2015, 36 (7): 1001-1008. DOI: 10.1016/S1872-2067(15)60855-5

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提出了一种(NH₄)₂SiF₆处理提高SBA-15介孔材料水热稳定性的改良方法. 采用SBA-15介孔材料中预引入Al³⁺离子, 再进行1%SiO₂计量的(NH₄)₂SiF₆处理, 最后用强酸洗脱预引入的Al³⁺. 结果显示, 由此处理的SBA-15材料, 其水热稳定性明显优于相同条件下未预引入Al³⁺时(NH₄)₂SiF₆处理的样品. 两者在800 ℃、100%水蒸气处理12 h后, 虽然均能很好保持其介观有序度、形貌及六方孔道结构, 但前者的比表面积可高达271 m²/g, 而后者仅为224 m²/g. 表明Al³⁺离子介入能大幅度提升(NH₄)₂SiF₆处理对SBA-15介孔材料的稳定化作用. 这主要得益于预引入的骨架Al³⁺在保障(NH₄)₂SiF₆处理修复SBA-15材料表面缺陷和进行表面疏水化、提升其水热稳定性的同时, 能减缓(NH₄)₂SiF₆释放的多余F^-离子对SBA-15材料骨架的刻蚀破坏作用. Al³⁺离子介入的这种提升作用与其引入方式和SBA-15材料所经受的温度密切相关.

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g-C₃N₄/rGO杂化催化剂的简易合成及其对罗丹明B的光催化降解作用

原博, 魏江霞, 胡天娇, 姚海波, 蒋振华, 方志薇, 楚增勇

2015, 36 (7): 1009-1016. DOI: 10.1016/S1872-2067(15)60844-0

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在空气中直接加热三聚氰胺和氧化石墨烯(GO)的混合物制备了g-C₃N₄/rGO杂化催化剂. 实验结果表明, 混合物中的g-C₃N₄保留了石墨型氮化碳原始的特征结构, g-C₃N₄和还原的氧化石墨烯(rGO)之间的异质结主要通过π-π作用构筑. 当原料中三聚氰胺/GO的质量比是800/1时, 所得催化剂对罗丹明B的催化作用最强, 其一阶动力学常数是纯g-C₃N₄的2.6倍. 这种强化作用主要是由于rGO促进了光生电子-空穴对的分离. 此外, g-C₃N₄/rGO还表现出显著的pH值敏感特性, 催化降解速率随pH的降低而增加. 当pH = 1.98时, 其一阶动力学常数是纯g-C₃N₄的8.6倍. 这是由于酸性条件下质子(H⁺)消耗掉光生电子, 促进了空穴对罗丹明B的氧化作用, 其中rGO充当了一个快速的光生电子转移平台.

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SAPO-34分子筛中多甲基苯分子与卤代甲烷偕甲基化反应的密度泛函理论研究

孔令涛, 沈本贤

2015, 36 (7): 1017-1022. DOI: 10.1016/S1872-2067(15)60842-7

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利用周期性密度泛函理论研究了SAPO-34分子筛催化转化卤代甲烷制取低碳烯烃反应的碳池主要成分多甲基苯分子的偕甲基化反应. 氯甲烷和溴甲烷分子在SAPO-34分子筛内的吸附能分别是-18和-22 kJ/mol, 由于氯和溴原子相似的电负性, 氯甲烷和溴甲烷分子的吸附能并未被精确区分. 以氯甲烷和溴甲烷为甲基化试剂, 得到了几种多甲基苯分子的偕甲基化反应能及能垒, 结果表明, 六甲基苯分子(HMB)的偕甲基化反应为放热反应, 而其余甲基苯分子的偕甲基化反应为吸热反应. 对于上述两种甲基化试剂, 体积最大的HMB均表现出最低的偕甲基化反应能垒, 这可能是由于分子筛骨架与多甲基苯分子之间的静电相互作用增强了HMB的反应活性所致.

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An efficient green synthesis of dispirohydroquinolines via a diastereoselective one-pot eight-component reaction

Sajjad Salahi, Malek Taher Maghsoodlou, Nourallah Hazeri, Mojtaba Lashkari, Santiago Garcia-Granda, Laura Torre-Fernandez

2015, 36 (7): 1023-1028. DOI: 10.1016/S1872-2067(15)60846-4

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The one-pot eight-component reaction between Meldrum's acid, an aromatic aldehyde, and an aryl amine was achieved in the presence of citric acid catalyst. The corresponding dispirohydroquinolines were obtained in good yields with excellent diastereoselectivity. This method is a combination of the Knoevenagel and Michael reactions.

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Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

Javad Hosseini, Mehdi Abdolmaleki, Hamid Reza Pouretedal, Mohammad Hossein Keshavarz

2015, 36 (7): 1029-1034. DOI: 10.1016/S1872-2067(15)60841-5

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An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodeposition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.

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氨功能化介孔MCM-41固载锰卟啉作为萘羟基化多相催化剂

杨福, 高树英, 熊翠蓉, 王海青, 陈进, 孔岩

2015, 36 (7): 1035-1041. DOI: 10.1016/S1872-2067(15)60836-1

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将不同含量的四(五氟苯基)卟啉锰固载于表面氨基功能化的MCM-41介孔分子筛, 所得样品通过粉末X射线衍射、氮气吸附脱附、傅里叶变换红外光谱、X射线光电子能谱、扫描电子显微镜、漫反射紫外-可见光谱、热重和差示扫描量热、电感耦合等离子体进行了表征. 结果表明, 四(五氟苯基)卟啉锰通过Mn与氨基的轴向配位固载于MCM-41. 所制备的样品作为多相催化剂在以间氯过氧苯甲酸为氧化剂选择氧化萘反应中表现出良好的催化性能, 且多次使用后没有明显的活性损失.

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Cinnamomum tamala leaf extract-mediated green synthesis of Ag nanoparticles and their use in pyranopyrazles synthesis

Sneha Yadav, Jitender M. Khurana

2015, 36 (7): 1042-1046. DOI: 10.1016/S1872-2067(15)60853-1

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A novel, biochemical, and eco-friendly method has been developed for the synthesis of Ag nanoparticles using an aqueous leaf extract of readily accessible Cinnamomum tamala as reducing and stabilizing agents. These Ag nanoparticles were used to catalyze the synthesis of pyranopyrazoles. The green nature and ease of recovery and reusability of the catalyst, together with high yields of products, make this protocol attractive and useful.

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Palladium particles from oxime-derived palladacycle supported on Fe₃O₄/oleic acid as a catalyst for the copper-free Sonogashira cross-coupling reaction

Kazem Karami, Samaneh Dehghani Najvani, Nasrin Haghighat Naeini, Pablo Hervés

2015, 36 (7): 1047-1053. DOI: 10.1016/S1872-2067(15)60837-3

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An oxime-derived palladacycle was synthesized using 4-bromobenzoxime and pyridine in CHCl₃, and characterized by FT-IR and ¹H NMR spectroscopy. This Pd complex was supported on Fe₃O₄/oleic acid and shown to be an efficient catalyst for the copper-free Sonogashira cross-coupling reaction of various aryl halides with phenylacetylene in air and in ethanol or mixed aqueous medium. The oxime-derived palladacycle gave highly active palladium nanoparticles for the organic synthesis. The coupling products were obtained in high yields with low Pd loading and the heterogeneous catalyst can be separated by an external magnet and reused six times without loss of its activity. The characterization of the catalyst was carried out by XRD, SEM and TEM. Both TEM and XRD revealed that the palladium nanoparticles were well dispersed with diameters from 5 to 10 nm and average size 9.97 nm.

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KSF supported 10-molybdo-2-vanadophosphoric acid as an efficient and reusable catalyst for one-pot synthesis of 2,4,5-trisubstituted imidazole derivatives under solvent-free condition

Laxmikant D. Chavan, Sunil G. Shankarwar

2015, 36 (7): 1054-1059. DOI: 10.1016/S1872-2067(15)60830-0

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The one-pot three-component cyclocondensation has been developed involving the reaction of benzil with an aromatic aldehydes and ammonium acetate under thermal solvent-free conditions in the presence of a KSF supported 10-molybdo-2-vanadophosphoric acid catalyst. 10-Molybdo-2-vanadophosphoric acid was immobilized on KSF with a 20% loading, which showed the highest catalytic activity. The catalyst was fully characterized using FT-IR spectroscopy, thermal analysis, XRD and SEM analysis techniques. There are several distinct advantages to this protocol, including high yields, short reaction time, operational simplicity and a recyclable catalyst with a facile work-up procedure.

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V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂用于正丁烷催化氧化脱氢反应

徐兵, 朱雪峰, 曹中卫, 杨丽娜, 杨维慎

2015, 36 (7): 1060-1067. DOI: 10.1016/S1872-2067(15)60839-7

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采用浸渍法制备了不同V₂O₅担载量的V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂, 钒物种的前驱体为偏钒酸铵. 对制备的催化剂进行了一系列表征, 并对催化剂上正丁烷选择性氧化脱氢制取丁烯进行了反应研究. 表征结果(包括比表面积、X射线衍射、傅里叶红外光谱、氢气程序升温还原和拉曼光谱)显示, 不同碱土金属元素掺杂的催化剂显示不同的钒价态信息和催化性能. 其中掺杂Ca, Sr, Ba的催化剂, 正钒酸盐相很难被还原, 因此催化剂的氧化还原循环难以建立, 导致以上三种催化剂在正丁烷氧化脱氢反应中活性较低. 然而, Mg掺杂的催化剂却显示出较高的催化活性和选择性. 实验结果表明: 在Mg掺杂的载体上担载5% V₂O₅的催化剂上600 ℃时可获得高达30.3%的正丁烷转化率和64.3%的烯烃总选择性. 这与V₂O₅担载量为5%时, 在获得高度分散的钒氧化合物物种时可使MgO晶相稳定存在密切相关.

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Electricity production by a microbial fuel cell fueled by brewery wastewater and the factors in its membrane deterioration

Afşin Y. Çetinkaya, Emre Oğuz Köroğlu, Neslihan Manav Demir, Derya Yılmaz Baysoy, Bestamin Özkaya, Mehmet Çakmakçı

2015, 36 (7): 1068-1076. DOI: 10.1016/S1872-2067(15)60833-6

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Electricity production from brewery wastewater using dual-chamber microbial fuel cells (MFCs) with a tin-coated copper mesh in the anode was investigated by changing the hydraulic retention time (HRT). The MFCs were fed with wastewater samples from the inlet (inflow, MFC-1) and outlet (outflow, MFC-2) of an anaerobic digester of a brewery wastewater treatment plant. Both chemical oxygen demand removal and current density were improved by decreasing HRT. The best MFC performance was with an HRT of 0.5 d. The maximum power densities of 8.001 and 1.843 μW/cm² were obtained from reactors MFC-1 and MFC-2, respectively. Microbial diversity at different conditions was studied using PCR-DGGE profiling of 16S rRNA fragments of the microorganisms from the biofilm on the anode electrode. The MFC reactor had mainly Geobacter, Shewanella, and Clostridium species, and some bacteria were easily washed out at lower HRTs. The fouling characteristics of the MFC Nafion membrane and the resulting degradation of MFC performance were examined. The ion exchange capacity, conductivity, and diffusivity of the membrane decreased significantly after fouling. The morphology of the Nafion membrane and MFC degradation were studied using scanning electron microscopy and attenuated total reflection-Fourier transform infrared spectroscopy.

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一步温和水热法制备具有改善光催化活性和稳定性的碳包覆CdS纳米粒子

邹帅, 伏再辉, 向超, 吴文锋, 汤森培, 刘亚纯, 尹笃林

2015, 36 (7): 1077-1085. DOI: 10.1016/S1872-2067(15)60827-0

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首次报道在130 oC低温条件下, 以乙酸镉和葡萄糖分别作为镉源和碳源, 硫脲同时充当硫源和葡萄糖水热碳化的催化剂, 通过一步水热碳化法制备了碳包覆的CdS (CdS@C)纳米材料. 与相同条件下制备的纯CdS相比, 合成的CdS@C粒子具有更小的粒子尺寸、良好的分散性以及更均匀的粒子分布. 而且, 葡萄糖在水热碳化过程中能够促使CdS优先形成立方晶相. 此外, 粒子表面的碳物种能拓宽CdS的可见光吸收范围, 稍微降低它的带隙能, 减缓CdS的光生电子-空穴对的复合和光腐蚀. 因此, 它能改善CdS在可见光辐射下催化氧化降解甲基橙的活性和稳定性.

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V@CN催化的芳烃的氧气羟基化反应

李岩, 李冰, 陈婷, 周志成, 王军, 黄军

2015, 36 (7): 1086-1092. DOI: 10.1016/S1872-2067(14)60319-3

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制备了V@CN催化剂, 并用于氧气条件下芳烃的直接羟基化反应. 结果表明, 在V@CN催化剂作用下, 带有不同吸电子基团(CN, NO₂, COOH, CF₃和COCH₃)的芳烃均可被O₂氧化得到相应的酚, 产率中等. 含有卤素(F, Cl和Br)的芳烃也可在该催化体系作用下转化为相应的酚.

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Stereoselective synthesis of vic-halohydrins and an unusual Knoevenagel product from an organocatalyzed aldol reaction: A non-enamine mode

P. B. Thorat, S. V. Goswami, V. P. Sondankar, S. R. Bhusare

2015, 36 (7): 1093-1100. DOI: 10.1016/S1872-2067(14)60317-X

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Stereoselective synthesis by an aldol reaction between chloroacetone and aldehyde was studied using a synthesized chiral organocatalyst and triethylamine. The reaction gave α-chloro-β-hydroxy ketones in excellent yield with high anti selectivity and enantioselectivity. The chiral organocatalyst was also used in the Knoevenagel reaction, which gave α-cyano-β-hydroxy ketones at a low temperature and the usual Knoevenagel product at a high temperature. Both products were obtained in good to moderate yield with good anti selectivity in the case of α-cyano-β-hydroxy ketone derivatives.

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Ni(II), Co(II), and Cu(II) complexes incorporating 2-pyrazinecarboxylic acid: Synthesis, characterization, electrochemical evaluation, and catalytic activity for the synthesis of 2H-indazolo[2,1-b]phthalazine-triones

Behnaz Afzalian, Joel T. Mague, Maryam Mohamadi, S. Yousef Ebrahimipour, Behjat Pour amiri, Esmat Tavakolinejad Kermani

2015, 36 (7): 1101-1108. DOI: 10.1016/S1872-2067(14)60318-1

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Three complexes containing 2-pyrazinecarboxylate (pzca^-), including [Ni(pzca)₂(H₂O)₂], [Co(pzca)₂(H₂O)₂], and [Cu(pzca)₂(H₂O)₂], have been synthesized and characterized using physicochemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complexes were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.

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Selective oxidation of alcohols over nickel zirconium phosphate

Abdol R. Hajipour, Hirbod Karimi, Afshin Koohi

2015, 36 (7): 1109-1116. DOI: 10.1016/S1872-2067(14)60315-6

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Nickel zirconium phosphate nanoparticles were found to function as efficient catalysts for the selective oxidation of a wide range of alcohols to their corresponding ketones and aldehydes using H₂O₂ as an oxidizing agent and without any organic solvents, phase transfer catalysts, or additives. The steric and electronic properties of various substrates had significant influence on the reaction conditions required to achieve acetylation. The results showed that this method can be applied for the chemoselective oxidation of benzyl alcohols in the presence of aliphatic alcohols. The catalyst used in the current study was characterized by ICP-OES, XRD, NH₃-TPD, Py-FTIR, N₂ adsorption-desorption, SEM and TEM. These analyses revealed that the interlayer distance in the catalyst increased from 0.75 to 0.98 nm when Ni²⁺ was intercalated between the layers, whereas the crystallinity of the material was reduced. The nanocatalyst could also be recovered and reused at least seven times without any discernible decrease in its catalytic activity. This new method for the oxidation of alcohols has several key advantages, including mild and environmentally friendly reaction conditions, short reaction time, excellent yields and a facile work-up.

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自下而上法制备金-介孔二氧化硅复合纳米管用作还原4-硝基苯酚的催化剂

彭永胜, 冷文光, 董彬, 格日乐, 段洪东, 高艳安

2015, 36 (7): 1117-1123. DOI: 10.1016/S1872-2067(14)60310-7

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采用自下而上方法制备了金-介孔二氧化硅复合纳米管, 其中金纳米粒子作为催化剂嵌在介孔二氧化硅纳米管管壁内侧. 金纳米颗粒的团聚、脱落和晶粒尺寸生长都可以被有效限制, 而且催化剂负载量和尺寸大小均可实现简单控制. 管壁中的介孔孔道、纳米管末端开口以及一维中空管道可以协同促进反应物扩散, 从而提高4-硝基苯酚还原反应活性. 循环实验证明这种复合纳米管催化剂具有良好的可重复使用性, 而且在反应过程中未出现金纳米粒子脱落或团聚现象.

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Bismuth triflate: A highly efficient catalyst for the synthesis of bio-active coumarin compounds via one-pot multi-componentreaction

Mahmoud. Abd, El Aleem. Ali, Ali. El-Remaily

2015, 36 (7): 1124-1130. DOI: 10.1016/S1872-2067(14)60308-9

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A series of coumarin-chalcone hybrid compounds and coumarins linked to pyrazoline was synthesized in good yield and short time using a simple and efficient method. This method involved the one-pot reaction of salicylaldehyde, an α-ketoester and an aromatic aldehyde (in the case of the coumarin-chalcone derivatives) in addition to hydrazine hydrate (in the case of the pyrazolyl coumarins) in the presence of a catalytic amount of bismuth triflate [Bi(OTf)₃, 5 mol%]. The synthesized compounds showed scavenging activity towards the free radical 2,2-diphenyl-1-picrylhydrazyl. All compounds were characterized using IR, ¹H NMR and ¹³C NMR spectroscopy.

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核壳结构催化剂Cr-Zn@SiO₂@SAPO-34催化合成气直接转化制低碳烃的性能

李津京, 潘秀莲, 包信和

2015, 36 (7): 1131-1135. DOI: 10.1016/S1872-2067(14)60297-7

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合成气直接转化高选择性制烃类产物仍是巨大的挑战. 本文合成了以Cr-Zn氧化物为核, SiO₂为中间过渡层, 再通过原位水热合成覆盖一层SAPO-34分子筛为壳的核壳结构催化剂. 合成气转化反应结果显示, 与纯Cr-Zn金属氧化物相比, 核壳结构催化剂将产物分布由甲醇和甲烷移动至C₂-C₄烃(所有烃类产物中占66.9%). 这表明核壳结构催化剂用于合成气一步法直接转化制液化石油气的反应具有可行性, 但是催化剂结构和组成有待于进一步优化, 以提高其催化反应性能.

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低压下碱金属碳酸盐催化一步法合成碳酸二甲酯

刘春, 张绍科, 蔡宝仪, 金子林

2015, 36 (7): 1136-1141. DOI: 10.1016/S1872-2067(14)60309-0

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报道了低压下碱金属碳酸盐催化环氧化物、CO₂和甲醇一步合成碳酸二甲酯(DMC)的方法, 系统考察了反应条件对一步合成DMC的影响规律. 在最优反应条件下(初始压力0.5 MPa, 反应温度120 ℃, 碳酸钠7.5 mol%), 以环氧乙烷为起始剂的DMC收率达到63.5%. 提出了碱金属碳酸盐催化一步法合成DMC的可能反应机理.

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Pd-O/CeO₂纳米管催化苯酚氧化羰基化反应

袁烨, 王志苗, 安华良, 薛伟, 王延吉

2015, 36 (7): 1142-1154. DOI: 10.1016/S1872-2067(14)60312-0

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以碳纳米管(CNTs)为模板, 采用液相沉积-水热法制备了管状纳米氧化铈(CeO₂-NT). 利用X射线衍射、透射电镜和N₂等温吸附-脱附技术对其结构进行了表征, 所得CeO₂-NT外径~25 nm, 长度大于300 nm, 管壁由粒径4-9 nm的CeO₂晶粒组成, 比表面积为108.8 m²/g. 以其为载体制备了Pd-O/CeO₂-NT催化剂, 程序升温还原结果发现, 该催化剂表面氧在低温下即可被还原, 具有较高的活性. 将Pd-O/CeO₂-NT用于催化苯酚氧化羰基化反应, 催化剂活性和碳酸二苯酯(DPC)选择性均高于零维CeO₂负载的Pd-O/CeO₂-P催化剂. 在优化的条件下, 苯酚转化率为67.7%, DPC选择性为93.3%. 但该催化剂再次使用时活性下降明显, 这是由于Pd-O/CeO₂-NT的管状结构在反应过程中被破坏, 并且活性组分Pd流失所致.

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