催化学报

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第34卷第10期目次

2013, 34 (10): 0-0.

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微介孔材料物理吸附准确性分析的理论与实践

张哲泠, 杨正红

2013, 34 (10): 1797-1810. DOI: 10.1016/S1872-2067(12)60691-9

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比表面积和孔径分布是表征催化剂和材料物理性质的基本参数,随着材料研究的日益广泛和深入,研究工作者对该参数的科学性和准确性要求日益提高. 但是,比表面积和孔径分布的分析方法—物理吸附法,长期以来被看作一种测量方法,其准确性并不为人们所关注,在实际工作中对其的理解存在着大量的误区. 本文从仪器硬件设计、实验操作及数据处理三方面对物理吸附法所涉及的准确度进行了探讨.

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用于木质素催化湿式氧化反应的纳米空心球钙钛矿催化剂

高鹏, 李昌志, 王华, 王晓东, 王爱琴

2013, 34 (10): 1811-1815. DOI: 10.1016/S1872-2067(12)60691-3

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利用尿素辅助溶剂热法合成了一系列LaFe_xMn_1-xO₃和La_0.9Sr_0.1MnO₃纳米空心球材料,并采用X射线衍射、透射电子显微镜和物理吸附等方法对其晶相、形貌和比表面积进行了表征. 在木质素的催化湿式氧化反应(CWAO)中,该催化剂表现出比传统的柠檬酸溶胶-凝胶法制备的钙钛矿材料更高的催化活性. 这主要是由于空心球结构所致. 当T=120℃,p(O₂)=0.2MPa时,CWAO反应1h后木质素转化率超过80%. 反应后组分离子溶出量很低,表明由于钙钛矿相结构的存在,催化剂在该反应条件下非常稳定.

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苯磺酰胺参与下二价钌催化环丙乙炔扩环反应

陈雨叶, 汪俊松, 李兴伟, 贾爱群

2013, 34 (10): 1816-1819. DOI: 10.1016/S1872-2067(12)60680-9

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将二价钌配合物用于催化环丙乙炔扩环生成四元环结构的反应,扩展了一系列环丙乙炔底物和磺酰胺底物,并得到了较高的产率.

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CO诱导的FeO(111)/Ru(0001)负载Au原子吸附位和电荷的改变

欧阳润海, 李微雪

2013, 34 (10): 1820-1825. DOI: 10.1016/S1872-2067(12)60664-0

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采用密度泛函理论研究了CO气氛对FeO(111)/Ru(0001)负载Au原子吸附位、电荷及其稳定性的影响. 首先考察了FeO(111)单层薄膜在Ru(0001)表面上的界面结构. 研究发现,表面莫尔超晶胞内的HCP区域有最小的Fe-O层间距(rumpling),且Fe和O原子均与衬底Ru形成化学键. Au原子在FeO/Ru(0001)上最稳定的吸附在HCP区域的Fe-bridge位. 其中,Au原子诱导两个Fe原子从O原子层的下面翻转到其上面,形成两个Au-Fe键,且Au带负电. 当把体系暴露在CO气氛下后,CO能诱导Au原子从原来最稳定的Fe-bridge位转移到其邻近的O-top位,伴随着Au的电荷从负变到正,形成非常稳定的Au⁺-CO羰基物. 结果表明,反应气氛对负载金属催化剂的化学状态及其稳定性的影响很大; 同时也强调了反应条件下催化剂原位表征的重要性.

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预处理对Ni-Co双金属沼气重整催化剂性能与结构的影响

赵健, 周伟, 马建新

2013, 34 (10): 1826-1832. DOI: 10.1016/S1872-2067(12)60648-2

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采用过量浸渍法制备了Ni-Co/La₂O₃-γ-Al₂O₃双金属催化剂, 并使用固定床石英反应器在850℃,0.1MPa和空速为6000mL g_cat^-1 h^-1的条件下考察了预处理对催化剂性能的影响. 运用X射线衍射、热重-差示扫描量热、透射电子显微镜、扫描电镜和X射线能谱分析等手段对催化剂进行了表征. 结果表明,与传统氢气还原预处理相比,经氢气和二氧化碳预处理后, 催化剂性能明显提高,且能基本消除该催化剂上沼气重整反应的诱导期. 511 h的稳定性实验结果表明,催化剂经氢气和二氧化碳预处理后具有很好的稳定性和抗积碳性,平均积碳速率仅为0.2 mg g_cat^-1 h^-1. 表征结果显示,经氢气和二氧化碳预处理后,催化剂具有更好的抗烧结和抗积碳性能,反应后金属颗粒较小,分布较均匀,粒径分布范围较窄,从而增强了催化剂的稳定性.

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载体对钒铬氧化物催化剂结构及催化3-甲基吡啶氨氧化反应活性的影响

姜枫, 邓生财, 牛磊, 肖国民

2013, 34 (10): 1833-1838. DOI: 10.1016/S1872-2067(12)60650-0

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通过等体积浸渍法制备了Nb₂O₅,MgF₂,TiO₂和SiO₂负载和未负载的钒铬氧化物催化剂,并应用X射线衍射、N₂吸附-脱附、H₂程序升温还原和NH₃程序升温脱附对催化剂进行了表征. 结果表明,催化剂比表面积较大时有利于CrVO₄-I(单斜)的生成,比表面积较小则有利于CrVO₄-III(斜方)的生成. 在310-400℃下3-甲基吡啶氨氧化制备3-氰基吡啶反应中,具有较高催化活性的催化剂与V物种还原性较高和表面活性位数量较多有关; 而高的3-氰基吡啶选择性则与催化剂表面较低的酸性密切相关. 升高反应温度可大幅度提高催化剂的活性,且其选择性基本不变.

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Desulfurization of liquid fuels using air-assisted performic acid oxidation and emulsion catalyst

Ahmad Imtiaz, Ahmad Waqas, Ishaq Muhammad

2013, 34 (10): 1839-1847. DOI: 10.1016/S1872-2067(12)6668-8

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Catalytic oxidative desulfurization (ODS) of model oil and commercial oil samples was investigated using an air-assisted performic acid oxidation system with a phase transfer or emulsion catalyst comprising a quaternary ammonium salt-based heteropolyoxometalate. Different emulsion catalysts with a Keggin type heteroployoxometalate anion (containing W, Mo, and V) and cetyltrimethylammonium bromide cation were prepared and characterized by X-ray fluorescence, Fourier transform infrared spectroscopy, and scanning electron microscopy. [C₁₆H₃₃N(CH₃)₃]₃[PW₉Mo₃O₄₀] was the most effective catalyst in the current oxidation system, which reduced the sulfur content of the model oil from 1275 μg/g to 57 μg/g. The reactivity order of different model sulfur compounds was thiophene < dibenzothiophene < 4,6-dimethyldibenzothiophene. The ODS of model sulfur compounds followed first order kinetics with apparent activation energy from 29 to 27 kJ/mol. The catalysts also performed efficiently in the ODS of the industrial oil samples, including untreated naphtha, light gas oil, heavy gas oil, and Athabasca oil sands derived bitumen, for which sulfur removal rates were 83%, 85%, 68% and 64%, respectively.

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吸附NO_x的功能化硅胶用于催化温和条件下醇的选择性氧化

张华, 付罗岭, 钟红敏

2013, 34 (10): 1848-1854. DOI: 10.1016/S1872-2067(12)60657-3

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利用接枝方式将2,2,6,6-四甲基哌啶(TEMPO)固载到SPE柱填料硅胶上制备了功能化硅胶,其吸附NO_x应用于催化醇的选择性氧化反应中. 并利用元素分析、红外光谱、N₂吸附-脱附和NO_x程序升温脱附对催化剂进行了考察. 结果表明,所制备催化剂中TEMPO固载量为0.292 mmol/g,NO_x吸附量为0.749 mmol/g; 常温常压下1 mmol芳香醇在0.5g该催化剂作用下进行选择性氧化反应2h,原料转化率和产物选择性均高达99%. 该催化剂提高了醇分子在孔道内部与TEMPO和NO_x接触几率,促进了反应进行,根据反应现象,对该体系催化机理进行了推测.

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利用第一性原理研究氧化铟在甲醇水蒸气重整反应中的催化作用

林森, 叶欣欣

2013, 34 (10): 1855-1860. DOI: 10.1016/S1872-2067(12)60662-7

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基于第一性原理方法,证明了甲醛在In₂O₃(110)表面可以选择性地转化为CO₂. 水分解得到的OH物种有利于甲醛脱氢得到CHO,后者不易直接脱氢,其H原子被周围的OH捕获生成CO和H₂O. 最后,相比较其从表面直接脱附,CO更容易获得一个晶格氧生成CO₂. 计算结果表明,在没有PdIn合金参与催化的甲醇水蒸气重整反应过程中,In₂O₃确实扮演着非常重要的角色,进而从理论上证实了甲醇在氧化铟表面选择性生成CO₂的实验结果.

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Poly(4-vinylpyridinium butane sulfonic acid) hydrogen sulfate: An efficient, heterogeneous poly(ionic liquid), solid acid catalyst for the one-pot preparation of 1-amidoalkyl-2-naphthols and substituted quinolines under solvent-free conditions

Ali Reza Kiasat, Arash Mouradzadegun, Seyyed Jafar Saghanezhad

2013, 34 (10): 1861-1868. DOI: 10.1016/S1872-2067(12)60659-7

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Poly(4-vinylpyridinium butane sulfonic acid) hydrogen sulfate has been used as an efficient dual acidic catalyst for the one-pot preparation of 1-amidoalkyl-2-naphthols and substituted quinolines under solvent-free conditions. The catalyst was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and thermo-gravimetric analysis. The results revealed several advantages to our new catalyst system, including its reusability, facile work-up procedure, eco-friendly reaction conditions, short reaction time, and high product yields.

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Nanostructure-based electrochemical sensor for the voltammetric determination of benserazide, uric acid, and folic acid

Sakineh Esfandiari Baghbamidi, Hadi Beitollahi, Seyed Zia Mohammadi, Somayeh Tajik, Somayeh Soltani-Nejad, Vahhab Soltani-Nejad

2013, 34 (10): 1869-1875. DOI: 10.1016/S1872-2067(12)60655-X

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A carbon paste electrode modified with carbon nanotubes and ferrocene was fabricated. An electrochemical study of the modified electrode and an investigation into its efficiency for the electrocatalytic oxidation of benserazide, uric acid and folic acid were undertaken. The electrode was also used to study the electrocatalytic oxidation of benserazide using cyclic voltammetry, chronoamperometry, and square wave voltammetry (SWV). We found that the oxidation of benserazide at the surface of the modified electrode occurs at a potential about 285 mV lower than that of unmodified carbon paste electrode. SWV gave a linear dynamic range from 8.0×10^-7 to 7.0×10^-4 mol/L. The detection limit was 1.0×10^-7 mol/L for benserazide. This modified electrode was used for the determination of benserazide, uric acid, and folic acid in an urine sample.

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CdS/石墨烯纳米复合物的可见光催化效率和抗光腐蚀行为

严佳佳, 王坤, 许晖, 钱静, 刘巍, 杨兴旺, 李华明

2013, 34 (10): 1876-1882. DOI: 10.1016/S1872-2067(12)60677-9

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制备了一系列CdS纳米晶/石墨烯(CdS/GR)复合物,并在可见光照条件下评价了其光催化降解亚甲基蓝的光催化效率和抗光腐蚀行为. 研究表明,石墨烯的引入加速了CdS纳米晶(NCs)光生电子的迁移速率,抑制了其光生电子-空穴的复合,有效改善了其光催化降解有机污染物的性能. CdS/GR复合物中的石墨烯含量显著影响其光催化效率,其中石墨烯含量为4.6%的光催化剂效率最高,其光电流是CdS NCs的2.3倍. 利用光电化学和X射线衍射技术进一步证实,石墨烯的引入抑制了CdS NCs光腐蚀的发生,提高了CdS/GR复合物的光催化稳定性.

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Multiwall carbon nanotube paste electrode with 3,4-dihydroxy-cinnamic acid as mediator for the determination of glutathione in pharmaceutical and urine samples

Mohsen Keyvanfard, Hassan Karimi-Maleh, Khadijeh Alizad

2013, 34 (10): 1883-1889. DOI: 10.1016/S1872-2067(12)60661-5

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A sensitive and selective electrochemical sensor for the determination of glutathione (GSH) was developed using a modified multiwall carbon nanotube paste electrode with 3,4-dihydroxy-cinnamic acid as a mediator. This modified electrode showed very high electrocatalytic activity for the anodic oxidation of GSH. Under the optimized conditions, the electrocatalytic peak current showed a linear relationship with GSH concentration in the range of 0.5-400.0 μmol/L with a detection limit of 0.1 μmol/L GSH. The relative standard deviations for seven successive assays of 5.0 and 25.0 μmol/L GSH were 2.2% and 2.7%, respectively. The modified electrode was used for the determination of GSH compounds in real urine samples.

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Succinimide-N-sulfonic acid catalyzed synthesis of bis(indolyl)methane and coumarin derivatives under mild conditions

Farhad Shirini, Nader Ghaffari Khaligh

2013, 34 (10): 1890-1896. DOI: 10.1016/S1872-2067(12)60669-X

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A mild and simple procedure is described for the synthesis of bis(indolyl)methane and coumarin derivatives using succinimide-N-sulfonic acid as an efficient, cheap, and reusable catalyst under mild conditions.

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Papain enzyme supported on magnetic nanoparticles：Preparation, characterization and application in the fruit juice clarification

Leila Mosafa, Majid Moghadam, Mohammad Shahedi

2013, 34 (10): 1897-1904. DOI: 10.1016/S1872-2067(12)60663-9

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The preparation, characterization, and application of silica-coated magnetic nanoparticles for papain immobilization is reported. Papain was covalently attached onto the (3-chloropropyl) trimethoxysilane-modified silica-coated magnetic nanoparticles. The enzyme-immobilized nanoparticles were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, and vibrating sample magnetometry techniques. Response surface methodology combined with statistical analyses using Minitab were employed to evaluate optimum operating conditions to immobilize papain on the magnetic nanoparticles. The optimum conditions were: temperature = 27.3 ℃, pH of the enzyme solution = 7.1, concentration of papain = 3.3 mg/mL, and immobilization time = 10 h. Compared with the free papain, the immobilized papain displayed enhanced enzyme activity, better tolerance to variations in the medium pH and temperature, improved storage stability, and good reusability. Both the free and immobilized enzymes were effective for the clarification of pomegranate juice.

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Precursors of active Ni species in Ni/Al₂O₃ catalysts for oxidative dehydrogenation of ethane

Lucie Smoláková, Šárka Botková, Libor Čapek, Peter Priecel, Agnieszka Sołtysek, Martin Kout, Lenka Matějová

2013, 34 (10): 1905-1913. DOI: 10.1016/S1872-2067(12)60672-X

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Ni/Al₂O₃ catalysts for oxidative dehydrogenation (ODH) of ethane were prepared by impregnation of Al₂O₃ with nickel acetate or nickel nitrate, and by mechanical mixing of NiO and Al₂O₃. The Ni-based catalysts were characterized by N₂ adsorption-desorption, X-ray diffraction, diffuse reflectance UV-visible diffuse reflectance spectroscopy, and temperature-programmed reduction of hydrogen. The results showed that formation of crystalline NiO particles with a size of < 8 nm and/or non-stoichiometric NiO species in the Ni/Al₂O₃ catalysts led to more active species in ODH of ethane under the investigated reaction conditions. In contrast, tetrahedral Ni species present in the catalysts led to higher selectivity for ethene. Formation of large crystalline NiO particles (22-32 nm) over Ni/Al₂O₃ catalysts decreased the selectivity for ethene.

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钴纳米粒子催化水相费托合成

王航, 寇元

2013, 34 (10): 1914-1925. DOI: 10.1016/S1872-2067(12)60674-3

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水相费托合成可以在远低于传统温度下实现,其低温高效的特点使其具有重要的应用潜力. 本文制备了水相稳定且可循环利用的Co纳米粒子并应用于水相费托反应,150℃下活性为7.4×10^-7mol_CO g_Co^-1 s^-1,C₅₊选择性接近40%,是目前纯钴水相费托合成的最好结果,而其它方法合成的催化剂在150℃时活性低下. 对催化剂进行了粒径、结构、成分测定和原位红外光谱检测,研究了催化剂在反应中的重构过程和B掺杂效应.

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沉淀煅烧法合成(CuAg)_0.15In_0.3Zn_1.4S₂光催化剂及可见光下的制氢性能

张广山, 张文, John C. Crittnn, 陈勇生, Disuk Minkt, 王鹏

2013, 34 (10): 1926-1935. DOI: 10.1016/S1872-2067(12)60675-5

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研究了沉淀煅烧法制备的纳米级(CuAg)_0.15In_0.3Zn_1.4S₂光催化剂以及产氢效率,并采用X射线衍射、透射电镜、扫描电镜、N₂吸附-脱附、紫外-可见吸收光谱等手段对催化剂进行了表征. 结果表明,(CuAg)_0.15In_0.3Zn_1.4S₂的结晶度、比表面积和吸收可见光能力与煅烧温度和煅烧时间有关. 在可见光下,以KI为电子给体,考察了不同条件对光催化产氢能力的影响. 发现在600℃煅烧5h时所制的(CuAg)_0.15In_0.3Zn_1.4S₂光催化剂产氢活性最高,产氢速率为1750 μmol g^-1 h^-1,量子效率在420±5nm达到12.8%,比未煅烧催化剂的光催化活性提高了约6倍.

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Synthesis of hexahydroquinolines using the new ionic liquid sulfonic acid functionalized pyridinium chloride as a catalyst

Ardeshir Khazaei, Mohammad Ali Zolfigol, Ahmad Reza Moosavi-Zare, Javad Afsar, Abdolkarim Zare, Vahid Khakyzadeh, Mohammad Hassan Beyzavi

2013, 34 (10): 1936-1944. DOI: 10.1016/S1872-2067(12)60678-0

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Sulfonic acid functionalized pyridinium chloride [pyridine-SO₃H]Cl has been synthesized as a novel Brönsted acidic ionic liquid and characterized on the basis of its FT-IR, ¹H and ¹³C NMR, MS, thermogravimetry, and derivative thermogravimetry data. The material has also been used as a highly efficient, homogeneous, and reusable catalyst for the preparation of hexahydroquinolines according to the one-pot multi-component condensation of arylaldehydes, dimedone (5,5-dimethylcyclohexane-1,3-dione), β-ketoesters, and ammonium acetate under solvent-free conditions.

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催化氧化处理工业废气中高浓度甲醛

魏日出, 陈洪林, 张小明, 索继栓

2013, 34 (10): 1945-1950. DOI: 10.1016/S1872-2067(12)60696-2

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制备了用于温和条件下催化氧化去除工业废气中高浓度甲醛(HCHO)的1%Pt-4%CeO₂/AC催化剂. 将高浓度甲醛的催化氧化过程与双甘膦氧化制备草甘膦的反应过程集成在一起,使草甘膦合成过程中产生和排放出来的甲醛(100-300 mg/m³)在通过催化剂床层时被完全除去. 系统研究了温度、空速和甲醛含量对甲醛去除率的影响. 在气体空速(GHSV)低于20000 h^-1时废气中几乎所有的甲醛都被氧化,处理后的废气中的甲醛含量低于0.1 mg/m³,甲醛的转化率为99.1%-100%. 当GHSV为30000- h^-1,催化剂床层温度为12℃时,生产废气通过催化剂床层后的甲醛含量小于1.5 mg/m³,甲醛的转化率为97.56%-99.99%. 1%Pt-4%CeO₂/AC催化剂的中试试验结果表明,处理后最终尾气中甲醛含量小于10 mg/m³,有效地防止了甲醛对人们健康的危害,具有良好的产业化前景.

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Catalytic properties of nanosized zinc aluminates prepared by green process using Opuntia dilenii haw plant extract

C. Ragupathi, J. Judith Vijaya, S. Narayanan, L. John Kennedy, Seeram Ramakrishna

2013, 34 (10): 1951-1958. DOI: 10.1016/S1872-2067(12)60682-2

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Various nanosized zinc aluminate (ZnAl₂O₄) samples were prepared by a conventional and a microwave method both with and without using Opuntia dilenii haw plant extract, and were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), high resolution scanning electron microscopy (HRSEM), energy dispersion scanning (EDX), temperature dependent conductance measurements, thermoelectric power measurements, ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The formation of a pure ZnAl₂O₄ phase was confirmed by XRD and FT-IR. A change in morphology from nanosized plates to nanosized sheets with, respectively, the conventional and microwave heating methods was clearly shown by HRSEM. UV-Vis diffusion reflectance spectroscopy measured the band gaps of ZnAl₂O₄ nanosized plates and nanosized sheets as 3.5 and 3.9 eV, respectively. The synthesized ZnAl₂O₄ was single crystalline and has three photoluminescence emissions at 482, 528, and 540 nm. ZnAl₂O₄ nanosized sheets prepared by the microwave method showed higher catalytic activity for the oxidation of benzyl alcohol (85% conversion) than ZnAl₂O₄ nanosized plates prepared by the conventional method (60% conversion).

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