催化学报

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第35卷第2期目次

2014, 35 (2): 0-0.

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过渡金属氧化物掺杂对铜锰氧化物催化CO氧化性能的影响

蔡丽娜, 胡臻皓, Peter Brnton, 李文翠

2014, 35 (2): 159-167. DOI: 10.1016/S1872-2067(12)60699-8

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以乙酸铜和乙酸锰为铜锰前驱体，以NH₄HCO₃为沉淀剂，相应金属硝酸盐为掺杂剂，采用共沉淀法制备了不同过渡金属氧化物掺杂的铜锰氧化物催化剂.?采用N₂物理吸附、X射线衍射，氢气-程序升温还原和原位红外漫反射光谱等方法对催化剂进行了表征，考察了系列催化剂上CO反应性能.?结果表明，掺杂过渡金属氧化物可以调变催化剂对CO的吸附能力，进而影响催化剂性能.

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采用溶胶-凝胶-溶剂热路径合成H₃PW₁₂O₄₀/TiO₂和H₄SiW₁₂O₄₀/TiO₂及其光催化降解二硝基甲苯

冯长根, 尚海茹, 刘霞

2014, 35 (2): 168-174. DOI: 10.1016/S1872-2067(12)60736-0

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以非离子表面活性剂P123为结构导向剂，采用溶胶-凝胶与溶解热相结合方法，制备了两类介孔材料H₃PW₁₂O₄₀/TiO₂和H₄SiW₁₂O₄₀/TiO₂，并对其进行了表征.?X射线粉末衍射和拉曼光谱分析表明，所制催化剂为锐钛矿晶型，体系中H₃PW₁₂O₄₀和H₄SiW₁₂O₄₀的Keggin结构经400?℃焙烧后仍保持完整.?H₃PW₁₂O₄₀/TiO₂和H₄SiW₁₂O₄₀/TiO₂的平均粒径分别为15.49和7.75?nm.?N₂吸附-脱附和扫描电镜结果表明，P123的加入使催化剂的粒径减小，比表面积和孔体积明显增大，其中H₃PW₁₂O₄₀/TiO₂和H₄SiW₁₂O₄₀/TiO₂的比表面积分别高达252.2和250.0?m²/g.?紫外漫反射吸收光谱表明，与纯TiO₂相比，复合催化剂的吸收光谱发生了明显的红移，且吸收强度明显增大.?催化剂对DNT降解实验表明，在最佳操作条件下降解率可高达95%.?

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国产航空煤油裂解催化剂Pt/Zr_xTi_xAl_1-2xO₂的性能

焦毅, 王健礼, 朱权, 李象远, 陈耀强

2014, 35 (2): 175-184. DOI: 10.1016/S1872-2067(12)60732-2

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采用共沉淀法制备了一系列Zr_xTi_xAl_1-2xO₂复合氧化物载体材料，考察了其作为裂解催化剂载体对航空煤油裂解反应的影响.?采用全自动吸附仪、X射线衍射、扫描电镜/能谱仪联用、NH₃-程序升温脱附等手段对催化剂进行了表征.?结果表明，当ZrO₂：TiO₂：Al₂O₃质量比为1：1：3时催化剂具有最大的比表面积和孔容；具有最强的表面酸性和最集中的强酸中心密度，且具有良好的再生功能.?实验结果表明，载体ZrO₂：TiO₂：Al₂O₃质量比为1：1：3时催化剂上650?℃裂解产气量较热裂解提高了2.1倍，700?℃时提高1.4倍.?另外，该系列载体材料经1000?℃焙烧5?h后，所制得的催化剂几乎失去了催化活性.

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MOF(Fe)的制备及其氧气还原催化性能

宋国强, 王志清, 王亮, 李国儒, 黄敏建, 银凤翔

2014, 35 (2): 185-195. DOI: 10.1016/S1872-2067(12)60729-3

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以硝酸铁为金属离子前驱体、均苯三甲酸为有机配体，采用水热法合成了金属有机骨架MOF（Fe）催化剂，应用X射线衍射、N₂吸附-脱附、透射电镜、红外光谱和热重等方法对催化剂的结构进行了表征，并采用循环伏安法测试了催化剂在碱性电解质中的氧气还原（ORR）催化性能，同时也采用旋转圆盘电极进一步研究了催化剂的ORR的动力学行为.?结果表明，所制MOF（Fe）具有很好的晶型结构、大比表面积、丰富的微孔以及较高的热稳定性. 且表现出很好的ORR催化活性. ORR的反应历程随电位的改变而改变：电位在-0.3到0.50 V范围内，ORR为2电子途径；随着电位从-0.50 V升至-0.95 V，ORR从2电子向4电子途径转变. 另外，该催化剂在碱性电解质中也表现出较好的氧气析出（OER）催化性能，这为制备用于ORR和OER的高效非贵金属催化剂提供了新的途径.

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Nanocrystalline titanium dioxide catalyst for the synthesis of azlactones

Priyanka Anandgaonker, Ganesh Kulkarni, Suresh Gaikwad, Anjali Rajbhoj

2014, 35 (2): 196-200. DOI: 10.1016/S1872-2067(12)60741-4

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Titanium dioxide nanoparticles were prepared by a electrochemical reduction method using parameters such as current density, solvent polarity, distance between electrodes, and concentration of stabilizers to control the size of the nanoparticles. The nanoparticles were characterized by UV-Vis spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy, and their catalytic performance was tested for the synthesis of a series of 4-aryldiene-2-phenyl-5(4)-oxazolones from the cyclodehydration and condensation of the respective aldehyde, hippuric acid and acetic anhydride. Easy availability, reusability and eco-friendliness were some prominent features of the nanocrystalline titanium dioxide catalyst.

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Electrocatalysis of dopamine in the presence of uric acid and folic acid on modified carbon nanotube paste electrode

Mohammad Mazloum-Ardakani, Mahboobe Abolhasani, Bibi-Fatemeh Mirjalili, Mohammad Ali Sheikh-Mohseni, Afsaneh Dehghani-Firouzabadi, Alireza Khoshroo

2014, 35 (2): 201-209. DOI: 10.1016/S1872-2067(12)60734-7

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A chemically modified carbon paste electrode (CPE), consisting of 2,2'-[(1E)-(1,2-phenylenebis(azanylylidene)] bis(methanylylidene)]bis(benzene-1,4-diol) (PBD) and multiwalled carbon nanotubes (CNTs), was used to study the electrocatalytic oxidation of dopamine using cyclic voltammetry, chronoamperometry, and differential pulse voltammetry (DPV). First, the electrochemical behavior of the modified electrode was investigated in buffer solution. Then the diffusion coefficient, electrocatalytic rate constant, and electron-transfer coefficient for dopamine oxidation at the surface of the PBD-modified CNT paste electrode were determined using electrochemical approaches. It was found that under optimum conditions (pH = 7.0), the oxidation of dopamine at the surface of such an electrode occurred at about 200 mV, lower than that of an unmodified CPE. DPV of dopamine at the modified electrode exhibited two linear dynamic ranges, with a detection limit of 1.0 μmol/L. Finally, DPV was used successfully for the simultaneous determination of dopamine, uric acid, and folic acid at the modified electrode, and detection limits of 1.0, 1.2, and 2.7 μmol/L were obtained for dopamine, uric acid, and folic acid, respectively. This method was also used for the determination of dopamine in a pharmaceutical preparation using the standard addition method.

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X射线光电子能谱法研究UV_{254 nm}光催化、O₃强化UV_{254 nm}光催化和真空紫外光催化降解甲醛中Pt-TiO₂薄膜的表面性质

傅平丰, 张彭义

2014, 35 (2): 210-218. DOI: 10.1016/S1872-2067(12)60740-2

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以Pt-TiO₂为光催化剂，研究了气相甲醛分别在35 h连续UV_{254 nm}光催化、O₃强化UV_{254 nm}（O₃+UV_{254 nm}）光催化和真空紫外（UV_{254+185 nm}）光催化中的降解效率，考察了副产物O₃的去除率，采用X射线光电子能谱（XPS）法分析Pt-TiO₂在不同光催化前后Pt的电子态和累积有机产物，研究纳米Pt对甲醛降解和O₃去除的强化机理. 连续光催化降解实验表明，以纳米Pt改性TiO₂可以同时增强甲醛和O₃的去除率，特别是O₃的去除率可提高3.1-3.4倍. 对催化剂C 1s和O 1s峰分别经分峰拟合处理后，发现Pt-TiO₂上累积的含羰基和羟基的有机物含量按以下顺序减少：UV_{254 nm}光催化 > O₃强化UV_{254 nm}光催化 > 真空紫外光催化，而在连续35 h光催化降解过程中，催化剂的失活现象却按相反的方向变得越来越不明显. 负载的金属Pt在O₃+UV_{254 nm}和UV_254+185nm光催化过程中被氧化成PtO_ads和Pt⁴⁺物种，而在UV_{254 nm}光催化过程中金属Pt未被氧化，所以推测是气相中的O₃和羟基自由基参与金属Pt的氧化过程. Pt-TiO₂表面高价态的Pt氧化物种可作为光生电子捕获中心，强化光生载流子的分离过程，增强Pt-TiO₂的光催化活性. Pt氧化物种可作为O₃分解的活化中心，使Pt-TiO₂对O₃的分解效率远高于纯TiO₂. 以XPS对比研究在三种不同光催化环境中Pt-TiO₂表面性质，可以解释在UV_{254+185 nm}光催化过程中纳米Pt对甲醛和O₃同时去除的强化机理，并说明了催化剂不失活的内在原因.

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丝网印刷法制备高催化活性对电极

赵春雨, 史彦涛, 钟志勇, 马廷丽

2014, 35 (2): 219-226. DOI: 10.1016/S1872-2067(12)60737-2

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对电极在染料敏化太阳能电池（DSCs）中主要起催化氧化还原反应及收集电荷的作用，铂对电极常用的制备方法为磁控溅射法，但其成本较高，制备条件苛刻. 本文通过引入低成本的表面活性剂Span-85，所制得的铂对电极的附着力、透光率和均匀性显著改善，实现了面积可控，与两步浸泡法和旋涂热解法制备的对电极在DSCs中的光电转换效率分别为7.30%，6.96%和7.03%. 紫外-可见吸收光谱、扫描电镜和附着力测试等结果表明，（1）添加表面活性剂有利于增加附着力及改善透光率和均匀性；（2）使用该法制备的Pt/FTO对电极的透光率与两步浸泡法制作的相同，且铂粒子分布更加均匀. 电化学阻抗图谱、塔菲尔极化曲线和循环伏安曲线结果表明，丝网印刷方法制备的Pt/FTO对电极具有更加优异的催化性能，且该法更有利于降低其生产成本和大规模生产.

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铑-ImiFerroPhos配合物对β-取代-α,β-不饱和磷酸酯的不对称氢化

段正超, 王联芝, 左晓宇, 胡向平, 郑卓

2014, 35 (2): 227-231. DOI: 10.1016/S1872-2067(12)60742-6

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将手性二茂铁双膦配体ImiFerroPhos应用到β-取代-α，β-不饱和磷酸酯的不对称氢化反应中，在温和的反应条件下，以高收率及较高对映选择性合成了一系列β-取代的手性磷酸酯，最高获得了92%的ee值.

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NaOH modified WO₃/SiO₂ catalysts for propylene production from 2-butene and ethylene metathesis

Surasa Maksasithorn, Damien P. Debecker, Piyasan Praserthdam, Joongjai Panpranot, Kongkiat Suriye, Sirachaya Kunjara Na Ayudhya

2014, 35 (2): 232-241. DOI: 10.1016/S1872-2067(12)60760-8

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A WO₃/SiO₂ catalyst is used in industry to produce propylene from 2-butene and ethylene metathesis. Catalysts with various WO₃ loading (4% to 10%) were prepared by impregnation and tested for the metathesis of ethene and trans-2-butene. Ion exchange of NaOH onto the WO₃/SiO₂ catalyst was used to mitigate the acidity of the catalysts in a controlled way. At low WO₃ loading, the treatment with large amounts of NaOH resulted in a significant decrease in metathesis activity concomitant with significant W leaching and marked structural changes (XRD, Raman). At higher WO₃ loading (6% to 10%), the treatment with NaOH mainly resulted in a decrease in acidity. FT-IR experiments after adsorption of pyridine showed that the Lewis acidic sites were poisoned by sodium. Nevertheless, the metathesis activity remained constant after the NaOH treatment. This suggested that the remaining acidity on the catalyst was enough to ensure the efficient formation of the carbene active sites. Interestingly, Na poisoning resulted in some modification of the selectivity. The mitigation of acidity was shown to favor propene selectivity over the formation of isomerization products (cis-2-butene, 1-butene, etc.). Moreover, treatment with NaOH led to a shorter induction period and reduced coke formation on the WO₃/SiO₂ catalyst.

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Silica-bonded propylpiperazine-N-sulfamic acid as recyclable solid acid catalyst for preparation of 2-amino-3-cyano-4-aryl-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromenes and hydroxy-substituted naphthalene-1,4-dione derivatives

Fahime Khorami, Hamid Reza Shaterian

2014, 35 (2): 242-246. DOI: 10.1016/S1872-2067(12)60761-X

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An efficient method for the synthesis of 2-amino-3-cyano-4-aryl-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromenes and hydroxy-substituted naphthalene-1,4-dione derivatives, using silica-bonded propylpiperazine-N-sulfamic acid as a solid acid, green, heterogeneous catalyst, under ambient and solvent-free conditions, is described. A simple procedure, high yields, short reaction time, safety, and reusability of the catalyst are advantages of these protocols.

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Electrocatalytic measurement of H₂O₂ concentration using bis(N-2-methylphenyl-salicyldenaminato)copper(Ⅱ) spiked in a carbon paste electrode

Hossein Khoshro, Hamid R. Zare, Rasoul Vafazadeh

2014, 35 (2): 247-254. DOI: 10.1016/S1872-2067(12)60753-0

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The electrochemical behavior of a bis(N-2-methylphenyl-salicyldenaminato)copper(Ⅱ) complex spiked in a carbon paste electrode (BMPSCu-CPE) and its electrocatalytic reduction of H₂O₂ were examined using cyclic voltammetry, chronoamperometry, and differential pulse voltammetry. Cyclic voltammetry was used to study the redox properties of BMPSCu-CPE at various potential scan rates. The apparent charge transfer rate constant and the transfer coefficient for the electron transfer between BMPSCu and the carbon paste electrode (CPE) were 1.9±0.1 s^-1 and 0.43, respectively. BMPSCu-CPE had excellent electrocatalytic activity for H₂O₂ reduction in 0.1 mol/L phosphate buffer solution (pH 5.0), and it decreased the overpotential by 300 mV as compared to CPE alone. The diffusion coefficient and kinetic parameters such as the heterogeneous catalytic electron transfer rate constant and electron transfer coefficient for the reduction of H₂O₂ at the BMPSCu-CPE surface were also determined using electrochemical methods. Differential pulse voltammetry showed two linear dynamic ranges of 1.0-10.0 and 10.0-300.0 μmol/L and a detection limit of 0.63 μmol/L H₂O₂. The BMPSCu-CPE has excellent reproducibility and long term stability, and it was successfully applied for the determination of H₂O₂ in two pharmaceutical samples: an antiseptic solution and a hair dying cream.

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Low temperature adsorption of CO on modified, vicinal Cu(100) surfaces：A comparative study

Przemysław Jan Godowski, Jens Onsgaard

2014, 35 (2): 255-259. DOI: 10.1016/S1872-2067(12)60747-5

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The experimental results of the adsorption of CO on clean and potassium-modified vicinal Cu(100) surfaces at 125 K were present. We studied three surfaces under identical experimental conditions. At 125 K, potassium forms disordered structure on vicinals and CO adsorbs only on sites not occupied by K. It was found that a small percent of the CO molecules dissociate on the stepped interfaces. The influence of steps dominates over pre-adsorbed alkali atoms at 125 K.

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Tribromo melamine as novel and versatile catalyst for the formylation and acetylation of alcohols

Maryam Hajjami, Arash Ghorbani-Choghamarani, Zahra Karamshahi, Masoomeh Norouzi

2014, 35 (2): 260-263. DOI: 10.1016/S1872-2067(12)60748-7|

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Tribromo melamine has been found to be an efficient and green organocatalyst for the acetylation and formylation reactions of alcohols with acetic anhydride and ethyl formate at room temperature and under mild reaction conditions.

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Cyanoethylation of alcohols and amines by cesium-modified zeolite Y

Sara Zamanian, Ali Nemati Kharat

2014, 35 (2): 264-269. DOI: 10.1016/S1872-2067(12)60751-7

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Zeolite Y modified by cesium and magnesium ions was prepared by ion-exchange and impregnation methods, and its activity in the cyanoethylation of aliphatic and aromatic alcohols and amines was investigated. During the preparation of some samples, the transformation of zeolite Y into a pollucite-type phase occurred. This phase exhibited good activity in the cyanoethylation of aliphatic alcohols. The prepared solids modified by the impregnation method were more active than the ion-exchanged solids. The activities of the catalysts, in contrast to other basic solids, were scarcely affected by the presence of air or moisture. A correlation between catalyst basicity and catalytic activity is discussed. The catalysts were characterized by X-ray diffraction, volumetric nitrogen adsorption surface area measurement, and CO₂temperature-programmed desorption. Scanning electron microscopy revealed that the particles of the modified nanocatalysts were < 40 nm. The reaction of acrylonitrile with linear alcohols in the presence of the catalysts was accelerated by microwave irradiation.

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Effects of Bi and Ni on the properties of a vanadium phosphorus oxide catalyst

Yun Hin Taufiq-Yap, Choon Seon Yuen, Nawi @ Mohamed Nurul Suziana, Ramli Irmawati

2014, 35 (2): 270-276. DOI: 10.1016/S1872-2067(12)60749-9

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Vanadium phosphorus oxide (VPO) catalysts were synthesized by the dihydrate method which involved the two steps for the preparation of the dihydrate (VOPO₄×2H₂O) and the precursor hemihydrate (VOHPO₄×0.5H₂O). Bi and Ni salt were added into the mixture of VOPO₄×2H₂O and isobutanol, and the obtained precursors were calcined in a flow of a n-butane/air mixture to produce the promoted VPO catalysts. The catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption, inductively coupled plasma-atomic emission spectroscopy, scanning electron microscopy (SEM), and H₂ temperature-programmed reduction (H₂-TPR). Their catalytic properties were tested using a fixed-bed microreactor. All the catalysts gave main XRD peaks at 2θ = 22.9°, 28.5°, and 30.0°, attributing to the (020), (204), and (221) planes of the pyrophosphate phase (VO)₂P₂O₇, respectively. The promoted catalysts have smaller crystallite size and higher specific surface areas. SEM micrographs revealed the formation of more prominent plate-like crystallites that were arranged as rosette clusters. H₂-TPR results showed that the promoted catalysts had lower reduction peak temperatures and possessed higher amounts of V⁵⁺-O^2- and V⁴⁺-O^- pairs, which gave higher selectivity and activity in the selective oxidation of n-butane to maleic anhydride.

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