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Chinese Journal of Catalysis
2012, Vol. 33, No. 12
Online: 18 January 2013


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Zhou and coworkers in the article on pages 1877–1882 showed that a montmorillonite-supported copper(I) catalyst prepared by a simple ion exchange method has high activity in the N-arylation of nitrogen heterocycles with aryl chlorides or bromides, and it can be recycled.

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Table of Contents for Vol. 33 No. 12 2012, 33 (12):  0-0.  Abstract ( 995 )   PDF (1894KB) ( 779 )

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Contents for Volume 33 (2012) 2012, 33 (12):  1-1.  Abstract ( 886 )   [Full Text(HTML)] () PDF (958KB) ( 755 )

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Author Index for Volume 33 (2012) 2012, 33 (12):  2-2.  Abstract ( 903 )   [Full Text(HTML)] () PDF (342KB) ( 560 )

Research Briefing

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Thermoregulated phase-separable catalysis for Rh nanoparticle catalyzed selective hydrogenation of 1,5-cyclooctadiene XU Yi-Cheng, WANG Yan-Hua, ZENG Yan, SONG Ying, ZHAO Jia-Qi, JIANG Jing-Yang, JIN Zi-Lin 2012, 33 (12):  1871-1876.  DOI: 10.1016/S1872-2067(11)60473-7 Abstract ( 2015 )   [Full Text(HTML)] () PDF (365KB) ( 779 )   Through the study of the critical solution temperature of ionic liquids [CH3(OCH2CH2)nN+Et3][CH3SO3–] (ILPEG, n = 12, 16, 22), ILPEG-stabilized Rh nanoparticle catalysts have been found to function as thermoregulated phase-separable catalysts and have been shown to be efficient and recyclable for the selective hydrogenation of 1,5-cyclooctadiene (1,5-COD) to cyclooctene (COE). Under optimized conditions, the conversion of 1,5-COD and selectivity for COE were 99% and 90%, respectively. The Rh catalyst could be recovered by simple phase separation and reused for ten times without loss of activity or selectivity.

Research papers

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Montmorillonite-Supported Copper(I) for Catalyzing N-Arylation of Nitrogen Heterocycles QI Xiao-Long, ZHOU Li-Mei, JIANG Xiao-Hui, FAN Hong-Wei, FU Hai-Yan, CHEN Hua 2012, 33 (12):  1877-1882.  DOI: 10.1016/S1872-2067(11)60458-0 Abstract ( 2168 )   [Full Text(HTML)] () PDF (337KB) ( 826 )   Montmorillonite-supported copper (I) catalyst has been prepared by a simple ion exchange method. The resulting catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectrometry, with results showing that Cu+ had been successfully intercalated into the interlayer of Montmorillonite. The catalyst showed high levels of activity towards the N-arylation of nitrogen heterocycles with aryl chlorides or bromides. Furthermore, the catalyst could be reused up to four times without any significant loss in activity.

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Flower-Like Co-Ni/C Bimetallic Catalysts for the Selective Hydrogenation of o-Chloronitrobenzene JIE Ya-Ling, XIAO 南, LING Zheng, LIU Yue, YU Chang, QIU Jie-Shan 2012, 33 (12):  1883-1888.  DOI: 10.1016/S1872-2067(11)60451-8 Abstract ( 2152 )   [Full Text(HTML)] () PDF (5100KB) ( 729 )   Three dimensional flower-like Co-Ni/C bimetallic catalysts composed of interlaced carbon flakes with highly dispersed metal nanoparticles were synthesized by a facile hydrothermal/solvothermal process followed by a heat treatment in flowing N2. The sizes of the metal nanoparticles were from 26 to 4 nm, which became smaller as the Co/Ni molar ratio increased. The catalytic activities for the selective hydrogenation of o-chloronitrobenzene to o-chloroaniline were tested. The conversion of o-chloronitrobenzene over the bimetallic Co-Ni/C catalysts was increased by up to 200% compared with that over a mono-metallic Co/C catalyst, which was due to a synergistic interaction between the Co and Ni species. Hydrogen temperature-programmed desorption results showed that new active sites were formed in the Co50Ni50/C catalyst due to the formation of a Co-Ni alloy, which gave the improved activity of the Co50Ni50/C catalyst.

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Characterization and Catalytic Performance in n-Hexane Cracking of HEU-1 Zeolites Dealuminated Using Hydrochloric Acid and Hydrothermal Treatments LIU Xiao-Ling, WANG Yan, WANG Xu-Jin, ZHANG Ya-Fei, GONG Yan-Jun, XU Qing-Hu, XU Jun, DENG Feng, DOU Tao- 2012, 33 (12):  1889-1900.  DOI: 10.1016/S1872-2067(11)60454-3 Abstract ( 2051 )   [Full Text(HTML)] () PDF (622KB) ( 816 )   A series of modified HEU-1 zeolites were prepared using hydrochloric acid treatment, hydrothermal treatment, and a combination of these. The parent and modified HEU-1 zeolites were characterized by X-ray diffraction, N2 adsorption-desorption isotherms, X-ray fluorescence, temperature-programmed desorption of ammonia, Fourier-transform infrared spectroscopy of adsorbed pyridine, and 27Al solid-state magic-angle spinning nuclear magnetic resonance techniques. The catalytic cracking performances of the modified HEU-1 zeolites were evaluated on a fixed-bed microreactor at 625 °C, atmospheric pressure, and an n-hexane weight hourly space velocity of 2.0 h−1. The results showed that extra-framework alumina could be removed by directly treating with hydrochloric acid, and framework alumina could be removed by hydrothermal treatment. Acidity characterization showed that the weak acid sites of HEU-1 zeolites could be adjusted using acid treatment, and the number of strong acid sites could be reduced using hydrothermal treatment. The framework nSi:nAl ratio was improved by using a combination of hydrothermal treatment and acid leaching. The acidities of the HEU-1 zeolites were adjusted and both the mesopore volume and external surface area were enhanced. In n-hexane cracking reactions, the dealuminated HEU-1 zeolite obtained by hydrothermal treatment for 4 h at 600 °C and then washing with hydrochloric acid exhibited the highest propylene production as a result of suppression of the hydrogen transfer reaction. At 625 °C, the selectivity for propylene on HEU-1(HT4-HCl) increased to 35.2% from 21.9%, and the lifetime of HEU-1(HT4-HCl) was also prolonged from not more than 10 to 40 h.

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Effect of Dispersion on Catalytic Performance of Supported Pt Catalysts for CO Oxidation CHEN Sheng-Neng, CHEN Jun-Yu, ZHAO Yue, CHEN Ming-Shu, WAN Hui-Lin 2012, 33 (12):  1901-1905.  DOI: 10.1016/S1872-2067(11)60447-6 Abstract ( 2231 )   [Full Text(HTML)] () PDF (765KB) ( 949 )   A series of ceria, silica, and γ-alumina-supported platinum catalysts were prepared by the incipient-wetness impregnation method. Transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to determine the dispersion of Pt. For the Pt/CeO2 catalysts, XRD studies suggest that Pt was better dispersed as its concentration decreased. This observation correlated well with XPS analysis. For catalysts with the same Pt mass loading, TEM and XRD results suggest that Pt dispersion displays an increasing order as Pt/SiO2 < Pt/γ-Al2O3 < Pt/CeO2. Catalytic activities for CO oxidation were investigated. Results showed that the 0.25 wt% Pt/CeO2 exhibited a higher activity than other oxide supported catalysts with a turnover frequency of 2.2 × 10-3 CO2 per total Pt per second at room temperature.

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Cobalt Porphyrin Immobilized on Montmorillonite: A Highly Efficient and Reusable Catalyst for Aerobic Oxidation of Alcohols to Carbonyl Compounds ZHOU Xian-Tai, JI Hong-Bing 2012, 33 (12):  1906-1912.  DOI: 10.1016/S1872-2067(11)60461-0 Abstract ( 2016 )   [Full Text(HTML)] () PDF (510KB) ( 604 )   The highly efficient aerobic oxidation of alcohols to carbonyl compounds was achieved catalyzed by cationic meso-tetrakis (1-methyl-4-pyridyl, TM4PyP) metalloporphyrins immobilized in montmorillonite interlayers. Cobalt porphyrin (CoTM4PyP-MT) showed excellent activity and selectivity in the aerobic oxidation of benzyl alcohol, where 90% yield of benzaldehyde was obtained. CoTM4PyP-MT can be five times reused without significant loss of activity.

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Preparation of Ru-[bmim]BF4 Catalyst Using NaBH4 as Reducing Agent and Its Performance in Selective Hydrogenation of Benzene XUE Wei, QIN Yan-Fei, LI Fang, WANG Yan-Ji, WANG Zhi-Miao 2012, 33 (12):  1913-1918.  DOI: 10.1016/S1872-2067(11)60469-5 Abstract ( 1973 )   [Full Text(HTML)] () PDF (583KB) ( 1004 )   A Ru-[bmim]BF4 catalyst was prepared in a mixture of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF4) and H2O using NaBH4 as a reducing agent. The Ru-[bmim]BF4 catalyst showed higher selectivity for cyclohexene than a catalyst reduced by N2H4·H2O because of the influence of boron. When Ru-[bmim]BF4 was reused, higher activity and lower selectivity were obtained because the number of Ru active sites increased through leaching of the ionic liquid. The used catalyst also contained ZnOHF formed in the reaction between F– and ZnSO4, which was an additive in the reaction. Under the influence of the ionic liquid as a template, ZnOHF grew along the (001) direction and exhibited rod-like morphology.

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Carbon Paste Electrode Prepared from Chemically Modified Multiwall Carbon Nanotubes for the Voltammetric Determination of Isoprenaline in Pharmaceutical and Urine Samples Ali A. ENSAFI, Hajar BAHRAMI, Hassan KARIMI-MALEH, Shadpour MALLAKPOUR 2012, 33 (12):  1919-1926.  DOI: 10.1016/S1872-2067(11)60465-8 Abstract ( 1803 )   [Full Text(HTML)] () PDF (404KB) ( 916 )   A carbon paste electrode with added multiwall carbon nanotubes chemically modified with N-(3,4-dihydroxyphenethyl)- 3,5-dinitrobenzamide was used as the electrochemical sensor for the determination of trace amounts of isoprenaline. The modified electrode showed good electrocatalytic activity for the anodic oxidation of isoprenaline, which was due to a substantial decrease in the anodic overpotential. Under the optimum conditions, measurements using square wave voltammetry had a linear range in the range of 0.3 to 125.0 µmol/L of isoprenaline and a detection limit of 0.1 µmol/L. The diffusion coefficient and kinetic parameters were determined using electrochemical methods. The relative standard deviation for seven successive assays of 1.0 and 20.0 µmol/L isoprenaline were 1.9% and 2.4%, respectively. This electrochemical sensor was successfully applied for the determination of isoprenaline in human urine and injection solution samples.

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Influence of Mn/(Mn+Ce) Ratio of MnOx-CeO2/WO3-ZrO2 Monolith Catalyst on Selective Catalytic Reduction of NOx with Ammonia XU Hai-Di, FANG Zhi-Tao, CAO Yi, KONG Shuang, LIN Tao, GONG Mao-Chu, CHEN Yao-Qiang 2012, 33 (12):  1927-1937.  DOI: 10.1016/S1872-2067(11)60467-1 Abstract ( 1991 )   [Full Text(HTML)] () PDF (607KB) ( 1026 )   A series of monolith MnOx-CeO2/WO3-ZrO2 catalysts with different mass ratios of Mn/(Mn+Ce) were prepared and used for the selective catalytic reduction (SCR) of NOx with NH3 in the presence of excess O2. The catalysts were characterized by N2 adsorption, oxygen storage capacity, X-ray diffraction, X-ray photoelectron spectroscopy, NH3/NO temperature-programmed desorption, and H2 temperature-programmed reduction. The best catalyst had the mass ratio of Mn/(Mn+Ce) = 0.5. It gave 90% NOx conversion in the range of 173-355 ºC at the gas hourly space velocity of 10000 h-1, and characterization results showed that a higher oxidation activity of NO to NO2, more surface Ce and Mn with a larger Ce3+/Ce4+ ratio, lower NH3 and NO desorption temperatures, and excellent redox ability were together responsible for its best NH3-SCR performance.

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Synthesis of Mixed Alcohols from CO Hydrogenation over Iron and Nickel Metal Phosphide Catalysts SONG Xian-Gen, DING Yun-Jie, CHEN Wei-Miao, DONG Wen-Da, PEI Yan-Peng, ZANG Juan, YAN Li, Lü Yuan 2012, 33 (12):  1938-1944.  DOI: 10.1016/S1872-2067(11)60460-9 Abstract ( 2238 )   [Full Text(HTML)] () PDF (515KB) ( 905 )   A series of silica supported iron and nickel metal phosphides with different molar ratios of P to metal were synthesized by the temperature programmed reduction method. Their catalytic performance for CO hydrogenation in a fixed bed reactor was tested with the conditions of 553 K, 5.0 MPa, and H2:CO = 2 (molar ratio). With the FePx/SiO2 catalysts (x denotes the molar ratio of P to metal), the product was a mixture of oxygenates containing methanol as the major component. With the NiPx/SiO2 samples, the liquid product was mainly methanol. The Fe2P, Fe3P, Ni, Ni2P, Ni3P, and Ni12P5 phases were stable during CO hydrogenation, while most of the metallic Fe phase transformed into iron carbide.

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1,3,5-Tris(hydrogensulfato) Benzene: A New and Efficient Catalyst for Synthesis of 4,4'-(arylmethylene)bis(1H-pyrazol-5-ol) Derivatives Zahed KARIMI-JABERI, Baharak POOLADIAN, Masoud MORADI, Ehsan GHASEMI 2012, 33 (12):  1945-1949.  DOI: 10.1016/S1872-2067(11)60477-4 Abstract ( 2021 )   [Full Text(HTML)] () PDF (101KB) ( 1005 )   1,3,5-Tris(hydrogensulfato) benzene (THSB) was easily prepared by the reaction between phloroglucinol and chlorosulfonic acid in dichloromethane at room temperature. This compound was then used as an efficient catalyst for the synthesis of 4,4'-(arylmethylene)bis(1H-pyrazol-5-ols) through the condensation reactions of 1-phenyl-3-methylpyrazol-5-one with several different aromatic aldehydes in ethanol at 75 °C. The present methodology offers several advantages over existing methodologies, such as excellent yields, simple procedure, easy work-up and ecofriendly reaction conditions.

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Solvent-Free Selective Cross-Aldol Condensation of Ketones with Aromatic Aldehydes Efficiently Catalyzed by a Reusable Supported Acidic Ionic Liquid Abolghasem DAVOODNIA, Ghazaleh YASSAGHI 2012, 33 (12):  1950-1957.  DOI: 10.1016/S1872-2067(11)60470-1 Abstract ( 1995 )   [Full Text(HTML)] () PDF (468KB) ( 1084 )   A newly prepared catalyst consisting of acidic ionic liquid 1-(4-sulfonic acid)butylpyridinium hydrogen sulfate supported on silica was used to catalyze the cross-aldol condensation of ketones with aromatic aldehydes under solvent-free conditions. The highly active and selective catalyst gave good to excellent yields of the desired cross-aldol products without the occurrence of any self-condensation reactions. Reaction times were short, the procedure and work-up were simple, and no volatile or hazardous organic solvents were necessary. Moreover, the catalyst could be reused at least four times with only a slight reduction in activity.

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Effect of Precipitation Temperature on the Performance of CuO/ZnO/CeO2/ZrO2 Catalyst for Methanol Steam Reforming ZHANG Lei, PAN Li-Wei, NI Chang-Jun, SUN Tian-Jun, ZHAO Sheng-Sheng, WANG Shu-Dong, HU Yong-Kang, WANG An-Jie 2012, 33 (12):  1958-1964.  DOI: 10.3724/SP.J.1088.2012.20750 Abstract ( 1685 )   [Full Text(HTML)] () PDF (524KB) ( 686 )   A series of CuO/ZnO/CeO2/ZrO2 catalyst samples for methanol steam reforming were prepared by a co-precipitation procedure, and the effect of precipitation temperature on the catalytic performance was investigated. All the samples were characterized by N2 adsorption, X-ray diffraction, temperature-programmed reduction, and N2O titration. It is shown that the precipitation temperature remarkably influenced the catalyst structure and property. When the precipitation temperature was 60 oC, the catalyst exhibited the best activity with suppressed CO formation. Compared with commercial catalyst (CB-7), the CeZr as support instead of the Al2O3 can dramatically improve the conversion at low temperature, effectively inhibit the CO generation, reduce the subsequent CO removing process, which was helpful for methanol stream reforming technology using in the proton exchange membrane fuel cell applications.

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Influence of MnOx Loading on Activity of MnOx/Ce0.7Zr0.2La0.1O2-Al2O3 Catalyst for Catalytic Combustion of Diesel Soot ZHU Yi, PAN Hao, CHEN Shan-Hu, WANG Shi-Dan, ZHAO Ming, GONG Mao-Chu, CHEN Yao-Qiang 2012, 33 (12):  1965-1973.  DOI: 10.3724/SP.J.1088.2012.20746 Abstract ( 1962 )   [Full Text(HTML)] () PDF (1137KB) ( 1374 )   A series of MnOx/Ce0.7Zr0.2La0.1O2-Al2O3 supported catalysts with the Ce0.7Zr0.2La0.1O2:Al2O3 mass ratio of 1:1 and different MnOx loadings were prepared by the incipient wetness method. The catalysts were characterized by X-ray diffraction, low temperature N2 adsorption-desorption, X-ray photoelectron spectroscopy, O2 temperature-programmed desorption, and H2 temperature-programmed reduction. The catalytic performance of these catalysts for the combustion of diesel soot was investigated. It is found that surface-adsorbed active oxygen species and low-temperature reducibility of MnOx are the determinants of catalytic activity. When the MnOx loading is 5%, the catalyst activity decreases owing to the loss of active oxygen species, which are necessary for the catalytic combustion. When the MnOx loading is increased to 10%, the catalyst activity is dramatically increased because of the enhanced reducible manganese species. Interestingly, the optimal values for reducible manganese species and surface-adsorbed oxygen species can be achieved in the catalyst with 20% MnOx, and so the catalyst exhibits the best catalytic activity, giving a light-off temperature about 179 oC lower than that of the non-catalytic soot combustion. With a further addition of MnOx species up to 30%, its catalytic activity is deteriorated mainly due to the decrease in surface-trapped oxygen species and upper shift of the reduction temperature.

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Preparation of Ag(Au)/Graphene-TiO2 Composite Photocatalysts and Their Catalytic Performance under Simulated Sunlight Irradiation JIANG Ling-Xiao, LI Ke-Xin, YAN Liu-Shui, DAI Yu-Hua, HUANG Zhi-Min 2012, 33 (12):  1974-1981.  DOI: 10.3724/SP.J.1088.2012.20820 Abstract ( 1841 )   [Full Text(HTML)] () PDF (707KB) ( 1549 )   To improve the solar utilization efficiency of TiO2, the graphene-TiO2 and Ag(Au)/graphene-TiO2 composite photocatalysts were prepared by solvothermal reduction and photoreduction deposition technique, respectively. The phase structure, morphology, porosity, optical absorption property as well as composition and structure of as-prepared materials were characterized. The results indicated that TiO2 interacts with graphene via Ti–O–C covalent bonds and Ag or Au nano-particles evenly deposite on the graphene and TiO2 surface. The photocatalytic activity and degradation kinetics of the as-prepared photocatalysts were studied by the degradation of aqueous rhodamine B and methyl orange under solar simulating Xe lamp irradiation. The results indicated that the composite photocatalysts exhibit higher photocatalytic activity compared with pure TiO2 due to enhanced quantum efficiency, narrowed band gap, and perfect textural properties.

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Polyacrylamide Gel Preparation, Photocatalytic Properties, and Mechanism of BiVO4 Particles SUN Jun-Hui, YANG Hua, XIAN Tao, WANG Wei-Peng, FENG Wang-Jun 2012, 33 (12):  1982-1987.  DOI: 10.3724/SP.J.1088.2012.20901 Abstract ( 1837 )   [Full Text(HTML)] () PDF (438KB) ( 772 )   BiVO4 particles were prepared by a polyacrylamide gel method and characterized by X-ray diffraction, scanning electron microscopy, and ultraviolet-visible diffuse reflectance spectroscopy. The results demonstrate that the as-prepared BiVO4 particles crystallize in a monoclinic scheelite-type structure, are regularly shaped like spheres with a uniform size of ~400 nm, and have a bandgap energy of 2.49 eV. The photocatalytic activity of BiVO4 particles was evaluated by the degradation of methylene blue under simulated sunlight irradiation. The effects of O2, N2, ethanol, and KI on the photocatalytic efficiency were investigated. Hydroxyl radicals (•OH) formed on the catalyst under simulated sunlight irradiation were detected by photoluminescence spectroscopy using terephthalic acid as a probe molecule. The photocatalytic degradation mechanism involved is discussed in detail. Based on the photocatalytic results, hydroxyl radicals and photogenerated h+ are suggested to be the two main active species toward the photocatalytic degradation of methylene blue by BiVO4.