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    Chinese Journal of Catalysis
    2010, Vol. 31, No. 10
    Online: 25 October 2010

    Cover:

    Thermoregulated ligand Ph2P(CH2CH2O)16CH3-stabilized rhodium nanoparticles with the property of thermoregulated phase-transfer catalysis in an aqueous/1-butanol biphasic system have been used as catalyst for the hydroformylation of higher olefins. The catalyst exhibited high activity and can be recycled. See the Communication on pages 1191–1194.

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    Research Briefing
    Hydroformylation of Higher Olefins by Thermoregulated Phase-Transfer Catalysis with Rhodium Nanoparticles
    LI Kaoxue, WANG Yanhua*, JIANG Jingyang, JIN Zilin
    2010, 31 (10):  1191-1194.  DOI: 10.1016/S1872-2067(10)60110-6
    Abstract ( 2419 )   [Full Text(HTML)] () PDF (595KB) ( 1019 )  
    Thermoregulated ligand Ph2P(CH2CH2O)16CH3-stabilized rhodium nanoparticles were investigated as the catalyst in the hydroformylation of higher olefins by thermoregulated phase-transfer catalysis in an aqueous/1-butanol biphasic system. Under optimized reaction conditions, the conversion of 1-octene and yield of aldehyde were 98% and 96%, respectively. The catalyst can be easily separated from the product by phase separation and was used for three times without evident loss in activity.
    Gas Phase Epoxidation of Propylene with TS-1 and in Situ H2O2 Produced by a H2/O2 Plasma
    SU Ji1, ZHOU Juncheng1,2, LIU Chunyan1, WANG Xiangsheng1, GUO Hongchen1,*
    2010, 31 (10):  1195-1199.  DOI: 10.1016/S1872-2067(10)60111-8
    Abstract ( 2734 )   [Full Text(HTML)] () PDF (496KB) ( 907 )  
    Gas phase epoxidation of propylene was performed by directly contacting propylene and gaseous H2O2 on the surface of TS-1 catalyst in an integrated reactor. The gaseous H2O2 was produced in situ by a H2/O2plasma. The H2O2 formation rate can be enhanced by increasing the power density of the H2/O2 plasma reactor. The yield and selectivity for propylene oxide (PO) can be increased by optimizing the reaction conditions and using suitable TS-1 catalysts. With a power injection of 3.5 W, flow rates of H2, O2, and propylene of 170, 8, and 18 ml/min, respectively, catalyst loading of 0.8 g, and epoxidation temperature of 110 oC, the yield and selectivity for PO and the utilization rate of H2O2 were 246.9 g/(kg•h), 95.4%, and 36.1%, respectively. During the gas phase reaction, no decline of TS-1 activity was observed.
    Research papers
    Nanosized Noble Metals Intercalated in Clay as Catalysts for Selective Hydrogenation
    Manikandan DHANAGOPAL1,2, DURAISWAMI Divakar1,3, Rupa A. VALENTINE1, Mangalaraja RAMALINGA VISWANATHAN2, Sivakumar THIRIPURANTHAGAN1,*
    2010, 31 (10):  1200-1208.  DOI: 10.1016/S1872-2067(10)60112-X
    Abstract ( 2498 )   [Full Text(HTML)] () PDF (959KB) ( 1101 )  
    The use of clay minerals in the synthesis of nanosized noble metal particles to give increased catalytic activity was investigated. Nanosized platinum and ruthenium catalysts intercalated in clay (montmorillonite/hectorite) were synthesised and their catalytic activity was evaluated for the selective hydrogenation of three different α,β-unsaturated aldehydes, namely, crotonaldehyde, cinnamaldehyde, and citral, in a gas phase microreactor. The metal nano-sol was prepared by the chemical reduction of its precursor by the micellar technique in the presence of cetyl trimethyl ammonium bromide (CTAB), and the micelle stabilized metal particles were intercalated in the clay mineral by ion exchange. TEM micrographs of the catalyst particles showed that the metal particles were in the nanometre range. The average diameters of the particles were 1–25 nm. The effects of temperature, metal loading, and hydrogen flow rate on the catalytic activity and selectivity for α,β- unsaturated alcohol were studied. The results were correlated with the structural properties of the catalysts. The products formed in each reaction over the different catalysts showed that the catalysts were very active for hydrogenation, and the selectivity for the desired product, namely, α,β-unsaturated alcohol, was good. The metal catalysts intercalated in montmorillonite showed better selectivity than that in hectorite because of its higher acidity. Increased selectivity for α,β-unsaturated alcohol was observed with increased flow rate of hydrogen.
    Para-Xylene Maximization Part VIII: Promotion of H-ZSM-5 Zeolite by Pt and HF Doping for Use as Catalysts in Toluene Alkylation with Methanol
    Ahmed K. ABOUL-GHEIT1,*, Ateyya A. ABOUL-ENEIN1, Ahmed E. AWADALLAH1, Salwa A. GHONEIM1, Eman A. EMAM2
    2010, 31 (10):  1209-1216. 
    Abstract ( 2321 )   [Full Text(HTML)] () PDF (341KB) ( 1837 )  
    Toluene was alkylated with methanol in a flow type reactor at temperatures between 300 and 500 °C using H-ZSM-5 zeolite, 0.2%Pt/H-ZSM-5 and hydrofluorinated 0.2%Pt/H-ZSM-5 with HF concentrations of 1.0%, 2.0%, 3.0%, or 4.0%. Pt primarily enhances toluene conversion, total xylenes production, and p-xylene relative to its thermodynamic equilibrium. As the concentration of HF increases from 1.0% to 3.0%, the catalyst activity increases because of the increase in the number of acid sites and their strength. Additionally, the surface area and Pt dispersion also increases. An advantage of increased HF doping is that the formation of voluminous trimethylbenzene (TMB) byproducts is inhibited. However, at a HF concentration of 4.0%, Al and Si are partially leached and then deposited mostly in the wider catalytic pores. This was determined by evaluating the pore volume distribution and we determined that reactivity inhibition was ob-viously present and was due to diffusion restriction.
    Catalytic Oxidation of Aryl Alkyl Sulfides Using Immobilized Vanadyl Ions within Nanoreactors of Al-MCM-41
    Zamanifar ELHAM, Farzaneh FAEZEH*
    2010, 31 (10):  1217-1220.  DOI: 10.1016/S1872-2067(10)60114-3
    Abstract ( 2192 )   [Full Text(HTML)] () PDF (305KB) ( 1095 )  
    VOSO4 immobilized within nanoreactors of Al-MCM-41 (VO2+/Al-MCM-41) was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption, and chemical analysis techniques. The prepared VO2+/Al-MCM-41 successfully catalyzes the oxidation of aryl alkyl sulfides and up to 99% conversion and 90% selectivity for the corresponding sulfoxides were obtained with H2O2 as oxidant in acetonitrile at room temperature in 30 min.
    Preparation of Cost-Effective TiO2-Outerloaded Porous Lava Composites Using Supercritical CO2 and Their Photocatalytic Activity for Methylene Blue Degradation
    MA Minyuan, LI Youji*, CHEN Wei, LI Leiyong
    2010, 31 (10):  1221-1226.  DOI: 10.1016/S1872-2067(10)60115-5
    Abstract ( 2624 )   [Full Text(HTML)] () PDF (739KB) ( 838 )  
    Cost-effective TiO2-outerloaded lava composites (TOLs) were prepared using supercritical CO2 and sealing lava as well as tetrabutyl titanate as a support and a precursor, respectively. The important factors affecting methylene blue (MB) oxidation efficiency were investigated including the initial concentration of MB, the pH, and catalyst concentration. The results show that TOLs have a higher degradation efficiency than pure TiO2 and TiO2-loaded lava composites (TLLs) because of the high adsorption capacity of MB and the small crystalline size of the TiO2 particles in addition to a synergetic effect for adsorption and photocatalytic degradation. The optimum conditions were a MB concentration of 1.5 mg/L at pH 8 with a TOLs concentration of 6.8 mg/L for the fastest MB degradation. Additionally, the used TOLs retained high activity for MB photocatalytic degradation.
    Efficient Synthesis of α-D-Glucose-1-Phosphate by Maltodextrin Phosphorylase Immobilized on Amino-functionalized Magnetic Nanoparticles
    DONG Qing, OUYANG Liming, LIU Jianwen, XU Jianhe*
    2010, 31 (10):  1227-1232.  DOI: 10.1016/S1872-2067(10)60116-7
    Abstract ( 2878 )   [Full Text(HTML)] () PDF (449KB) ( 838 )  
    α-D-Glucose-1-phosphate (Glc-1-P) is an expensive intermediate in the biosynthesis of nucleotide glucose. This paper describes a biocatalytic system for the efficient synthesis of Glc-1-P from the low cost raw materials: maltodextrin and phosphate at ordinary tempera-tures. After molecular cloning and the expression of a maltodextrin phosphorylase (MalPase) gene from E. coli (Escherichia coli) K12, the resultant recombinant enzyme was immobilized on amino-functionalized magnetic nanoparticles for recycling and repeated use. Conditions for the biocatalytic reaction were optimized and the immobilized MalPase could be easily recovered and reused over eight cycles in the re-peated synthesis of Glc-1-P. After simple purification steps approximately 440 mg of crude product was obtained with a moderate isolation yield of 70.5%.
    Adsorption-Oxidation Reaction Mechanism of NO on Na-ZSM-5 Molecular Sieves with a High Si/Al Ratio at Ambient Temperature
    LIU Huayan1,2, ZHANG Zekai2, XU Yuanyuan2, CHEN Yinfei2,*, LI Xi1
    2010, 31 (10):  1233-1241.  DOI: 10.1016/S1872-2067(10)60117-9
    Abstract ( 2575 )   [Full Text(HTML)] () PDF (554KB) ( 1067 )  
    The oxidation reaction mechanism of NO by O2 over Na-ZSM-5 molecular sieves with a high SiO2/Al2O3 ratio was studied at ambient temperature by temperature-programmed surface reaction (TPSR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results show that the NO catalytic oxidation process is accompanied by a significant adsorption of NO2 and it exhibits a dynamic equilibrium between NO2 adsorption and the reaction of NO. TPSR and in situ DRIFTS characterization of the adsorbed NOx species revealed that adsorbed NO3 formed on the surface of the Na-ZSM-5 molecular sieve as a result of the reaction between adsorbed NO and gaseous O2. The oxidation of NO3 with NO produced weakly-adsorbing NO2 and N2O4 which were released once the adsorption reached saturation. Therefore, the strongly-adsorbing NO3 was an intermediate of the NO oxidation reaction and its presence promoted NO adsorption.
    Copolymerization of Propylene Oxide and CO2 Catalyzed by a Rare Earth Borohydride-Diethylzinc-Glycerine Ternary System
    LIU Guangxuan, LI Cong, CHEN Dan, NI Xufeng, JIANG Liming*, SHEN Zhiquan
    2010, 31 (10):  1242-1246.  DOI: 10.3724/SP.J.1088.2010.00425
    Abstract ( 2323 )   [Full Text(HTML)] () PDF (516KB) ( 910 )  
    A ternary catalytic system composed of rare earth borohydrides, diethylzinc, and glycerine has been developed and found to be effective for the copolymerization of propylene oxide (PO) with carbon dioxide. The effect of catalyst composition and reaction conditions on the copolymerization was examined through orthogonal experiments. With Y(BH4)3•3THF-ZnEt2-glycerine molar ratio of 3:60:20, the highest turnover frequency (TOF) of 4908 g/(mol•h was achieved at 80 oC and 3.0 MPa of CO2 using 1,2-dimethoxyethane as solvent. The poly(propylene carbonate) had a carbonate unit content of 95.7% and number-average molecular mass of 6.97x104.
    Water Gas Shift Activity of Pt/CexZr1-xO2 Catalysts in Sulfur-Containing Syngas
    LIU Bing1,2, LI Wenzhao1, XU Hengyong1,*
    2010, 31 (10):  1247-1252.  DOI: 10.3724/SP.J.1088.2010.00327
    Abstract ( 2058 )   [Full Text(HTML)] () PDF (557KB) ( 872 )  
    A series of Pt/CexZr1-xO2 catalysts were prepared by the wet-impregnation method, characterized by X-ray diffraction and tem-perature-programmed reduction, and tested in the water gas shift (WGS) reaction. The results show that the CexZr1-xO2 solid solution has higher redox ability, and doping ceria with zirconium apparently changes the pore structure. The Pt catalysts supported on CexZr1-xO2 has higher Pt dispersion and WGS activity in pure reforming syngas. The WGS activity dropped in sulfur-containing syngas over the Pt/CexZr1-xO2 catalysts. The loss of activity increases with the increase of H2S content, but the deactivation of the catalyst due to H2S adsorp-tion is reversible and can be readily reversed in the reducing atmosphere of the WGS mixture without H2S.
    Epoxidation of Propylene Catalyzed by Reaction-Controlled Phase Transfer Catalyst with in-Situ H2O2
    ZHANG Hengyun, Lü Ying, LI Jun, GAO Shuang*, XI Zuwei
    2010, 31 (10):  1253-1256. 
    Abstract ( 2353 )   [Full Text(HTML)] () PDF (482KB) ( 986 )  
    The epoxidation of propylene catalyzed by a reaction-controlled phase transfer catalyst with H2O2 generated by the oxidation of 2-ethylanthrahydroquinone with molecular oxygen in the organic solvent was investigated. Effects of reaction temperature, reaction time, H2O2 concentration, catalyst concentration, and additives on the epoxidation were studied. Under the suitable conditions, the yield of pro-pylene oxide, based on 2-ethylanthrahydroquinone, was above 85.6% in the fifth cycle. The results of 31P MAS NMR of the recovered cata-lyst showed that the catalyst composition tended to being stable after the third cycle.
    Influence of Precipitation Methods on Precursors and Properties of Cu-Based Catalyst for Methanol Synthesis
    LIN Shengda, TANG Haodong, Lü Zhaobo, LIU Cailai, CEN Yaqing, LIU Huazhang*
    2010, 31 (10):  1257-1262.  DOI: 10.3724/SP.J.1088.2010.00325
    Abstract ( 2126 )   [Full Text(HTML)] () PDF (539KB) ( 1277 )  
    Cu/ZnO/Al2O3 catalyst samples for methanol synthesis were prepared by co-precipitation (CP), two-stage precipitation (TP), and fractional precipitation (FP) methods, respectively. The evaluation results showed that the methanol yields over the catalyst prepared by FP is the best, which is 46.3% higher than that over the catalyst prepared by CP and 9.3% higher than that over the catalyst prepared by TP. The catalyst samples and their precursors were characterized by X-ray diffraction, thermogravimetry, infrared spectroscopy, N2 adsorption-desorption, temperature-programmed reduction, and N2O titration. The results revealed that the precursor prepared by FP has higher amounts of (Cu,Zn)2CO3(OH)2 and (Zn,Cu)5(CO3)2(OH)6 phases and a lower amount of the (Cu,Zn)6Al2(OH)16 CO3•4H2O phase. Therefore, after calcination the catalyst has a higher amount of CuO-ZnO solid solution and carbonate formed at high temperature.
    Mechanism of the Influence of Lanthanum and Cerium on the Stability of Y Zeolite
    YU Shanqing*, TIAN Huiping, DAI Zhenyu, LONG Jun
    2010, 31 (10):  1263-1270. 
    Abstract ( 2284 )   [Full Text(HTML)] () PDF (726KB) ( 1146 )  
    The influence of lanthanum and cerium cations on the stability of Y zeolite was studied by X-ray diffraction, X-ray photoelectron spectroscopy, solid-state NMR spectroscopy, scanning electron microscopy, and energy dispersion spectroscopy. Although the stability of Y zeolite could be enhanced by the introduction of La or Ce cation, the La showed more remarkable effect than Ce. These results were con-firmed theoretically by density functional calculation. There was a strong interaction between the rare earth species and Y zeolite clusters, which restrained the formation of extra-framework alumina and evidently enhanced the stability of Y zeolite. Furthermore, the interaction between La species and Y zeolite was stronger.
    Highly Crystalline TiO2 Whisker Modified with Pt and Its Photocatalytic Performance
    DING Yulan, BAI Yang, LI Wei, CHEN Shanshan, ZHU Yudan, ZHU Yinhua, ZHU Yinhua, YANG Zhuhong*, LU Xiaohua
    2010, 31 (10):  1271-1276.  DOI: 10.3724/SP.J.1088.2010.00408
    Abstract ( 2292 )   [Full Text(HTML)] () PDF (727KB) ( 2743 )  
    Highly thermally stable anatase TiO2 whisker has been synthesized by ion-exchange and calcination at high temperature (800oC) using K2Ti2O5 as the precursor. Pt nanoparticles (1%) were loaded on this TiO2 to prepare a Pt/TiO2 catalyst by the glycol-colloidal method. The catalyst samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray fluo-rescence, and N2 adsorption-desorption measurements. Photocatalytic performance of the Pt/TiO2 catalyst was measured by phenol degrada-tion. The catalytic activity of Pt/TiO2 was 2.3 times that of TiO2 whisker, and the activity on per unit surface area was high. The Pt/TiO2 cata-lyst was stable after reuse 10 times, and it maintained 91% of its initial activity because the loss of Pt was only 6%.
    Water-Soluble Imine Ligand/Palladium-Catalyzed Suzuki Reaction at Room Temperature
    LIU Chun*, NI Qijian, HU Pingping, YUAN Hao, JIN Zilin
    2010, 31 (10):  1277-1280.  DOI: 10.3724/SP.J.1088.2010.00412
    Abstract ( 2156 )   [Full Text(HTML)] () PDF (336KB) ( 1189 )  
    A new air-stable and water-soluble imine ligand (I) has been synthesized and its single crystal structure has been characterized. This N,O-bidentate ligand, with the possible hemilability and the property of green chemistry, is efficient in the palladium-catalyzed Suzuki cross-coupling of aryl bromide and aryl-boronic acid at room temperature in aqueous ethanol. Under the optimized reaction conditions (i.e., n(ArBr) = 0.5 mmol, n(ArB(OH)2) = 0.75 mmol, x(PdCl2) = 1%, x(I) = 2 mol%, n(K2CO3) = 1.0 mmol, and c(EtOH) = 50% aqueous solu-tion), a 99% isolated yield of the product was obtained in 20 min.
    CO2 Reforming of Toluene from Biomass Tar over Ni/Palygorskite Catalyst
    SHI Peichao1, CHEN Tianhu1,*, ZHANG Xianlong2, CHEN Dong1, SONG Lei1, LI Jinhu1
    2010, 31 (10):  1281-1285. 
    Abstract ( 2230 )   [Full Text(HTML)] () PDF (432KB) ( 713 )  
    A nickel catalyst supported on palygorskite (PG) with large surface area was prepared by equal volume impregnation. Catalytic reforming of biomass tar over Ni/PG was studied using toluene as the model compound in the presence of CO2. X-ray diffraction, transmission electron microscopy and CO2-temperature programmed desorption were used to characterized the catalyst samples. The influence of CO2 amount, reaction temperature, and Ni loading on toluene conversion, hydrogen yield, and carbon deposit was investigated. The results showed that three desorption peaks of CO2 appeared on both PG and the Ni/PG catalyst. The toluene conversion and H2 yield increased with the increase in the amounts of CO2 and Ni content as well as the reaction temperature. At 800 oC and CO2/PhCH3 molar ratio of 0.2–0.26, the toluene conversion was the highest; the H2 yield reached the highest at CO2/PhCH3 molar ratio of 0.2. Carbon deposition decreased with increasing the CO2 amount and reaction temperature.
    A Combined Bond-Valence and Periodic DFT Study of the Active Sites in M1 Phase of MoVTeNbO Composite Oxide Catalyst
    ZHU Yihan, LU Weimin*, DONG Xue, WANG Yang, MA Fei
    2010, 31 (10):  1286-1292.  DOI: 10.3724/SP.J.1088.2010.00415
    Abstract ( 2630 )   [Full Text(HTML)] () PDF (572KB) ( 919 )  
    A combined bond-valence and periodic DFT study was carried out to interpret the nature of the d electrons in the active sites of the MoVTeNbO composite oxide catalyst (M1 phase). On investigating all the possible distribution of the coupled d electrons and oxygen vacancies, the most efficient combination of M-M-Te (M = Mo or V) active sites for propane selective oxidation has been argued. Besides, MoO6 octahedra primarily stabilizes the crystal structure of M1 phase by attaining strong covalent Mo–O bonding in the equatorial plane, while VO6 octahedra plays a minor role. Nb species that has been considered to stabilize the M1 phase was found to have mainly ionic inter-actions with the framework and act as a structure-directing agent in forming the pentagonal channels in the M1 phase.
    Effects of Calcium and Vanadium Ions on the Epoxidation of Cyclohexene with H2O2 Catalyzed by Vanadium Bromoperoxidase
    ZHANG Biaoming1,2, CAO Xupeng1, XUE Song1, XIAO Tonghu3, ZHANG Wei1,4,*
    2010, 31 (10):  1293-1299.  DOI: 10.3724/SP.J.1088.2010.00438
    Abstract ( 2516 )   [Full Text(HTML)] () PDF (538KB) ( 1111 )  
    Vanadium bromoperoxidase (V-BPO) from a marine macro-alga Corallina officinalis can catalyze the epoxidation of cyclohexene in the presence of KBr to form epoxycyclohexane using H2O2 as the oxidant. A process intensification strategy has been developed by the integration of V-BPO pretreatment, continuous feeding of H2O2, and optimizing reaction conditions in order to improve the epoxidation pro-ductivity. The BPO activity and thermostability increased significantly when the V-BPO solution was dialyzed with a buffer containing 1.0 mmol/L vanadium ion and 1.0 mmol/L calcium ion. The apparent enzyme activity was improved when the H2O2 was fed continuously using a constant flow pump. When combined with the optimal reaction conditions (including buffer, pH, temperature, enzyme concentration, and KBr and H2O2 concentrations), the space-time yield of epoxycyclohexane and its yield to hydrogen peroxide reached 4.79 g/(L•h) and 74%, respectively. These values are 78% increasing than the highest values reported previously.
    Effect of Heat Treatment on the Photoelectrocatalytic Performance of TiO2 Nanotube Array Film
    ZHANG Xi1, LING Yunhan2,*, LIAO Lei1, NIU Zhiyuan2, CHEN Shilei2, ZHAO Chenggen1
    2010, 31 (10):  1300-1304.  DOI: 10.3724/SP.J.1088.2010.00418
    Abstract ( 2219 )   [Full Text(HTML)] () PDF (772KB) ( 1016 )  
    Well-aligned and uniform titanium dioxide nanotube array films were fabricated in-situ on titanium substrate by electrochemical anodic oxidation. The resulting amorphous films were crystallized and annealed at 500 oC in different atmospheres such as the oxygen, air, argon, and hydrogen. The photoelectrocatalytic performance of the as-annealed nanotube array films was investigated using methane blue (MB) as a target pollutant. The MB degradation kinetics met the law of first order reaction and the rate constants were 4.967, 3.127, 1.989, and 1.625 h-1 at 0.5 V bias, respectively. Electrochemical impedance spectroscopy analysis revealed that the MB degradation was governed by the charge transfer characteristic of the nanotube. The improvement of light absorbance and excitation and the lower transfer impedance might be critical factors for the efficient photoelectrocatalysis of TiO2 array films annealed in oxygen.