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    Chinese Journal of Catalysis
    2013, Vol. 34, No. 3
    Online: 02 April 2013

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    Xu and coworkers reviewed a topic of selective catalytic dehydration, oxidation, or hydrogenation of polyols to value-added chemicals. The characteristics of structure of polyols were analyzed. The challenge and responding resolvent in the process of conversion were also discussed. Based on the research status of selective catalytic transformation of ployols to value-added chemicals in recent years, the research hotspots in future were prospected.See pages492–507 in this issue.

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    Table of Contents
    Table of Contents for Vol. 34 No. 3
    2013, 34 (3):  0-0. 
    Abstract ( 460 )   PDF (1086KB) ( 764 )  
    Special Column on Progress in Catalysis in China during
    Preface to Special Column on Progress in Catalysis in China during 1982-2012
    Jie Xu, Qin Xin
    2013, 34 (3):  399-400.  DOI: 10.1016/S1872-2067(12)60550-6
    Abstract ( 788 )   [Full Text(HTML)] () PDF (311KB) ( 711 )  
    Progress in catalysis in China during 1982-2012: Theory and technological innovations
    XIN Qin, LIN Liwu
    2013, 34 (3):  401-435.  DOI: 10.1016/S1872-2067(11)60463-4
    Abstract ( 1219 )   [Full Text(HTML)] () PDF (930KB) ( 1931 )  

    The development of catalytic science and technology in China dates from the early 20th century. In the beginning, the efforts of our predecessors gave an initial period of steady development. Then in the 1960s, there were serious obstacles by human factors during which the development of catalysis was stagnant and we lost more than ten years of development opportunity. In the 1980s, catalysis in China entered a period of rapid expansion. During this period, three main research sectors, namely, Chinese Academy of Sciences (CAS), universities, and industries, were rapidly established and development recovered. Researchers carried out research using reaction kinetics as the main method and means. In basic research, the discovery of novel catalytic materials, characterization methods, and novel catalytic reactions were the main research directions. The introduction of surface science and nanoscience has greatly promoted and deepened the basic exploration of catalysis. Catalysis is now changing from an art to a science. In different historical periods, researches in applied catalysis were determined by national needs and these have made notable contributions to many fields, such as the optimal utilization of coal, petroleum and natural gas, advanced materials, and protection of environment as well as human health. Currently, China has begun contributing to important progress in catalysis and is moving towards becoming a regular contributor.

    Progress in development and application of solid-state NMR for solid acid catalysis
    ZHENG Anmin, HUANG Shing-Jong, WANG Qiang, ZHANG Hailu, DENG Feng, LIU Shang-Bin
    2013, 34 (3):  436-491.  DOI: 10.1016/S1872-2067(12)60528-2
    Abstract ( 1248 )   [Full Text(HTML)] () PDF (3144KB) ( 2034 )  

    Solid acid catalysts have been widely used in petrochemical industry and their catalytic activities are normally dictated by their acidities. Unlike conventional acidity characterization techniques such as titration, infrared, or temperature-programmed desorption, detailed acid features of solid acids, such as type, distribution, concentration, and strength of acid sites may be attained by advanced methods involving pertinent probe molecules and state-of-the-art solid-state nuclear magnetic resonance (SSNMR) techniques,i.e. double resonance and two-dimensional correlation spectroscopies. In addition, in situ solid-state NMR method is capable of probing the guest/host properties of the reactant at the active centers of the catalystsas well as the intermediate species formed during conversion. Itprovides direct experimental evidence for exploring the mechanism of catalytic reaction. In this report, the fundamental theory and the recent developments in solid-state NMR are reviewed with specific focus on relevant applications in structure and acidity characterization of solid acid catalysts and catalytic mechanisms.

    Advances in selective catalytic transformation of ployols to value-added chemicals
    MA Jiping, YU Weiqiang, WANG Min, JIA Xiuquan, LU Fang, XU Jie
    2013, 34 (3):  492-507.  DOI: 10.1016/S1872-2067(11)60501-9
    Abstract ( 1368 )   [Full Text(HTML)] () PDF (689KB) ( 1258 )  

    In this review, we discuss recent progress in the catalytic transformation of polyols to value-added chemicals, including 5-hydroxymethylfurfural (HMF), ethylene glycol (EG), 1,2-propylene glycol (1,2-PG) and 1,3-propylene glycol (1,3-PG). The challenges and solving of the synthesis of HMF from different carbohydrates, such as fructose, glucose and cellulose are analyzed. For the conversion of HMF, we focus on the catalytic oxidation of HMF to 2,5-diformylfuran and 2,5-furandicarboxylic acid and their applications to polymers. Advances in thecatalytic hydrogenolysis of polyols including cellulose, sugar alcohols and glycerol to diols such as EG, 1,2-PG and 1,3-PG are reviewed, and the reaction mechanismswere discussed. Research topics are suggested for future research from this review onthe selective catalytic transformation of ployols to value-added chemicals.

    Research progress in metal-free carbon-based catalysts
    SUN Xiaoyan, WANG Rui, SU Dangsheng
    2013, 34 (3):  508-523.  DOI: 10.1016/S1872-2067(11)60515-9
    Abstract ( 978 )   [Full Text(HTML)] () PDF (962KB) ( 1332 )  

    Metal-free carbon-based catalysts are one of the most active research directions in nanomaterials and catalysis. The advantages that nanocarbon catalysts have over metal catalysts include high efficiency, environmental compatibility, low energy consumption, and corrosion resistance. Nanocarbon can efficiently catalyze alkane conversion, chemical synthesis, energy catalysis and other heterogeneous catalytic processes. This review highlights recent progress in the development of metal-free carbon-based catalysts, including understanding their surface properties, catalytic performance and reaction mechanism and macroscopic architecture. The state-of-the-art and future challenges of metal-free heterogeneous catalysis are also discussed.

    Advances in photocatalysis in China
    ZHENG Yun, PAN Zhiming, WANG Xinchen
    2013, 34 (3):  524-535.  DOI: 10.1016/S1872-2067(12)60548-8
    Abstract ( 1501 )   [Full Text(HTML)] () PDF (1240KB) ( 2120 )  

    We briefly describe the developments in photocatalysis research in China in the three time periods of 1975?1985, 1985?1995, and 1995?2012, focusing on advances in photocatalytic materials and their modifications, applications, and reaction mechanisms. This short review also indicates some vital problems and future development trends in photocatalysis for water splitting, CO2 reduction, environmental purification, and selective organic photosynthesis.

    Articles
    Ordered mesoporous manganese oxide as catalyst for hydrogen peroxide oxidation of norfloxacin in water
    SUI Minghao, SHE Lei, SHENG Li, WEI Jinjie, ZHANG Lingdian, HUANG Shuhang
    2013, 34 (3):  536-541.  DOI: 10.1016/S1872-2067(11)60492-0
    Abstract ( 2511 )   [Full Text(HTML)] () PDF (756KB) ( 931 )  

    Ordered mesoporous manganese oxide (om-MnOx) was prepared and used in oxidation by hydrogen peroxide of norfloxacin (NFX). The om-MnOx was prepared using a hard template method. The catalytic activity of om-MnOx was investigated by evaluating the changes in degradation efficiency and antibacterial activity of NFX. om-MnOx exhibited significant catalytic activity for the degradation of NFX in water by hydrogen peroxide. Lower pH conditions favored the catalytic activity of om-MnOx/hydrogen peroxide. The presence of om-MnOx achieved a greater reduction in the antibacterial ability of NFX than that was obtained with hydrogen peroxide alone. The inhibiting effect of t-butanol indicated that om-MnOx enhanced the generation of hydroxyl radicals. Byproducts from NFX were detected during the om-MnOx-catalyzed hydrogen peroxide process, and possible reaction pathways were proposed.

    Synthesis and pervaporation performance of highly reproducible zeolite T membranes from clear solutions
    ZHANG Xiaoliang, SONG Xin, QIU Lingfang, DING Minzheng, HU Na, ZHOU Rongfei,CHEN Xiangshu
    2013, 34 (3):  542-547.  DOI: 10.1016/S1872-2067(11)60478-6
    Abstract ( 1040 )   [Full Text(HTML)] () PDF (948KB) ( 925 )  

    Zeolite T membranes with very good permeation performance were successfully synthesized on porous mullite supports by the secondary growth method with homemade microsized seeds from clear solutions. The influence of synthesis parameters such as the molar ratios of SiO2/Al2O3 and H2O/SiO2, alkalinity, synthesis temperature, and crystallization time on membrane growth and permeation performance was investigated systematically. It is found that these parameters strongly affect the zeolite T growth and pervaporation performance of the membranes. Under the optimized synthesis conditions of 1SiO2:0.015Al2O3:0.41(Na2O+K2O):30H2O, the crystallization time was shortened to 6 h at 423 K and a continuous and dense T-type zeolite layer as thin as 5 μm formed on the surface of the support. It significantly improved the membrane density and permselective properties. A permeation flux and separation factor of 4.20 kg/(m2·h) and 7800, respectively, were obtained with the as-synthesized membrane for 10 wt% water-90 wt% #em/em#-propanol mixtures at 348 K. It also exhibited a very good pervaporation performance for water/ethanol mixtures separation. This high quality zeolite T membrane could be reproducibly prepared.

    Solvent-free thermal decomposition of methylenediphenyl di(phenylcarbamate) catalyzed by nano-Cu2O
    WANG Qingyin, KANG Wukui, ZHANG Yi, YANG Xiangui, YAO Jie, CHEN Tong, WANG Gongying
    2013, 34 (3):  548-558.  DOI: 10.1016/S1872-2067(11)60494-4
    Abstract ( 739 )   [Full Text(HTML)] () PDF (963KB) ( 674 )  

    Methylene di(phenylisocyanate) (MDI) was prepared by thermal decomposition of methylenediphenyl di(phenylcarbamate) (MDPC) under solvent-free conditions with a nano-Cu2O catalyst. The preparation of nano-Cu2O was investigated in detail to obtain the optimal catalytic performance. The thermal decomposition reaction conditions, including reaction temperature, reaction pressure, and reaction time, were studied in the presence of nano-Cu2O. The results show that Cu2O prepared using a hydrolysis method and then calcined at 300℃ in Ar atmosphere for 2 h exhibited the optimal catalytic activity. The optimal reaction conditions were as follows: mass ratio of catalyst to MDPC 6.0 × 10-4, reaction temperature 220℃, reaction time 12 min, and reaction pressure 0.6 kPa. Under these conditions, the conversion of MDPC reached 99.8% and 86.2% MDI selectivity was achieved.

    Knoevenagel condensation reaction over acid-base bifunctional MgO/HMCM-22 catalysts
    ZHANG Wenfei, LIANG Jinhua, LIU Yanqiu, SUN Shoufei, REN Xiaoqian, JIANG Min
    2013, 34 (3):  559-566.  DOI: 10.1016/S1872-2067(11)60493-2
    Abstract ( 916 )   [Full Text(HTML)] () PDF (795KB) ( 1083 )  

    MgO/HMCM-22 catalysts were prepared by impregnation and characterized by X-ray diffraction, N2 physical adsorption-desorption, scanning electron microscopy, Fourier-transform infrared spectroscopy, temperature-programmed desorption of NH3, and temperature-programmed desorption of CO2. The results show that there were no significant structural changes in theMCM-22 zeolite after modification. Increasing the MgO loading increased the strength and content of the base, whereas the strength of the strong acid decreased significantly and the amount of weak acidic sites increased slightly. Knoevenagel condensation reactions were carried out as the probe reactions over the catalysts. Both acidic sites and basic sites significantly promoted the reaction. The conversion of benzaldehyde reached 92.6% under the optimal conditions. The catalytic performance of MgO/HMCM-22 and MgO/NaMCM-22 was better than that of HMCM-22 and MgO. The MgO/HMCM-22 catalysts gave good catalytic performance for Knoevenagel condensation reactions and exhibited obvious acid-base synergetic effects.

    Soot combustion performance and H2-TPR studyonceria-basedmixed oxides
    SHENG Yeqin, ZHOU Ying, LU Hanfeng, ZHANG Zekai, CHEN Yinfei
    2013, 34 (3):  567-577.  DOI: 10.1016/S1872-2067(11)60495-6
    Abstract ( 944 )   [Full Text(HTML)] () PDF (692KB) ( 1234 )  

    Ceria (CeO2) catalysts doped with different metal ions were prepared by sol-gel or impregnation methods, and their catalytic activityfor soot combustion was evaluated by thermogravimetry. Temperature-programmed reduction was used to investigate the influence of their redox properties on soot combustion performance. The results indicate that the oxidation temperature of soot can be significantly reduced using catalysts containing transition metals, which provide increased surface and lattice oxygen compared with undoped CeO2. The ability of each catalyst to deliver active oxygen at low temperature (200-400℃) plays an important role in determining catalytic performance. However, incorporation of structure promoter, alkali metals, and alkaline earth metals increase the delivery of active oxygen only at moderate temperature (above 400℃), which accelerate the combustion rate of soot.

    Nanoparticulate palladium catalyst stabilized by supported on feather keratin for Suzuki coupling reaction
    MA Hengchang, BAO Zhikang, HAN Guobin, YANG Ningning, XU Yufei, YANG Zengming, CAO Wei, MA Yuan
    2013, 34 (3):  578-584.  DOI: 10.1016/S1872-2067(11)60472-5
    Abstract ( 787 )   [Full Text(HTML)] () PDF (558KB) ( 1113 )  

    Palladium nanoparticlessupported in afeather keratin matrix were efficient catalyst for the coupling reactions of aryl bromides with arylboronic acid in aqueous medium under mild reaction conditions. The biopolymer-based catalyst demonstrated excellent activity for substrates with a wide range of functional groups. The product biaryls were precipitated from the reaction mixture with good to excellent yields and purities. The catalyst was recovered from the reaction solution easily by simple filtration, and can be reused at least seven times.

    La-doped titaniananocrystals with superior photocatalytic activity prepared by hydrothermal method
    JIAO Yanchao, ZHU Mingfeng, CHEN Feng, ZHANG Jinlong
    2013, 34 (3):  585-592.  DOI: 10.1016/S1872-2067(11)60483-X
    Abstract ( 784 )   [Full Text(HTML)] () PDF (1072KB) ( 965 )  

    Potassium titanate (KTO) nanobars were synthesized by a hydrothermal method and used as a precursor to synthesize TiO2 nanocrystals. La doping of the TiO2 nanocrystals was achieved by introducing La3+ into the hydrothermal media. The hydrothermal transition of KTO to TiO2 was investigated under various conditions,finding that the pH of the hydrothermal media, the temperature, and the pre-treating procedure play important roles in the phase transition. X-ray diffraction and transmission electron microscopywere used to characterize the crystal phase and morphology of the samples and the transition process of the hydrothermal reaction. The content of La3+ in the samples was measured by inductively coupled plasma atomic emission spectroscopy. The photocatalytic activity of the La-doped TiO2(LaT) was measured under UV light with the degradation of methyl orange (MO, 10 mg/L).The results showed that the photocatalytic activity of TiO2 was enhanced remarkably by La-doping. LaT hydrothermally prepared with 0.15 mol/L La3+at under 180℃ showedthe optimal reaction constant of 0.11 min-1 for the degradation of MO, about 9.20 and 3.69 times than those of bare TiO2 and P25, respectively.

    Study of crystallization process of SAPO-11 molecular sieve
    LI Bing, TIAN Peng, QI Yue, ZHANG Lin, XU Shutao, SU Xiong, FAN Dong, LIU Zhongmin
    2013, 34 (3):  593-603.  DOI: 10.1016/S1872-2067(12)60542-7
    Abstract ( 915 )   [Full Text(HTML)] () PDF (1208KB) ( 914 )  

    The crystallization process of SAPO-11 was studied using a combination of X-ray diffraction, scanning electron microscopy, X-ray fluorescence, nuclear magnetic resonance, and X-ray photoelectron spectroscopy. In the initial stage of crystallization, SAPO-11 was formed along with an unknown crystalline material composed of Si-P-Al. As crystallization evolved, the crystalline material dissolved. The SAPO-11 formation rate increased greatly, which is characteristic of fast crystallization. After 2.33 h, the relative crystallinity of SAPO-11 reached ~100% and remained at a high level until crystallization was complete. Si was incorporated into the SAPO-11 framework from the initial stage of crystallization. The Si content of the solid samples increased with crystallization time. Most of the Si atoms existed as Si islands in the SAPO-11 framework, resulting in the presence of multiple coordination environments, i.e., Si(nAl, (4-n)Si), n=0-4. X-ray photoelectron spectroscopy analysis revealed Si enrichment on the external surfaces of the SAPO-11 crystals. Based on the experimental results, the distribution of Si in the crystals is not uniform, showing an increasing trend from the core to the surface.

    Fixed-bed process of liquid-phase ammoximation of cyclohexanone over titanosilicates
    ZHUO Zuoxi, LIN Longfei, DENG Xiujuan, WANG Yuning, LIU Yueming
    2013, 34 (3):  604-611.  DOI: 10.3724/SP.J.1088.2013.20939
    Abstract ( 886 )   [Full Text(HTML)] () PDF (585KB) ( 743 )  

    Liquid-phase ammoximation of cyclohexanone to the corresponding oxime was conducted in a fixed-bed reactor over titanium silicalite (TS-1), which was proved to be a feasible and universal process. The primary rules of ammoximation were explored in the fixed-bed reactor system.The initial results indicated that the utilization of H2O2 was enhanced obviously through this mode, which is attributed to successful hydroxylamine generation and smooth contact with ketones. Further investigations of H2O2 reaction behavior showed that the proper weight hourly space velocity of H2O2 and the concentrations of ammonia and ketone both play a key role in highly efficient utilization of H2O2. The cyclohexanone and H2O2 conversion, cyclohexanone-oxime selectivity, and H2O2 efficiency reached 18.7%, 94.7%, 99.5%, and 98.7%, respectively, under the optimum reaction conditions of temperature of 333 K, ammonia concentration higher than 2%, cyclohexanone/H2O2 molar ratio of 5, and WHSV (H2O2)of 0.083h-1 with 85% t-BuOH as solvent.

    Vapor-phase silylation of MCM-22 zeolite with various SiO2/Al2O3 molar ratios
    GAO Ningning, XIE Sujuan, LIU Shenglin, LIU Kefeng, LI Xiujie, XU Longya
    2013, 34 (3):  612-619.  DOI: 10.3724/SP.J.1088.2013.20932
    Abstract ( 1099 )   [Full Text(HTML)] () PDF (514KB) ( 926 )  

    MCM-22 precursor with various SiO2/Al2O3 molarratios was treated by vapor-phase silylation. MCM-22 zeolite and its products of vapor-phase silylation were characterized by X-ray diffraction, solid state nuclear magnetic resonance, N2 adsorption-desorption, and toluene adsorption techniques. The results showed that Si(OH)2 pillaring structure was formed in the interlayer of MCM-22 with SiO2/Al2O3 molarratios of 50-100 without extraction of framework aluminum through vapor-phase silylation, resulting in the expansion of interlayer distance and the increase of micropore volume. The N2 adsorption-desorption isotherms of MCM-22 zeolite before and after silylation were analyzed by the density functional theory, and the specific surface area and pore volume of 10 member ring (10 MR) micropores and those of the supercage system were successfully obtained. As a result of vapor-phase silylation, the specific surface area and pore volume of the supercage system increased, while those of 10 MR micropores decreased. The equilibrium adsorption amount of toluene over MCM-22 zeolite with various SiO2/Al2O3 molar ratios was enhanced after vapor-phase silylation.