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    Chinese Journal of Catalysis
    2008, Vol. 29, No. 3
    Online: 25 March 2008

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    Articles
    Density Functional Theory Study of Nitridation of ZSM-5 Zeolite
    WU Guangjun;YANG Yali;WANG Guichang;ZHANG Fuxiang;GUAN Naijia
    2008, 29 (3):  203-205. 
    Abstract ( 2048 )   [Full Text(HTML)] () PDF (214KB) ( 841 )  
    Density functional theory was used to predict the preferred oxygen site substituted by a nitrogen atom in the nitridation of the ZSM-5 zeolite. Calculations were performed on an 8T cluster of ZSM-5 by the Gaussian 98 program at the B3LYP/6-311G(d,p)level. The calculated results showed that the most preferred oxygen sites substituted by nitrogen are O11and O21sites. Because the O11atom located at the Bronsted acid site is one of the most preferred sites for nitrogen substitution, nitridation can decrease the strength of Bronsted acid on the surface of the ZSM-5 zeolite.
    Catalytic Properties of Supported Pd/SBA-15 Catalyst for Selective Hydrogenation of Alkadienes
    LIU Jingyu;LU Haimeng;LING Zhengguo;SHI Lihua;XU Bolian;FAN Yining*
    2008, 29 (3):  206-208. 
    Abstract ( 2247 )   [Full Text(HTML)] () PDF (175KB) ( 812 )  
    The structure and catalytic properties of the supported Pd/SBA-15 catalyst for selective hydrogenation of C10-C13alkadienes have been studied using microreactor tests combined with temperature-programmed reduction, CO chemisorption, BET surface area measurements, and high-resolution transmission electron microscopy. The Pd/SBA-15 catalyst exhibits higher catalytic activity and selectivity than the commercial Pd/γ-Al2O3 catalyst for the reaction. The catalytic properties of the Pd/SBA-15 catalyst are closely related to Pd loading. With increasing Pd loading, Pd dispersion and the selectivity for alkenes decrease remarkably.
    Suzuki Reactions of Aryl Bromides Catalyzed by Hydroxyapatite-Supported Manganese
    QIAO Jiangbin;ZHU Wenfang;ZHUO Guanglan*;ZHOU Hao;JIANG Xuanzhen
    2008, 29 (3):  209-211. 
    Abstract ( 2233 )   [Full Text(HTML)] () PDF (149KB) ( 786 )  
    Suzuki cross-coupling reactions between aryl bromides and phenylboronic acids were studied over a hydroxyapatite-supported Mn catalyst (MnHAP) for the first time. An increased yield was obtained over the fluoride ion-exchanged hydroxyapatite-supported Mn catalyst (MnFAP). Under optimized conditions, the yield was about 70%. The effect of solvent compositions and different substituents were studied over the MnFAP catalyst. The DMF-H2O mixture with a DMF/H2O volume ratio of 1/3 was the best solvent. Moderate yields (18%-46%) were obtained for all tested aryl bromides and phenylboronic acids substituted by different groups.
    Glycerol Dehydration to Acrolein over Activated Carbon-Supported Silicotungstic Acids
    NING Lili;DING Yunjie;*;CHEN Weimiao;GONG Leifeng;LIN Ronghe;L Yuan;XIN Qin
    2008, 29 (3):  212-214. 
    Abstract ( 2247 )   [Full Text(HTML)] () PDF (181KB) ( 1228 )  
    Activated carbon(AC)-supported silicotungstic acid (H4[SiW12O40]·nH2O, HSiW) catalysts were employed to produce acrolein from glycerol dehydration. The results indicated that catalysts with 10% HSiW loading exhibited the highest activity and selectivity. The space time yield of acrolein reached 68.5 mmol/(g\5h), which is the best result ever reported in the literature. The properties of the catalysts were closely related to the HSiW dispersion and the relative quantities of strong acid sites.
    Influencing Factors in Catalytically Bactericidal Process of Ag-Ce/AlPO4 Catalyst in Water
    CHANG Qingyun;HE Hong*;QU Jiuhui;ZHAO Jincai
    2008, 29 (3):  215-220. 
    Abstract ( 2026 )   [Full Text(HTML)] () PDF (369KB) ( 779 )  
    Influencing factors in the catalytically bactericidal process over a Ag-Ce/AlPO4 catalyst against E.coli in water were investigated. The bactericidal effect of the catalyst decreased with the increase in initial bacterial concentration. A 100% inactivation of E.coli using Ag-Ce/AlPO4 at 25 ℃ was achieved in 120 min when the initial bacterial concentration was 5×105 CFU/ml. Therefore, this catalytic method is sufficient for disinfection of drinking water. Once the initial bacterial concentration was fixed, the bactericidal activity increased with increasing temperature from 25 to 40 ℃. The pH value also played an important role in the bactericidal process. The Ag-Ce/AlPO4 catalyst exhibited high bactericidal activity under weak alkaline conditions, while almost no bactericidal effect was observed at acidic pH. Electron spin resonance was used to detect the reactive oxygen species involved in the bactericidal process at different pH values. Hydroxyl radical·OHwith strong oxidative ability proved to be formed under weak alkaline conditions and was not observed at acidic pH. These results give evidence of our proposed catalytically bactericidal mechanism, in which·OHis the key intermediate responsible for the efficient inactivation of E.coli by Ag-Ce/AlPO4 in water at room temperature.
    Preparation of Cu/La/CeO2-Al2O3 and Its Catalytic Activity for Selective Reduction of NO with Propylene
    GUO Xikun*;LIN Shudong
    2008, 29 (3):  221-227. 
    Abstract ( 1981 )   [Full Text(HTML)] () PDF (652KB) ( 881 )  
    The CeO2-Al2O3 composite support was prepared by the coprecipitation method with a mixed Al-(NO3)3-Ce(NO3)3 aqueous solution dropping into a mixed NH4HCO3-NH3·H2O aqueous solution. The Cu/La/CeO2-Al2O3 catalyst was prepared by impregnation of CeO2-Al2O3 with promoter La and active component Cu aqueous solution. The catalytic activity of the catalyst for the selective reduction of NO with propylene in excess oxygen was investigated. The relationship between the catalytic activity and the structure of the catalyst was also explored by means of scanning electron microscopy, atomic force microscopy,X-raydiffraction, surface area measurement, infrared spectroscopy, thermogravimetry,X-rayphotoelectron spectroscopy, and temperature-programmed reduction. The CeO2-Al2O3 could remarkably enlarge the catalyst surface area and pore size, increase the amount of Lewis acidity, and enhance the reducibility. The La promoter could further enlarge the catalyst surface area and pore size and increase the amount of Brnsted acidity and the thermal stability. Consequently, the catalyst exhibited higher activity for the selective reduction of NO with propylene in excess oxygen. The NO conversion decreased slightly even in the presence of water vapor.
    Partial Oxidation of Methane to Syngas over Pt/MgO Catalyst
    YANG Min;*;Helmut PAPP
    2008, 29 (3):  228-232. 
    Abstract ( 2147 )   [Full Text(HTML)] () PDF (299KB) ( 800 )  
    Pt/MgO catalyst samples with different Pt loading were prepared by wet impregnation.X-raydiffraction,X-rayphotoelectron spectroscopy, transmission electron microcopy, and temperature-programmed surface reaction were used to characterize the catalyst samples. Partial oxidation of methane (POM) to syngas was performed in a fixed-bed microreactor. The results indicated that the Pt/MgO catalyst exhibited high activity and selectivity. The conversion of methane and selectivity for CO and H2 remained constant up to 120 h. The dispersed Pt existed in a metallic state, which was responsible for the high activity in the POM reaction. Both the state and the dispersion of active Pt were very stable, together with the high ability to resist carbon deposition, and therefore the catalyst showed high stability in the POM reaction.
    Mechanism of Light-Controlled Asymmetric Reduction of Acetophenone by Photosynthetic Bacteria
    WANG Mengliang*;HU Rui;GUO Xuelin;YAN Fukun;LIU Diansheng
    2008, 29 (3):  233-237. 
    Abstract ( 2316 )   [Full Text(HTML)] () PDF (246KB) ( 964 )  
    A new kind of asymmetric hydrogenation reaction catalyzed by Rhodobacter sphaeroides and the reaction mechanism have been studied. The advantages are that coenzyme (NADPH) can be regenerated in situ by the photosynthetic electron-transfer reactions of photosynthetic bacteria relying on light energy, and ketone compounds can be chiraly hydrogenated. Acetophenone was selected as the model substrate, and the whole cell catalytic system, the asymmetric reduction system of redox enzymes and the chromatophore coupled with redox enzymes system were built through preparation of chromatophore and isolation and purification of endocellular (S)-redox enzymes and (R)-redox enzymes of photosynthetic bacteria Rhodobacter sphaeroides. This result indicates that these cells have the capacity of capturing light energy to generate NADPH through photosynthetic electron-transfer reactions and the relative enzymatic activities. (S)-redox enzyme and (R)-redox enzyme were largely influenced by the amount of light in the environment. Effect of the electron donors and hydrogen donors on chemical yield in the reaction system was determined. A novel method for stereochemical control of the asymmetric reduction by photosynthetic bacteria was also reported. Enantioselectivity in asymmetric reduction of acetophenone was improved by illumination with fluorescent light. As a result, the yield of asymmetric reduction reaction was largely improved through promoting coenzyme NADPH regeneration.
    Hydroformylation of Monoterpenes in Aqueous/Organic Biphasic System
    LI Cheng;YUAN Maolin;FU Haiyan;ZHANG Ruimin;CHEN Hua*;LI Xianjun
    2008, 29 (3):  238-242. 
    Abstract ( 2027 )   [Full Text(HTML)] () PDF (238KB) ( 830 )  
    The catalytic properties of water-soluble rhodium complex RhCl(CO)(TPPTS)2[TPPTS: P(m-C6H4SO3Na)3] for monoterpenes hydroformylation in an aqueous/organic biphasic system have been investigated. The results showed that the activity for monoterpenes hydroformylation was accelerated by the addition of ionic surfactant. Under optimum reaction conditions, the conversion of myrcene, camphene, and limonene reached 92%, 72%, and 86%, respectively. Furthermore, the rhodium catalyst immobilized in the water phase could be easily separated from the organic products and reused several times without significant loss of activity and selectivity. The rhodium leaching into the organic phase was lower than 0.04% in each cycle.
    Breakage of the Peroxy Bond in Dihydroartemisinin Induced by Electrocatalysis of Copper(Ⅱ)
    HUANG Lianxi;HE Yanlin;YANG Peihui*
    2008, 29 (3):  243-246. 
    Abstract ( 2082 )   [Full Text(HTML)] () PDF (243KB) ( 820 )  
    The peroxy bond in dihydroartemisinin (DHA) is the most essential part for its anti-malarial and anti-tumor effect. The cleavage of the peroxy bond can affect its pharmacological activity. An electrochemical method was used to investigate the breakage of the peroxy bond in dihydroartemisinin induced by electrocatalysis of EDTA-Cu(Ⅱ). The effect of acidity and scan rate on this catalytic system was studied. The mechanism of the reaction at the electrode surface was also discussed. There was an irreversible reduction peak at-0.681V (vs SCE) for DHA in aB-Rbuffer solution containing 20% ethanol (pH=7.2). The reduction potential shifted about 94 mV toward the positive direction, and the reduction current increased in the solution containing 5.0×10-4mol/L DHA and 5.0×10-6mol/L EDTA-Cu(Ⅱ). Compared with EDTA-Fe(Ⅲ) and hemin, EDTA-Cu(Ⅱ) showed an obvious electrocatalytic effect to DHA in this system. These results indicated that EDTA-Cu(Ⅱ) can induce the cleavage of the peroxy bond of DHA and affect the pharmacological activity of DHA.
    Preparation of Immobilized MnP-PGMA/SiO2 Catalyst and Its Catalytic Activity for Ethylbenzene Oxidation
    ZHANG Yan;GAO Baojiao*;WANG Ruixin
    2008, 29 (3):  247-252. 
    Abstract ( 2197 )   [Full Text(HTML)] () PDF (421KB) ( 883 )  
    Ploy(glycidyl methacrylate) (PGMA) was grafted on the surface of silica gel particles in a solution polymerization system, and PGMA/SiO2 was prepared. Subsequently, meso-tetra(4-hydroxylphenyl)porphyrin (THPP) was bound on PGMA/SiO2 through the ring-opening reaction between the epoxy groups of the grafted PGMA and the hydroxyl groups of THPP, resulting in the HPP-PGMA/SiO2. Further, the coordination reaction between HPP-PGMA/SiO2 and MnCl2 was performed, and the immobilized MnP (manganoporphyrin)-PGMA/SiO2 was obtained. The MnP-PGMA/SiO2 catalyst was used in the oxidation of ethylbenzene with molecular oxygen as the oxidant, and the transform of ethylbenzene into acetophenone was realized. The effects of various factors, such as the catalyst amount and MnP-immobilizing density, on the supported MnP-PGMA/SiO2 catalyst were examined. The results showed that the supported MnP-PGMA/SiO2 catalyst can effectively activate molecular oxygen and obviously catalyze the oxidation of ethylbenzene to acetophenone. MnP-PGMA/SiO2 exhibited high catalytic activity and selectivity, and the yield of acetophenone reached 18% under the conditions ofp(O2)=0.1 MPa, T=95 ℃, and t=12 h, but the content of α-methyl benzoic alcohol was very small. As a biosimulation catalyst, MnP in the supported catalyst had an optimum amount for the reaction, and the excess amount would inhibit the catalyst activity. The supported MnP-PGMA/SiO2 catalyst with a smaller MnP-immobilizing density had higher catalytic activity, and the catalytic activity increased slowly when the catalyst was reused.
    Preparation and Catalytic Ozonation Activity of SnO2
    ZENG Yufeng;LIU Zili;*;LIU Hongwei
    2008, 29 (3):  253-258. 
    Abstract ( 2117 )   [Full Text(HTML)] () PDF (358KB) ( 835 )  
    Heterogeneous catalytic ozonation technology is a new ozone oxidation method and can degrade organic compounds that cannot be oxidized or degraded by ozone alone at room temperature and normal pressure. A SnO2 catalyst was prepared by the precipitation method and used in decolorization of molasses fermentation wastewater through ozonation. Effects of precipitants and calcination temperature on the catalytic ozonation activity of SnO2 were studied byX-raydiffraction, infrared spectroscopy (IR), and thermal analysis (TG-DSC). The results showed that the SnO2 catalyst exhibited considerably high catalytic activity for the catalytic ozonation decolorization of molasses fermentation wastewater. The decolorization rate of the wastewater was enhanced from 43.04% (using ozone oxidation alone) to 60.24%. The activity of the SnO2 catalyst was significantly affected by the precipitants. SnO2 prepared using ammonia as the precipitant showed higher degree of dehydroxylation and higher catalytic activity than those prepared using NaOH and Na2CO3 precipitants. The optimal calcination temperature of SnO2 was 723 K. The IR spectra of adsorbed pyridine showed that there were Lewis acid sites on the surface of the SnO2 catalyst. The IR spectra of O3 adsorbed on SnO2 showed that the terminal O atom of O3 was bonded to the surface hydroxyl group or a Lewis acid site to form a more active oxygen species that can oxidize and degrade the wastewater.
    Dispersion of Pt Catalysts Supported on Activated Carbon and Their Catalytic Performance in Methylcyclohexane Dehydrogenation
    LI Xiaoyun;MA Ding;BAO Xinhe*
    2008, 29 (3):  259-263. 
    Abstract ( 2226 )   [Full Text(HTML)] () PDF (380KB) ( 1002 )  
    Activated carbon-supported Pt catalysts were prepared by the conventional wetness impregnation method, and their catalytic activity for methylcyclohexane dehydrogenation was tested. The impact of different treatments (nitric acid oxidation and H2 heating treatment) of carbon supports on the reaction performance was addressed. The results of nitrogen adsorption and temperature-programmed desorption show that the carbon supports have almost identical porous texture but different types and amounts of surface oxygen groups. This led to different dispersion of Pt particles and thus different activity and stability of the catalysts.
    Preparation and Characterization of CeO2-TiO2 Composite Oxide and Its Catalytic Performance for CO Oxidation
    LIANG Feixue;ZHU Huaqing;QIN Zhangfeng;WANG Hui;WANG Guofu;WANG Jianguo*
    2008, 29 (3):  264-268. 
    Abstract ( 2348 )   [Full Text(HTML)] () PDF (406KB) ( 889 )  
    A series of CeO2-TiO2 composite oxide samples with differentn(Ce)/n(Ti)were prepared by the sol-gel method. The phase structure, morphology, surface area, and redox properties of the composite oxide samples were investigated through N2 adsorption,X-raydiffraction, transmission electron microscopy, and temperature-programmed reduction, and their catalytic performance for CO oxidation was measured. The amorphous CeO2-TiO2 composite oxide was formed gradually whenn(Ce)/n(Ti)was higher than 0.10. Withn(Ce)/n(Ti)=0.10-0.30, the amorphous CeO2-TiO2 solid solution with high surface area was formed and exhibited the characteristics of neither CeO2 nor TiO2. Although CeO2-TiO2 had lower catalytic activity than either TiO2 or CeO2 for CO oxidation, the Pd/CeO2-TiO2 catalyst presented excellent performance for CO oxidation.
    Preparation and Characterization of La-Doped TiO2 Photocatalysts
    ZHAO Qinghua;QUAN Xuejun*;TAN Huaiqin;SANG Xuemei
    2008, 29 (3):  269-274. 
    Abstract ( 2317 )   [Full Text(HTML)] () PDF (382KB) ( 885 )  
    Lanthanum-doped TiO2, photocatalysts La3+-TiO2, were prepared by coprecipitation and sol-gel methods. Rhodamine B was used as the reactant to evaluate the photocatalytic activity of the catalyst samples. The results showed that the La3+-TiO2 catalyst prepared by coprecipitation exhibited obviously higher photocatalytic activity. The optimum preparation conditions of coprecipitation were lanthanum ions doped of 1%, calcination temperature of 800 ℃, and calcination time of2 h. The best catalyst samples were characterized byX-raydiffraction, N2 adsorption-desorption measurement, scanning electron microscopy, and electron probe microanalyses. The two photocatalysts prepared by coprecipitation and sol-gel both had mixed crystal structure of anatase and rutile, and the anatase contents were 80% and 70%, respectively. The higher photocatalytic activity of the La3+-TiO2 catalyst prepared by coprecipitation was mainly attributed to its more regular structure of anatase, larger crystal size, and hierarchical macro/mesoporous structure.
    Preparation and Characterization of Cu/SiO2 Catalyst and Its Catalytic Activity for Hydrogenation of Diethyl Oxalate to Ethylene Glycol
    WANG Baowei*;ZHANG Xu;XU Qian;XU Genhui
    2008, 29 (3):  275-280. 
    Abstract ( 2443 )   [Full Text(HTML)] () PDF (462KB) ( 974 )  
    The Cu/SiO2 catalyst for gas-phase hydrogenation of diethyl oxalate (DEO) to ethylene glycol (EG) was prepared through the homogeneous deposition-precipitation method. The catalyst was evaluated at different reaction temperatures, pressures, and molar ratios of H2/DEO to optimize the catalyst preparation method and reaction conditions. Characterizations were carried out using various methods such as TPR, XRD, BET, HRTEM, and SEM to study the thermal stability of the catalyst, the catalyst forming, and the distribution of the active site. From the results of these experiments, the best preparation method, Cu loading, reduction temperature, and reaction conditions were obtained. Under the optimized conditions, the DEO conversion and EG yield reached 94.8% and 76.0%, respectively.
    Photocatalytic Degradation of 2,4-Dichlorophenoxyacetic Acid, 4-Chlorophenol, and Oxalic Acid with Simultaneous Hydrogen Production under weak UV Light Illumination
    ZHANG Xianghua;LIU Hong*;LI Wenzhao;XU Hengyong
    2008, 29 (3):  281-286. 
    Abstract ( 2231 )   [Full Text(HTML)] () PDF (344KB) ( 901 )  
    Photocatalytic degradation of three organic pollutants,2,4-dichlorophenoxyacetic acid (2,4-D), 4-chlorophenol (4-CP), and oxalic acid (OA), with simultaneous hydrogen evolution was investigated with weak UV light illumination. The photocatalytic reactions were carried out in 160 ml solutions of the pollutants (1.0 mmol/L) using 1.0%Pt/TiO2 (1.0 g/L) as the catalyst. After2 hillumination, 38.43, 0.05, and 111.35 μmol of hydrogen and 73.80, 4.49, and 175.99 μmol of carbon dioxide were produced. Simultaneously, 83.83% of2,4-D, 36.19% of 4-CP, and 98.81% of OA were removed. These results showed that OA and2,4-D were good electron donors for the photocatalytic hydrogen evolution. On the other hand, under the illumination of a strong UV light source with light intensity 150 times that the weak UV light, more than 90% of2,4-D and 4-CP were removed within 5 min. The amounts of hydrogen produced were 113.02, 38.98, and 191.30 μmol for2,4-D, 4-CP, and OA solutions, respectively, and 195.60, 31.41, and 306.96 μmol of carbon dioxide was also produced. Therefore an appropriate combination of the processes of weak UV light and strong UV light can perform ultimate mineralization of organic pollutants with high hydrogen production and collective carbon dioxide of easy disposal. In this way the pollutants can be removed, and the light energy and chemical energy of the organic pollutants can be transferred to chemical energy in the form of hydrogen.
    TPD Studies on Ni/γ-Al2O3Catalysts Reduced by Atmosphere Plasma
    LI Daihong;XI Min;TAO Xumei;SHI Xinyu;DAI Xiaoyan;YIN Yongxiang*
    2008, 29 (3):  287-291. 
    Abstract ( 2221 )   [Full Text(HTML)] () PDF (305KB) ( 895 )  
    Ni/γ-Al2O3catalysts prepared by three different ways, general reduction (GR), plasma reduction after calcination (PR), and plasma direct reduction without calcination (PDR), were investigated by temperature-programmed desorption (TPD) with H2 and CO2,X-raydiffraction, and N2 adsorption. The results showed that H2 was adsorbed mainly on the Ni active sites, whereas CO2 was adsorbed mainly on the strong alkaline sites of the support. Compared with that on the GR catalyst, H2 and CO2 adsorbed on the PR and PDR catalysts increased a lot, and the desorption temperature of H2 decreased by 55 and 69 ℃, respectively. An estimation based on assumption of H2 showed that the dispersions of GR, PR, and PDR catalysts were 26%, 32%, and 58%, respectively. The catalysts reduced by plasma had better dispersion, more alkaline sites, and lower H2 desorption temperature. Plasma reduction that was performed at a low temperature for a short time could preserve the structure of the support and improve the dispersion of the active sites, which were responsible for the good performance of these catalysts.
    Synthesis of Ni-Mo2N/SiO2 Nanocomposite Catalyst and Its Catalytic Activity for Tetralin Hydrogenation
    WANG Zhiqiang;ZHANG Minghui*;LI Wei;TAO Keyi
    2008, 29 (3):  292-296. 
    Abstract ( 2472 )   [Full Text(HTML)] () PDF (329KB) ( 898 )  
    Mo2N/SiO2 was prepared by a temperature-programmed nitridation method. The Mo2N/SiO2 was impregnated with Ni salt solution and then was directly reduced by H2 to prepare a new Ni-Mo2N/SiO2 nanocomposite catalyst. The catalyst was characterized byX-raydiffraction, transmission electron microscopy, H2 chemisorption, ICP-AES, and N2 adsorption-desorption techniques and evaluated by tetralin hydrogenation. The results showed that the new nanocomposite catalyst had higher tetralin conversion than the conventional Ni2Mo3N/SiO2 catalyst or Ni/SiO2 catalyst. The correlation between the active components (Ni and Mo2N) was also studied by the separated-bed method. The synergistic effect of Ni and Mo2N in the Ni-Mo2N/SiO2 catalyst promoted its catalytic activity for tetralin hydrogenation, where Mo2N provided more adsorption sites for aromatics. The possible hydrogenation process of tetralin over the Ni-Mo2N/SiO2 catalyst was proposed.
    Electro-oxidation of Formic Acid on Nanostructured Pt-on-Au (Pt^Au) Electrocatalysts
    WANG Yuanhao;ZHAO Dan;XU Boqing*
    2008, 29 (3):  297-302. 
    Abstract ( 2757 )   [Full Text(HTML)] () PDF (462KB) ( 1098 )  
    Nanostructured Pt-on-Au electrocatalysts (coded as Ptm^Au, m shows the atomic Pt/Au ratio) were prepared by deposition of Pt on colloidal Au particles ((10.0±1.2) nm) and then employed for electro-oxidation of formic acid at concentrations of0.2-3.2mol/L by cyclic voltammetry. The electro-oxidation behavior of formic acid was greatly influenced by the morphology and dispersion of Pt deposits on the Au nanoparticles. The electro-oxidation of formic acid occurred mainly in the high potential range(0.6-1.0V vs SCE) when the Pt existed as a shell fully covering the Au particles in the Ptm^Au/C catalysts (m>0.2), which is similar to the electro-catalysis of a Pt/C catalyst. When the state of Pt deposits was varied from a mono-atomic Pt shell (m≈0.2) to very small flecks of Pt clusters or two-dimensional rafts (m<0.2) on the same Au particles, dramatic enhancement in the oxidation current of formic acid was observed in the low potential range(-0.2-0.6V vs SCE). The mass-specific activity of Pt at peak potential (0.38 V) in a Pt0.05^Au/C catalyst with a 100% Pt dispersion (EAS= 236 m2/g-Pt) was as high as about 40 times that of traditional Pt/C catalysts with about 30% Pt dispersion (EAS=74 m2/g-Pt). These results demonstrate that the catalytic activity of Ptm^Au/C catalysts for formic acid electro-oxidation could be dramatically enhanced by decreasing the size of Pt entities or increasing the Pt dispersion on Au particles. On varying the concentration of formic acid, we observed distinct volcano curves by correlating the electro-oxidation current with the concentration of formic acid for both Ptm^Au/C and Pt/C catalysts. Therefore, the determination of an appropriate concentration window for formic acid can be a key factor to the power densities of direct formic acid fuel cells using Pt-based electrocatalysts.
    Latest Research Progresses in Catalysts for the Purification of Exhaust Gases from Diesel Engines
    ZHAO Zhen*;ZHANG Guizhen;LIU Jian;LIANG Peng;XU Jie;DUAN Aijun;JIANG Guiyuan;XU Chunming
    2008, 29 (3):  303-312. 
    Abstract ( 2475 )   [Full Text(HTML)] () PDF (439KB) ( 1432 )  
    The pollutants in the exhaust gases of diesel engines lead to serious environmental pollution problems. The catalytic purification technology is one of the indispensable and most efficient technologies for the treatment of the exhaust gases from diesel engines. The study and development of efficient catalysts are the key in the catalytic purification technology. Taking the catalytic purification technology of NOx and diesel soot, which are the two most difficultly treated pollutants, as a main thread, we summarized the latest progresses in catalyst studies on catalytic reduction of NOx including selective catalytic reduction (SCR) and NOx storage-reduction (NSR), catalytic combustion of diesel soot, simultaneous removal of NOx and diesel soot, and four-way catalysts for the treatment of diesel engine exhaust gases. Moreover, the major problems and research directions in this area were proposed and discussed.