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Chinese Journal of Catalysis
2010, Vol. 31, No. 1
Online: 25 January 2010


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Ma and coworkers in their Article on pages 24–32 reported the dynamic changes in the surface structures of Fe-Pt(111) model systems under cycled reduction and oxidation treatments. Transformation of the surface Fe overlayers, subsurface Fe, and surface FeO overlayers at Pt(111) can be controlled by the redox potential of the environment.

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Recent Progress in Research of Some Carbonylation Reactions LIU Jianhua*;CHEN Jing;SUN Wei;XIA Chungu* 2010, 31 (1):  1-11.  Abstract ( 2803 )   [Full Text(HTML)] () PDF (1098KB) ( 2179 )   Carbonylation, the direct incorporation of carbonyl functionality into organic molecules, is one of the frontiers of green chemistry and one of the important transformation pathways of utilization of C1 resources. The recent research progress of oxidation carbonylation of amines/β-amino alcohols, alkoxycarbonylation of epoxides, carbonylative Suzuki coupling, carbonylative Sonogashira, and double carbonylation of aryl iodides has been presented, focusing on the carbonylation reactions studied by us in the past few years, with 81 references. The development and application prospects for carbonylation have been also discussed.

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New Carbon Materials as Catalyst Supports in Direct Alcohol Fuel Cells TANG Shuihua;SUN Gongquan;*;QI Jing;SUN Shiguo;GUO Junsong;XIN Qin;Geir Martin HAARBERG 2010, 31 (1):  12-17.  Abstract ( 2722 )   [Full Text(HTML)] () PDF (693KB) ( 1980 )   Electrocatalytic reactions in direct alcohol fuel cells involve solid, liquid, and gas phase transport and electron and proton transfer. Better supports for the electrocatalysts are needed to carry out the reactions successfully and give a longer lifetime for the electrocatalysts. An ideal carbon support should have a high specific surface area, good electric conductivity, suitable pore size, favorable surface functional groups, good corrosion resistance, and low cost. Much work has been done on developing new carbon materials and modifying the carbon materials by pretreatment with acid, alkali, oxidant, or polymer to meet these requirements. In this work, commercial carbon supports that include the widely used carbon black Vulcan XC-72R, acetylene black, black pearls 2000, Printex XE-2, and Ketjen Black EC were briefly reviewed. New carbon materials such as carbon nanofibers, carbon nanotubes, ordered porous carbon, mesocarbon microbeads, carbon nanohorns, carbon nanocoils, and carbon aerogels were reviewed in detail. These new carbon materials generally give better performance due to their special structure, better crystallinity, and faster mass transfer when compared to the commercial materials, and carbon nanotubes demonstrated the best performance up to the present time.

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Presulfidation of CoMo and NiMoP Catalysts by Ammonium Thiosulfate GE Hui;LI Xuekuan*;WANG Guofu;QIN Zhangfeng;L?Zhanjun;WANG Jianguo 2010, 31 (1):  18-20.  Abstract ( 2329 )   [Full Text(HTML)] () PDF (460KB) ( 978 )   Ammonium thiosulfate ((NH4)2S2O3) was used as a sulfiding agent for presulfiding CoMo and NiMoP catalysts. The effect of the amount of (NH4)2S2O3 on hydrodesulfurization (HDS) activity was investigated. For the CoMo series, the use of a proper amount of (NH4)2S2O3 gave a higher HDS activity than when the catalyst was sulfided by H2S. SO42– formed during presulfidation modified the Al2O3 support and decreased the interaction between the active phase and support, and the activity was enhanced. However, a smaller amount of (NH4)2S2O3 used for the presulfidation would result in insufficient sulfidation, while a larger amount of (NH4)2S2O3 increased the particle size of the active phases, and both were harmful to HDS activity. For the NiMoP series, the presulfided catalysts were less active than those sulfided by H2S. This was ascribed to the high metal content and the addition of P to the catalyst.

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Methanation of Carbon Dioxide over a Highly Dispersed Ni/La2O3 Catalyst SONG Huanling;YANG Jian;ZHAO Jun;CHOU Lingjun* 2010, 31 (1):  21-23.  Abstract ( 2784 )   [Full Text(HTML)] () PDF (449KB) ( 1002 )    The methanation of carbon dioxide on a Ni/La2O3 catalyst containing 10 wt% Ni prepared by the impregnation method was studied. The space-time yield of methane was 3000 g/(kg·h) at conditions of 350 oC, GHSV of 30000 h–1, 1.5 MPa pressure, and H2/CO2 molar ratio of 4/1. The selectivity for methane was 100% with different CO2 conversions. Combined with X-ray diffraction and H2 temperature-programmed reduction analyses, this suggested that the reaction mechanism on Ni/La2O3 may be different from that on Ni/γ-Al2O3. The formation of lanthanum oxycarbonate (La2O2CO3) can play an important role in the activation of CO2.

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Controlled Transformation of the Structures of Surface Fe (FeO) and Subsur-face Fe on Pt(111) MA Teng;FU Qiang#;CUI Yi;ZHANG Zhen;WANG Zhen;TAN Dali;BAO Xinhe* 2010, 31 (1):  24-32.  Abstract ( 2714 )   [Full Text(HTML)] () PDF (28968KB) ( 587 )   Monolayer Fe films on Pt(111) and their derived structures under different environments were investigated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The growth of monolayer Fe films was seen at 487 K. The surface composition and structure of the Fe/Pt(111) surface were monitored by XPS and STM during stepwise annealing under vacuum. Surface Fe was driven into the subsurface region during annealing above 800 K. This resulted in a Pt-skin surface of Pt/Fe/Pt(111). Oxidation of the Pt-skin structure in O2 produced a FeO surface structure, FeO/Pt(111). This was transformed into a surface Fe structure by mild reduction in H2 (600 K) and into subsurface Fe by further severe reduction (800 K). The transformation of surface Fe (FeO) and subsurface Fe in Pt(111) was reversible in cycled oxidation and reduction treatments. The results demonstrated the controlled preparation of various Fe-Pt surfaces. This can be important for the design of high-performance and low-cost catalysts.

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A First-Principle Study of Oxonium Ylide Mechanism over HSAPO-34 Zeolite WANG Yangdong;WANG Chuanming;LIU Hongxing;XIE Zaiku* 2010, 31 (1):  33-37.  Abstract ( 2600 )   [Full Text(HTML)] () PDF (3327KB) ( 1277 )    Based on density functional theory calculation with periodic boundary conditions, the possibility of the direct coupling of methanol into ethene by oxonium ylide mechanism was investigated. The calculated results indicate that the energy barriers for the formation of dimethyl ether and trimethyl oxonium ion inside HSAPO-34 zeolite are 1.68 and 0.93 eV, respectively. The suggested intermediate oxonium ylide is very unstable and the energy barriers for the formation of C–C bond are over 3.0 eV by concerted pathway. It is thus concluded that the methanol to olefin reaction cannot follow the oxonium ylide mechanism.

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Transesterification of Dimethyl Carbonate with Dodecanol to Didodecyl Car-bonate over KF/MgO Catalyst FAN Yanping;;WANG Qingyin;YANG Xiangui;YAO Jie;WANG Gongying;* 2010, 31 (1):  38-43.  Abstract ( 2344 )   [Full Text(HTML)] () PDF (5962KB) ( 1103 )   The catalytic activity of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification of dimethyl carbonate (DMC) with dodecanol (DoOH) was studied. The effects of KF loading and calcination temperature were investigated. The catalysts were characterized by X-ray diffraction,?Fourier transform infrared spectroscopy, scanning electron microscopy, and N2 adsorption-desorption. The results indicated that new phases K2MgF4 and K2CO3 were formed when KF/MgO was calcined in air at high temperature. K2MgF4 and K2CO3 were the main catalytic sites in this reaction. KF/MgO was an effective catalyst in this transesterification reaction and the optimized KF loading and calcination temperature were 30% and 873 K, respectively. The optimized reaction conditions were as follows: n(DoOH):n(DMC) = 4, catalyst amount 0.75%, reaction time 4 h. Under these conditions, the conversion of DMC and the yield of DDC were 86.7% and 86.2%, respectively.

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The Redox Properties of SnO2 Nanorods ZHAO Heyun;*;ZHAO Zhongze;ZHAO Yifen;LIU Qingju; 2010, 31 (1):  44-48.  Abstract ( 2626 )   [Full Text(HTML)] () PDF (2423KB) ( 2153 )   SnO2 nanorods were successfully synthesized in molten NaCl-KCl salt through calcination of SnO2 nanoparticles precursor prepared by solid state reaction at room temperature. The structure and morpho1ogy of SnO2 nanorods were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected-area electron diffraction, and X-ray photoelectron spectroscopy. The results showed that the SnO2 nanorods with 10–20 nm diameter and several micrometers length were rutile structure. The results of H2 temperature-programmed reduction demonstrated that the SnO2 nanorods had good redox performance. The redox mechanism was discussed in detail.

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A Density Functional Theory Study of 2-Chlorothiophene Adsorption on Rh(111) Surface CHEN Zhanhong;DING Kaining;XU Xianglan;LI Junqian;* 2010, 31 (1):  49-55.  Abstract ( 2302 )   [Full Text(HTML)] () PDF (5196KB) ( 1082 )   2-Chlorothiophene adsorbed on Rh(111) surface was investigated by the density functional theory. The results showed that 2-chlorothiophene was adsorbed preferably at the hol and bridge sites with the adsorbate molecular plane parallel to the Rh(111) surface. After adsorption, the molecular plane of the adsorbate was distorted along with the corresponding changes of bond lengths. The C–H(Cl, S) bonds tilted away from the surface. The upright adsorption was less stable than the parallel adsorption; however, the 2-thiophene ring remained flat. After the 2-chlorothiophene molecule was adsorbed on the surface at the hol and bridge sites, its aromaticity was damaged and the C atoms were a characteristic of sp3 hybrid. The 2-chlorothiophene molecule altogether obtained 0.77 electrons after the adsorption, while the metal surface altogether lost 1.19 electrons.

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Reaction of NO and NO2 with NH3 over V2O5/AC Catalyst SUN Dekui;LIU Zhenyu;*;GUI Guoqing;HUANG Zhanggen;LIU Qingya;XIAO Yong 2010, 31 (1):  56-60.  Abstract ( 2476 )   [Full Text(HTML)] () PDF (531KB) ( 1391 )   Temperature-programmed desorption, on-line mass spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy were preformed to study selective catalytic reduction (SCR) of NO and NO2 with NH3 over V2O5 and activated carbon (AC)-supported V2O5 (V2O5/AC). The results show that both protonated (NH4+) and molecularly coordinated (NH3) ammonia species form on the V2O5 surface and V=O bond is the primary active site. Both NO2 and NO can react with the adsorbed ammonia in the absence of oxygen, but the activity of NO2 is superior to that of NO. On the V2O5/AC surface, NO2 still can react with the adsorbed NH3 species to form N2, but NO shows little activity unless oxygen is present. SCR of NO on V2O5/AC proceeds through oxidation of NO to NO2 by oxygen on the AC surface followed by reaction of NO2 with NH3 species adsorbed and activated on the V2O5 surface.

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In Situ 13C MAS NMR Study on Reaction Mechanism of Isobutane Rearrange-ment over Sulfated Zirconia ZHANG Li;YUE Bin*;QIAN Linping;HE Heyong* 2010, 31 (1):  61-67.  Abstract ( 2237 )   [Full Text(HTML)] () PDF (1248KB) ( 793 )   In situ 13C MAS NMR was employed to study the reaction mechanism of isobutane rearrangement over sulfated zirconia using 2-13C-isobutane as a reactant. The effects of temperature and hydrogen atmosphere on the reaction were investigated. The results showed that the reaction of isobutane proceeded mainly via a monomolecular mechanism in its early stage, and then a bimolecular mechanism became dominant. Increasing temperature also led to the reaction from monomolecular to bimolecular mechanism. In the presence of hydrogen, the reaction of isobutane rearrangement, in particular that through the bimolecular pathway, was significantly inhibited.

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Influence of Fe Content on Catalytic Reduction of N2O with CH4 over FeAlPO-5 Catalyst ZHAO Xiaoxu;CHENG Dang-guo*;CHEN Fengqiu;ZHAN Xiaoli 2010, 31 (1):  68-71.  Abstract ( 1989 )   [Full Text(HTML)] () PDF (469KB) ( 813 )   Fe-substituted AlPO-5 zeolite (FeAlPO-5 catalyst) samples with different Fe contents were prepared by the hydrothermal method and used in catalytic reduction of N2O with CH4, exhibiting good low-temperature activity. The AlPO-5 and FeAlPO-5 samples were characterized by N2 physisorption, X-ray diffraction, and UV-visible spectroscopy. The results showed that the FeAlPO-5 samples had the typical structure as that of AlPO-5 zeolite. The Fe content had strong influence on the catalyst activity and the distribution of Fe species. The 2.4% FeAlPO-5 catalyst contained not only isolated FeIII and oligonuclear FeIII, being active for catalytic reduction of N2O with CH4, but also a considerable nanosized FeIII, being responsible for N2O decomposition.

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Probe Reactions Catalyzed by Surface Acid Sites of HTS-1 LIU Xuanyan;YIN Dulin;*;ZHU Huayuan;SHEN Gang 2010, 31 (1):  72-77.  Abstract ( 2514 )   [Full Text(HTML)] () PDF (536KB) ( 1046 )   Hydrolysis of 1,2-epoxycyclohexane as a probe reaction was employed to investigate the surface acid properties of titanium-silicate zeolite (HTS-1) catalyst under various conditions. The results indicated that the hydrolysis reaction was mainly affected by solvent polarity and diffusion limitation, and HTS-1 showed outstanding catalytic performance for this reaction. Quantitative and qualitative analysis of acidity and acid sites by means of pyridine adsorption was performed using UV-Vis and FT-IR spectroscopy, respectively, which can distinguish Brønsted acidic sites and Lewis acidic sites and to calculate precisely the surface acid amount of HTS-1. These results not only expand the applications of HTS-1 in fine chemical synthesis but also provide a basis for effectively improving the catalytic performance of HTS-1 in oxidation.

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Effect of Ethane Addition on Methane Dehydroaromatization over Mo/HZSM-5 Catalyst SUN Changyong;YAO Songdong;SHEN Wenjie;*;LIN Liwu;* 2010, 31 (1):  78-83.  Abstract ( 2571 )   [Full Text(HTML)] () PDF (2536KB) ( 2217 )   The effect of ethane addition on methane dehydroaromatization over a Mo/HZSM-5 catalyst was investigated. It was revealed that the ethane addition could not promote the conversion of methane but produced methane and increased coke deposition rate, causing rapid deactivation of the catalyst. However, ethane accelerated the formation of Mo active centers (Mo2C and/or MoOxCy species), shortening the induction period and moving the benzene formation forward.

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Preparation of Mesoporous Nanosized MoPO-AlPO4 and Its Catalytic Per-formance for Selective Oxidation of Isobutene WANG Xitao;BI Chao;ZHONG Shunhe*;XIAO Xiufen 2010, 31 (1):  84-89.  Abstract ( 2368 )   [Full Text(HTML)] () PDF (4616KB) ( 1175 )   MoPO-AlPO4 catalysts were prepared by sol-gel and impregnation methods. The effects of Mo species on crystal lattice oxygen activity and catalytic performance of MoPO-AlPO4 for selective oxidation of isobutene were investigated. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy, and temperature-programmed reduction. The results showed that the MoPO-AlPO4 prepared by the sol-gel method existed as mesostructured nanoparticles with larger surface area and more pores than the corresponding MoPO-AlPO4 prepared by the impregnation. Mo species appeared in tetrahedral coordination in the sample prepared by the sol-gel method and in both tetrahedral and octahedral coordinations in the sample prepared by impregnation. This indicated that the sample prepared by the sol-gel method had better dispersion of Mo species than that prepared by impregnation. The Mo species incorporated-mesoporous AlPO4 obviously improved the catalytic performance of MoPO-AlPO4 for selective oxidation of isobutene.

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Efficient Assembled Pd/C Catalyst Applied in Suzuki Coupling Reactions HUANG Zhongbin;YAN Xinhuan*;JIANG Lingchao;JIANG Hong 2010, 31 (1):  90-94.  Abstract ( 2826 )   [Full Text(HTML)] () PDF (1094KB) ( 1781 )   The Pd nanoparticles with diameters of 3–6 nm were obtained by the decomposition of Pd2(dba)3 (dba = dibenzalacetone). They were captured by activated carbon directly to prepare the assembled Pd/C catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction were used to characterize the size, distribution, and electronic state of Pd nanoparticles. This assembled catalyst showed extraordinary properties in Suzuki coupling reaction, which was over twice than the Pd/C catalyst prepared by the impregnation method. Under the conditions of 80 oC and 0.5 h, the catalyst can catalyze Suzuki reactions of aryl bromide with a coupling product yield of 98%. The assembled Pd/C catalyst can also catalyze the reaction of o-chloronitrobenzene with a yield of 64% in 1 h when the reaction temperature was 110 oC, and the yield can be higher than 90% with extending the reaction time.

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Reaction Behavior for Synthesis of Methyl Ethyl Ketone Oxime Catalyzed by Titanosilicate/H2O2 Systems YANG Junxia;YAO Mingkai;ZHAO Song;LIU Yueming*;WU Peng;HE Mingyuan 2010, 31 (1):  95-99.  Abstract ( 2744 )   [Full Text(HTML)] () PDF (477KB) ( 1556 )   In the preparation process of oxime over the titanosilicate/H2O2 system, the reaction performance of oxime influenced the efficiency and stability of the process directly. The reaction behavior of methyl ethyl ketone oxime produced from ammoximation of methyl ethyl ketone catalyzed by the Ti-MWW/H2O2 system was studied. The Ti-MWW and H2O2 together resulted in the hydrolysis of methyl ethyl ketone oxime to methyl ethyl ketone, NOx, etc. Thus, the system was from alkalescence to acidity. The same phenomena also existed in the TS-1/H2O2 system for cyclohexanone oxime production. This experimental result was beneficial for the increase of the efficiency and the stability of the process over the titanosilicate/H2O2 system.

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Influence of Chemical States of Fe and Mn on N2O Decomposition over LaFexMnyAl12-x-yO19 Catalysts TIAN Ming;WANG Xiaodong;*;ZHU Yanyan;WANG Junhu;ZHANG Tao;* 2010, 31 (1):  100-105.  Abstract ( 2353 )   [Full Text(HTML)] () PDF (4803KB) ( 1063 )    LaFexMnyAl12-x-yO19 hexaaluminate catalyst samples were prepared by a coprecipitation method and tested for N2O decomposition with high concentration (30%, V/V). The catalyst samples were characterized by X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption, ultraviolet-visible spectroscopy, and Mössbauer spectroscopy. The results showed that the partial substitution by Mn led to easier formation of phase-pure hexaaluminate compared with that by Fe under the investigated conditions. Fe3+ occupied both tetrahedral sites in spinel block and trigonal bipyramid sites in mirror plane for LaFexAl12-xO19 (x = 0.5, 1) hexaaluminate. Mn2+ preferentially entered tetrahedral sites at low Mn content (y = 0.5) for LaMnyAl12-yO19 hexaaluminate, whereas Mn3+ entered octahedral sites in spinel block at y = 1. The activity tests for N2O decomposition with high concentration demonstrated that Fe3+ in trigonal bipyramid sites of LaFexAl12-xO19 and Mn3+ in octahedral sites of LaMnyAl12-yO19 were the main active centers.

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Structure, Catalytic Oxidation Performance, and Sulfur Resistance of Mn-Based Catalysts Supported on Modified Mesoporous Al2O3 ZOU Zhiqiang;MENG Ming;*;YU Yifu;XIE Yaning;HU Tiandou;ZHANG Jing 2010, 31 (1):  106-111.  Abstract ( 2233 )   [Full Text(HTML)] () PDF (658KB) ( 1109 )   The manganese oxide catalysts supported on mesoporous Al2O3 modified by LaCeZr or YCeZr were prepared by successive impregnation. The structure of the catalysts was characterized by X-ray diffraction, N2 adsorption-desorption, X-ray absorption fine structure, X-ray photoelectron spectroscopy, and temperature-programmed reduction by H2. The state of manganese species and their reducibility were investigated and correlated with the CO and C3H8 oxidation performance of the catalysts. The results demonstrate that the manganese species mainly exist as Mn3O4 crystallites, which interact with the support Al2O3. The different interaction strength determines the reducibility and catalytic properties of the catalysts. The promoters LaCeZr or YCeZr effectively inhibit the interaction between Mn and Al oxides, increasing the mobility of Mn–O bond and the catalytic activity of the corresponding catalysts. Compared with YCeZr, the promoter LaCeZr improves the reducibility of MnOx to a larger extent, enhancing the activity more obviously. The catalysts modified by LaCeZr calcined at 650 oC exhibits high oxidation performance and sulfur resistance. In the presence of 0.035% SO2 in the feed, the CO oxidation activity of the catalyst can be well maintained, and the C3H8 oxidation activity decreases only a little.

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Preparation of Quaternary Phosphonium-Type Triphase Catalysts and Rela-tionship between Chemical Structure and Phase Transfer Catalytic Activity WANG Ling;GAO Baojiao*;WANG Shiwei 2010, 31 (1):  112-119.  Abstract ( 2435 )   [Full Text(HTML)] () PDF (511KB) ( 1240 )   Friedel-Crafts acylation reaction of crosslinked polystyrene (CPS) microspheres was conducted using two kinds of ω-chloroacyl chloride as reagents, and chloromethylation reaction of CPS microspheres was performed using 1,4-dichloromethyoxybutane without carcinogenic toxicity as reagent. By these reactions, exchangeable chlorine was introduced onto the surface of CPS microspheres and resulted in chemically modified CPS microspheres. Subsequently, the modified microspheres were transferred into quaternary phosphonium-type triphase catalysts via quaternary phosphonium (QP) reaction with triphenylphosphine. Three kinds of quaternary phosphonium-type triphase catalysts QP-CPS with different spacer arm lengths were obtained. The effects of main factors on quaternary phosphonium reaction were examined. The phase-transfer catalytic activity of the prepared triphase catalysts for esterification between benzyl chloride and sodium acetate was investigated. The results indicate that the stability of quaternary phosphonium is poor. The reaction temperature and time need to be controlled, and the solvent with higher polarity is adapted during synthesis. The prepared quaternary phosphonium-type triphase catalysts have higher activity for the synthesis of benzyl acetate, and the reaction species acetate ion can be effectively transferred between the liquid-solid-liquid phases. In comparison with quaternary ammonium-type catalyst QN-CPS, the quaternary phosphonium-type triphase catalyst QP-CPS has higher catalytic activity. The catalyst QP-CPS with a longer spacer arm has higher catalytic activity. The hydrophilic and hydrophobic properties of catalyst QP-CPS also greatly affect the phase-transfer catalytic activity.

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Low-Temperature Preparation and Photocatalytic Performance of F-Doped Nanosized TiO2 Thin Film CHEN Yanmin;ZHONG Jing;CHEN Feng*;ZHANG Jinlong 2010, 31 (1):  120-125.  Abstract ( 2389 )   [Full Text(HTML)] () PDF (626KB) ( 1165 )   F-doped TiO2 (FTO) sol was prepared using NH4F as the fluorine precursor by a hydrothermal method. FTO thin film was then prepared via dip-coating. The TiO2 thin film prepared from the TiO2 sol that was hydrothermally treated at 120 oC for 10 h had preferable transparence and high photocatalytic activity. F doping did not significantly change the grain size of TiO2 but greatly enhanced the photocatalytic activity of the TiO2 film. The optimal doping concentration of F corresponded to F/Ti molar ratio of 0.01. The photocatalytic activity of the FTO thin film was 23% higher than that of TiO2 thin film. X-ray photoelectron spectroscopy results showed that there were two forms of F element in the FTO thin film: surface chemically adsorbed F and substituent lattice F. Both surface adsorbed F and substituent lattice F played a role in the photocatalytic activity enhancement of the FTO thin film.

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Synchronistic Synthesis and Immobilization of Porphyrins on Microspheres GMA/MMA and Catalytic Performance of Immobilized Metalloporphyrins ZHAO Jing;GAO Baojiao*;GAO Xuechao 2010, 31 (1):  126-132.  Abstract ( 2318 )   [Full Text(HTML)] () PDF (521KB) ( 1227 )   The suspension polymerization of glycidyl methacrylate (GMA) and methyl methacrylate (MMA) was conducted, resulting in polymeric microspheres GMA/MMA. Subsequently, p-hydroxybenzaldehyde (HBA) was bonded on GMA/MMA, obtaining modified microspheres HBA-GMA/MMA. Adler reaction was performed by using microspheres HBA-GMA/MMA, benzaldehyde derivatives, and pyrrole in solution, so that the synchronistic synthesis and immobilization of porphyrins on the microspheres GMA/MMA were realized successfully, resulting in three kinds of porphyrin-supported microspheres. The effects of main factors on the process of synchronistic synthesis and immobilization of porphyrin were studied. Via the coordination reaction between the functional microspheres and cobalt salt, polymer-supported cobalt porphyrin was prepared. The catalytic activity of the catalysts was tested in the oxidation reaction of ethyl benzene by oxygen molecules. The results showed that the substitute structure of benzaldehyde derivatives, the acidity of the catalysts, and the polarity of solvents affected the synchronistic synthesis and immobilization of porphyrin greatly. The porphyrin-supported catalysts had obvious catalytic activity for the oxidation reaction. The immobilized cobalt porphyrin with strong electron-withdrawing substitute on phenyl ring has higher catalytic activity.