STUDY ON POLYMERIC CATALYST-PALLADIUM COMPLEX WITH RADIATION GRAFTING ACRYLONITRILE ON INORGANIC COMPOUND

Polymer bound palladium (Pd)complex catalysts with grafting acrylonitrile on inorganic compound(MgO,Y-molecular sieve and SiOz) by pre-radiation method were studied. The palladium - grafting polymers have been investigated by X-ray photoelectron spectrscopy(XPS). It is indicated that peak width of C1s and O1s spectra of MgO-g-PAN - Pd (radiation - induced graft) is wider than that of MgO -PAN - Pd(chemical method) and peak numbers of former are one more than later.According to the report in reference, this peak is attributed togroup. Thus, the graft acrylonitrile on MgO may complete through oxygen atoms in MgO and β-carbon atoms in acrylonitrile. The polymer catalyst obtained by radiation grafting is a higher active hydrogenation catalyst for olefines and better antitoxic than that of one obtained by chemical method, and it has selectivity for hydrogenation catalyst.     

CHARACTERIZATION OF RADIATION GRAFTING DEGREE OF POLYSTYRENEg-ACRYLIC ACID BY XPS

In this work, characterization of radiation grafting degree of polystyrene-g-acrylic acid by XPS was studied. It is found that along with the main peak C_(1s) there is a photoelectron peak at 289.0 eV that appears to be C_(1s) of-(?)-OH group and shows the presence ofpolyacrylic acid grafted on the polystyrene The grafting degree obtained by XPS is in agreement with that from the gravimetric method.     

THE EFFECT OF MODIFICATION OF COORDINATING GROUPS ON THE CATALYTIC BEHAVIORS OF POLYMER CATALYSTS

Several polymer-supported palladium complex catalysts containing two different coordinatinggroups were prepared and the cooperative effect of the coordinating groups on the catalytic behaviorsof polymer catalysts was studied. It was found that poly(acrylic acid-co-acrylonitrile)-Pd complex(PAA-AN-Pd) is a more active and stable catalyst for hydrogenation than both poly(acrylic acid)-Pd and poly(acrylonitrile)-Pd complexes. A marked change of catalytic behaviors of poly(N-substituted maleamic acid-co-styrene)-Pd complexes was observed in comparison with poly(maleicacid-co-styrene)-Pd complex. Acetophenone was reduced to 1-phenyl ethanol by poly(N-phenylmaleamic acid-Co-styrene)-Pd complex (N-1-Pd), but ethylbenzene was obtained using poly(maleicacid-co-styrene)-Pd complex as a catalyst. The influence of solvents, additives and N/Pd gramatomic ratio on the catalytic behaviors of the polymer complexes was investigated.     

SYNTHESIS OF HYDROCARBONS FROM CO_2 AND H_2 OVER Fe/C CATALYST

The production of hydrocarbons by hydrogenation of CO_2 is one ofthe most challenging aims in C_1 chemistry. In this work, we studiedCO_2 hydrogenation over iron catalyst supported on carbon under differentreaction conditions. The products of CO_2 hydrogenation on Fe/C catalyst weremainly hydrocarbons including more than 70% C_2~+ hydrocarbons. When thereaction temperature and pressure were elevated,the CO_2 conversion and theselectivity to hydrocarbon(HC) products increased. It was also found that theaddition of Cu onto Fe/C catalyst has an apperent effect on the activity andselectivity of Fe/C catalyst. It increased the CO_2 conversion and the selectivityto total HC Products to 62.8% and 100% respectively. The results obtainedfrom TPR and M(?)ssbauer spectroscopy proved that the iron was reduced mucheasier in Fe-Cu/C than in the Fe/C catalyst.     

Adsorption of HCN on Ni/Pt(111) Bimetallic Surfaces Investigated with Density Functional Theory Method

We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt(111) bimetallic surfaces(x = 1~4). The results have been compared with those obtained on pure Ni(111) and Pt(111) surfaces. For all bimetallic surfaces,HCN is preferentially tilted with the CN bond parallel to the surface,and adsorption energies increase with an increasing number of layer Ni atoms on the surface. The adsorption energies of HCN on all bimetallic surfaces are larger than that on the Pt(111) surface,whereas the adsorption energies of HCN on 3Ni@Pt(111) and 4Ni@Pt(111) are larger than that on the Ni(111) surface,indicating that the introduction of Ni to the Pt catalyst could increase the activity of bimetallic catalyst in the hydrogenation reaction for nitriles. Larger adsorption energy of HCN leads to a longer C–N bond length and a smaller CN vibrational frequency. The analysis of Bader charge and vibrational frequencies showed obvious weakening of the adsorbed C–N bond and an indication of sp2 hybridization of both carbon and nitrogen atoms.     

STUDIES ON REGULARITY OF POLY PHENYLSILSESQUIOXANE CHAINS

IR and ~(29)Si NMR were used to determine the structures of ladderlike polymer polyphenylsilsesquioxanes (PPS). It was found that PPS with lots of defects had a wide and strong absorption band in 1000—1400 cm~(-1) with only one sharp peak at 1137 cm~(-1) while two peaks (1130 and 1045 cm~(-1) were observed for PPS with perfect ladderlike structure. Branching and crosslinking of PPS lead to the reduction of 1045 cm~(-1) peak. ~(29)Si NMR spectra, however, showed two peaks (δ=-78 ppm and -87 ppm when δ_(HMDS)=0 ppm) for defective or branched PPS. The -87 ppm peak is related to the ladderlikely constructed Si atoms and -78 ppm corresponds to defective Si atoms. PPS with defects less than 0.1% chain units was obtained by azeotropic polycondensations.     

PRODUCTION OF LIGHT ALKENES FROM SYNGAS OVER Fe-MnO CATALYST SUPPORTED ON IIA METAL OXIDE

The alkene selectivity of CO hvdrogenation over Fe-MnO catalystis improved obviously by using NA metal oxide as catalyst support.Bettercatalytic pertformance of catalyst Fe-MnO/MgO can be achieved withaddition of LA metal as promoter.The selectivity is insensitive totemperature.but not to syngas space velocity.Two kinds of coking(I and Ⅱ)will form over the catalyst during CO hydrogenation.lt is interesting thatcoking(I)is favorable for production of light alkenes while cokiing(lI)is not.Other more.LA metal oxide supported Fe-MnO catalyst is able to inhibit thesecondary reactions of ethylene and hydrogenation of propylene.which isfavorable for the formation of light alkenes.     

ELECTRONIC STRUCTURE AND CHEMICAL BONDING OF TRISINDENYL SAMARIUM

The electronic structure and chemical bonding of Sm(Ind)3 were studied by using INDO calculation method.The results showed that the 6s 6P and 5d orbitals of Sm mixed with the atomic orbitals of ligands to some extent while the 4f orbital of Sm was strongly localized,participating in bonding less than 2%.The HOMO and the LUMO were of π-type.The chemical bond of Sm(Ind)3 is considerably covalent in character.The net charge distribution on the carbon atoms of the indenyl group is unequal.The Some bonds in Sm(Ind)3 THF is discussed.     

Influence of MgO contents on silica supported nano-size gold catalyst for carbon monoxide total oxidation

A series of nano-size gold catalysts were prepared by deposition-precipitation method using silica material promoted with different amounts of MgO as the carrier. The influences of MgO addition on the structure and property of the nano-size gold catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), O2 temperature-programmed desorption (O2-TPD), and inductively coupled with plasma atomic emission spectroscopy (ICP-AES) techniques. The total oxidation of CO was chosen as the probe reaction. The results suggest that for the gold catalysts supported on the silica material after MgO modification, the size of the gold particles is pronouncedly reduced, the oxygen mobility is enhanced, and the catalytic activity for low-temperature CO oxidation is greatly improved. The gold catalyst modified by 6 wt% MgO (Mg/SiO2 weight ratio) shows higher CO oxidation activity, over which the temperature of CO total oxidation is lower about 150 K than that over the silica directly supported gold catalyst.     

Electrocatalytic activity of porous nanostructured Fe/Pt-Fe electrode for methanol electrooxidation in alkaline media

An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodepo-sition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.     

KINETICS STUDY ON MELT GRAFTING ACRYLIC ACID ONTO LLDPE USING REACTIVE EXTRUSION

The kinetics of melt grafting acrylic acid(AA)onto linear low density polyethylene(LLDPE)by using reactive extrusion was investigated.The polymeric peroxides(POOP and POOH)generated by electron beam irradiation were used to initiate the graft reaction.The samples taken out from the barrel at five ports along screw axis were analyzed by FTIR.The spectra show that both the graft copolymerization and homopolymerization proceed in two stages:the graft degree(or mass of homopolymer)increases linearly with the reaction time in the initial stage,and then gradually in the second stage.The rate of graft copolymerization R_g is always faster than that of homopolymerization R_h in the present system and the activation energy is 131 kJ·mol~(-1) for graft copolymerization and 127 kJ·mol~(-1) for homopolymeirzation.These results were interpreted in terms of solubility and diffusion of monomer,as well as the reactivity and the concentration of reactive species. The relationships between reaction rate and monomer concentration and peroxide concentration were found to he:R_g ∝ [M]~(1.46)[POOP+POOH]~(0.53) and R_h ∝[M]~(1.08)[POOH]~(0.51),which indicate that the addition of monomer to polymeric radicals is a slow step for the graft copolymerization.     

纳米二氧化锆在甲醇合成催化剂Cu/Ga2O3/ZrO2中的作用

The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesoporous volume and more uniform diameter, more surface metal atoms and oxygen vacancies than the catalyst prepared with the conventional coprecipitation method. The modification of microstructure and electronic effect could result in the change of the reduced chemical state and decrease of reducuction temperature of copper, donating the higher activity and methanol selectivity to the catalyst. The results of methanol synthesis demonstrate that the Cu^＋ is the optimum active site. Also, the interaction between the copper and zirconia shows the synergistic effect to fulfil the methanol synthesis.     

TiO2担载镍催化剂上硝基苯液相加氢（英文）

The catalytic hydrogenation of nitrobenzene to aniline employing nickel impregnated on rutile,anatase,and high surface area titania supports has been investigated.The nickel is present in elemental state as fcc phase on the catalyst as evidenced by X-ray diffraction results.The Ni crystallite size was found to be greater for Ni/anatase.The temperature-programmed reduction results suggest a greater metal-support interaction for Ni/rutile.The observed order of catalytic activity for the hydrogenation of nitrobenzene is Ni/rutile > Ni/anatase > Ni/TiO2.A conversion of 99% was observed for Ni/rutile at 140 oC and hydrogen pressure of 1.96 MPa.Interestingly,aniline is the only product formed which demonstrates the catalytic hydrogenation of nitrobenzene proceeds with atom economy.Both Ni/rutile and Ni/anatase exhibited a better stability than Ni/TiO2.The hydrogenation proceeds with the preferential adsorption of hydrogen on nickel present in the catalyst surface,possibly assisted by TiOx species.     

采用柠檬酸合成高分散铜催化剂用于选择氢解反应

A highly dispersed Cu catalyst supported on silica was prepared by an incipient wetness impregnation method with citric acid.The synthesis was studied by nitrogen physisorption,X-ray diffraction,and temperature-programmed reduction by comparing with a reference prepared without citric acid.The catalyst precursor obtained after impregnation was X-ray amorphous.The precursor was readily transformed to crystalline CuO upon calcination.The CuO particles were of uniform size in a highly dispersed state and can be reduced to Cu at a lower temperature.The activity of the Cu catalyst obtained was an order of magnitude higher than that of the reference for the hydrogenolysis of methyl laurate to dodecanol.     

Plasma modification of polypropylene surfaces and grafting copolymerization of styrene onto polypropylene

The surface of polypropylene(iPP) is modified with glow discharge plasma of Ar,so that the modified surfaces of iPP films are obtained.The studies of scanning electron microscopy(SEM) show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared(FTIR) spectroscopy.The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated.The free radical of modification surfaces of iPP is measured by chemical method.The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene(St) in St.The grafting polymer of St onto iPP is characterized by FTIR.The grafting rate is dependent on plasma exposure time and discharge voltage.The studies show that homopolymerization of St is undergone at the same time during the grafting-copolymerization of St onto iPP.     

Study of a Ru-La/Zr02 Catalyst Prepared by Precipitation Method for Selective Hydrogenation of Benzene to Cyclohexene

A Ru-La/ZrO2 catalyst was prepared by the precipitation method, in which Ru was an active component, La was a promoter and ZrO2 was a dispersant. Comparing with the catalyst prepared by the chemical reduction method, the Ru-La/ZrO2 exhibited higher activity and better selectivity. At 140 ℃ and hydrogen pressure of 5 MPa, the C6H10 selectivity reached 70% at a C6H6 conversion of 35% for a reaction time was 5 min and the total La/Ru loading was 10%. Textural parameters of the catalyst were obtained by physical adsorption, BET surface area and specific pore volume measurements. The catalyst sample gave a BET area of 41 m2/g and a specific pore volume of 1.1 cm^3/g, and the most probable pore distribution was located at 5 to 10 nm. H2-TPR measurements showed that ruthenium oxide could be reduced to its metallic state at about 403 K. XRD determinations indicated that ruthenium and lanthanum were highly dispersed on the zirconia. A significant advantage of the Ru-La/ZrO2 catalyst is that it can be used directly in its unreduced state for the selective hydrogenation of benzene.     

Novel Carbon Nanotubes-supported NiB Amorphors Alloy Catalyst for Benzene Hydrogenation

The NiB amorphous alloy catalysts supported on CNTs and alumina were prepared by impregnation and chemical reduction. The gas-phase benzene hydrogenation was used as a probe reaction to evaluate the catalytic activity. The result showed that the NiB amorphous alloy catalyst supported on carbon nanotubes exhibited higher activity than that supported on alumina.     

PROMOTING EFFECTS OF Cs ON Fe/AlPO_4-5 CATALYST FOR CO HYDROGENATION

The positive effects of Cs added to Fe/AIPO_4-5 catalysts in CO hy-drogenation were studied.Cs-modified Fe/AIPO_4-5 catalysts prepared by im-pregnating method using non-aqueous acetone solution of iron nitrate werefound to be active and selective for CO conversion and light olefins formation.The characterizations of catalysts by TPR,TPD,XPS and Mssbauer techniquesindicated that the Cs addition promoted the reduction of the catalyst and adsorp-tion of CO on the surface of the reduced catalysts.A strong interaction betweeniron and AlPO_4-5 support was revealed.The results show that the AlPO_4-5molecular sieves not only can be used as the support of catalyst but also cancontrol the growth of carbon chain of the products and maintain the activity ofthe catalyst for CO hydrogenation.     

INFLUENCE OF VOCl_2-ADDITIVE IN Rh CATALYST ON CO HYDROGENATION

The influence of VOCl2 additive in the supported Rh catalysts derived from both Rh2 (CO )4 Cl2 and RhCl3 on CO hydrogenation was investigated. The VOCl2 additive as a promoter can effectively enhance the CO conversion and catalytic selectivity to ethanol. This effect is caused by the interaction of Rh with vanadium promoter. It is found that the Rh centers on which the gem- adsorbed CO could be formed are main active sites. The Rh2(CO)4Cl2 complex is better than the RhCl3 salt as the precursor of the Rh catalyst for the CO hydrogenation to ethanol.     

GRAFTING OF POLYSTYRENE ONTO A NANOMETER SILICA SURFACE BY MICROEMULSION POLYMERIZATION

The grafting of polystyrene onto a nanometer silica surface by microemulsion polymerization is described. Silicawas functionalized with 3-methacryloxypropyltrimethoxysilane coupling agent before polymerization. A mixture of ionic andnon-ionic surfactants as well as water-soluble and oil-soluble initiators were used. The effect of the amount of silica and ionicsurfactant on the graft polymerization was studied. The graft polymerization procedure for styrene was also applied to methylmethacrylate. Composite particles with a core-shell structure were obtained and the yield and grafting efficiency of monomerwere high.