Immobilization of the heteropoly acid (HPA) H4SiW12O40 (SiW12) on mesoporous molecular sieves (HMS and MCM-41) and their catalytic behavior

Supported catalysts, consisting of SiW12 immobilized on hexagonal mesoporous silica (HMS) and its aluminum-substituted derivative (MCM-41) with different loadings and calcination temperatures, have been prepared and characterized by X-ray diffraction, FT-IR and NH3-temperature programmed desorption. It is shown that SiW12 retains the Keggin structure on the mesoporous molecular sieves and no HPA crystal phase is developed, even at SiW12 loadings as high as 50 wt%. In the esterification of acetic acid by n-butanol, supported catalysts exhibit a higher catalytic activity and stability and held some promise of practical application. In addition, experimental results indicate that the loaded amount of SiW12 and the calcination temperatures have a significant influence on the catalytic activity, and the existence of aluminum has also an effect on the properties of supported catalysts.

Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.

Studies on preparation of iron phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, characterization and catalytic hydroxylation of phenol

Iron phenanthroline - and 8 - hydroxyquinoline complexes /Y zeolite, denoted a FePhen/Y and FeOx/Y respectively, were prepared; The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elemental analyses, diffuse reflectance UV-Vis,SEM,BET,and XRD methods; The influence of experimental parameters upon phenol conversion and product selectivities were investigated as well.

Superconductor mixed oxides La2-xSrxCuO4+/-lambda for catalytic hydroxylation of phenol in the liquid-solid phase

Superconductor mixed oxides are often used as catalysts at high temperature in gas-solid phase oxidations and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of La2-xSrxCuO4+/-lambda (x = 0, 0.1, 0.7, 1) mixed oxides in phenol hydroxylation at lower temperatures are studied, and we find that the value of x has a significant effect on catalytic activity: the lower its value, the higher the catalytic activity; a mechanism is proposed to explain the experimental phenomena.

Studies on preparation, characterization of cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, and catalytic hydroxylation of phenol

Cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, denoted as CoPhen/Y and CoOx/Y respectively, were prepared, The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elementary analyses, TG-DTA, diffuse reflectance UV-Vis, SEM, BET and XRD methods. The influence of experimental parameters upon phenol conversion and product selectivities was investigated as well.

Synthesis, characterization and catalytic activity for H2O2 decomposition of tetrabasic tungstovanadophosphate heteropoly rare earth element complexes with Dawson structure

Nine tetrabasic tungstovanadophosphate heteropoly rare earth element complexes with Dawson structure were synthesized. Their general molecular formulas are K15H4[Ln . (P2W16VO61)(2)] . xH(2)O(Ln = La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, Yb3+). Their structures and properties were investigated by IR, UV, NMR, ESR, XRD, TG-DTA. The results showed that the series of complexes have the same structure as K-16[Ce(P2W17O61)(2)] . 50H(2)O. At the same time, the catalytic activity of the complexes for H2O2-decomposition was also investigated.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

STUDIES ON SYNTHESIS, CHARACTERIZATION AND CATALYTIC PROPERTIES OF LAN+1NINO3N+1 MIXED OXIDES

A series of (AO) (ABO(3))(n)(A = La, B = Ni, n = 1 similar to 4) type mixed oxides were synthesized and characterized by means of XRD, XPS, IR, TPD, TPR. Their structure characteristics and redox properties were studied. The nonstoichiometry (lambda) of oxygen and the valence of transition metal Ni were determined by using chemical analysis method. The catalytic activities of this series of mixed oxides for complete oxidation of CO and CH4 were examined and the relationships among activity, composition and structure were discussed.

SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF LA2-XSRXCOO4+/-LAMBDA (X=0-2) IN COMPLETE OXIDATION

A series of mixed oxides La2-xSrxCoO4+/-lambda (x=0-2) with varying x values was synthesized. The crystal structure of this series of mixed oxides was studied by using XRD. The result showed that when x=0.25-1.5 the mixed oxides possessing K2NiF4 structure are formed. The valences of the transition metal Co and the relation between +/-lambda content and x value by using chemical analysis method have been measured, too. The redox property of this series of mixed oxides and different kinds of oxygen species were studied by IR, TPD, TPR, XPS and SEM methods. The catalytic activity in the complete oxidation of CO and CH4 was investigated and the relationships between the activity, composition and structure of the mixed oxides have been elucidated.

SYNTHESES AND CHARACTERIZATION OF [(MU-CF3CO2)(2)LN(MU-CF3CHO2)ALR(2)CENTER-DOT-2THF](2) AND THEIR CATALYTIC ACTIVITIES FOR POLYMERIZATION OF SOME POLAR MONOMERS

Three new bimetallic complexes were synthesized and crystalized by reactions of (CF3CO2)(3)Ln With R(1) AlR(2)(Ln=Nd and Y, R(1)=H, R=i-C4H9; Ln=Eu, R=R(1)=C2H5) in tetrahydrofuran solution, and their crystal structures were determined using a X-ray diffraction method. The structures and the questions on valence state and noncoplanarity in the structures were confirmed and cracked by means of H-1 NMR and C-13 NMR spectra, especially by C-13-H-1 COSY 2D NMR technique. A general formula of molecules of the three rare earth complexes was defined as follows: [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AlR(2) . 2THF](2) A mechanism on the formation of the new complexes was also proposed through the following five steps: alkylating, beta-elimination (or hydrogenation), hydrogen transfer, linkage and association. Both Y-Al and Eu-Al complexes function as a catalyst in polymerization of MMA and ECH. The polymer obtained from the first monomer is mainly syndiotactic chain structure and the polymerization of the last monomer shows higher catalytic activity. The Y-Al complex also capable of ring-opening polymerization of THF in case of adding-vary small amount of ECH and a oxonium ion mechanism of THF polymerization was suggested from the analysis of THF polymer terminal.

Synthesis and catalytic properties of layered double hydroxides pillared by heteropolyoxometalate

Layered double hydroxides (LDHs) pillared with heteropolyoxometalate have been synthesized via both restructuring of hydrotalcite-like compounds and direct anion exchange under microwave field. LDHs and their derivatives are both found to be efficient for alkylation of isobutane with butene with a higher butene conversion and selectivity towards C-8(0).

A STUDY OF THE CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .2. THE INTERACTION BETWEEN TRANSITION-METAL IONS AND THEIR CATALYTIC PROPERTY IN AMMONIA OXIDATION

It has been found that the interaction between the two transition metal Mn, Co ions on B-site and their Redox property an the important factors influencing the NO-selectivity in ammonia oxidation. The NO-selectivity is related to the redox ability of Mn3+

STRUCTURE AND CATALYTIC ACTIVITY FOR PROPYLENE OXIDATION OF BI-MO-NB COMPLEX OXIDE CATALYSTS

The structure and catalytic,activity for propylene oxidation of series oxides B2Mo3-3X-Nb2XO12-4X (X=0.00, 0.02, 0.05, 0.10, 0.15, 0.20, 0.25) have been studied by means of XRD, IR, Raman, SEM, ESR and so on. The results showed that in the range of X < 0.

CATALYTIC-OXIDATION AND FLOW DETECTION OF ACETAMINOPHEN AT A DICYANOBIS(1,10-PHENANTHROLINE)IRON(II)-MODIFIED ELECTRODE

Dicyanobis(1,10-phenanthroline)iron(II)-modified glassy carbon electrodes were shown to exhibit an electrocatalytic response for the oxidation of acetaminophen with a decrease of 100 mV in the potential required. It can also inhibit the oxidation of ascor