MoNi/gamma-Al2O3 Catalyst: Preparation and Catalytic Activity for Acetic Acid Hydrotreating

MoNi/gamma-Al2O3 catalysts were prepared by the impregnation method. The catalyst samples were characterized by XRD and TPR. The effects of Mo promoter content and the catalyst reducing temperature Oil hydrotreatment activity of the catalyst were studied under 200 degrees C and 3 MPa hydrogen pressure using acetic acid as the model compound. The XRD results indicate that the addition of Mo promoter is beneficial to the uniformity of nickel species on the catalyst and decreases the Interaction between nickel species and the support Which results in the decrease the of NiAl2O4 spinel formation. The addition of Mo promoter also decreases the reducing temperature of the catalyst. After the catalyst of 0.06 MoNi/gamma-Al2O3 being reduced Under the atmosphere of H-2/N-2(5/95, V/V), nickel oxide was reduced to Ni-0. The reaction was promoted obviously upon the addition of the MoNi/gamma-Al2O3 catalyst reduced at 600 degrees C. The Mo-modified Ni/gamma-Al2O3 catalyst reduced at 600 degrees C displayed the highest activity during the reaction, the conversion of acetic acid reached the highest point of 33.2%. The products included ethyl acetate and water.

The remarkable effect of In2O3 on the catalytic activity of In/HZSM-5 for the reduction of NO with CH4

In/HZSM-5/ln(2)O(3) catalyst that contained two different kinds of In induced by the impregnating and the physical mixing method respectively has shown remarkable activity for the CH4-SCR of NOx comparing with In/HZSM-5. The addition of In2O3 into In/HZSM-5 improved the NO conversion through enhancing the adsorption of NOx over In/HZSM-5.

Hydrothermal stability and catalytic activity of aluminum-containing mesoporous ethane-silicas

Aluminum was incorporated into the mesoporous framework of ethane-silica by one-pot condensation of Al(OiPr)(3) with 1,2-bis(trimethoxysilyl)ethane using octadecyltrimethylammonium chloride as surfactant. Powder X-ray diffraction patterns, nitrogen sorption analysis, and TEM results reveal the formation of an ordered mesoporous material with uniform porosity. Al-27 MAS NMR confirms the incorporation of aluminum in the framework. The synthesized materials exhibit extremely high hydrothermal stability in boiling water (no obvious change of mesostructure and textural properties was observed even after refluxing in water for 100 h), which could be mainly contributed to the ethane-bridged mesoporous framework. The aluminum-containing mesoporous ethane-silicas are efficient catalysts for the alkylation of 2,4-di-tert-butylphenol by cinnamyl alcohol to yield a flavan.

Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine

A series of novel ferrocenylphosphine-ketimine ligands 6 were prepared by reaction of (R,S-p)-PPFNH2-R or (S,S-p)-PPFNH2 with a variety of m-substituted acetophenones. A different catalytic activity was observed between ferrocenylphosphine-ketimine ligands and corresponding aldimine ligands. The efficiency and diastereomeric impact of these ferrocenylphosphine-ketimine ligands in Pd-catalyzed asymmetric allylic alkylation were first investigated, and higher enantioselectivity of over 98% e.e. with 95% yield was obtained by the use of ferrocenylphosphine-ketimine ligands. However, in Rh-catalyzed asymmetric hydrosilylation of aryl ketones, only 42% e.e. was obtained by the use of ferrocenylphosphine-ketimine ligands compared to 90% e.e. with the use of aldimine ligands. (C) 2003 Elsevier Ltd. All rights reserved.

Reduction property and catalytic activity of Ce1-XNiXO2 mixed oxide catalysts for CH4 oxidation

Ce1-XNiXO2 oxides with X varying from 0.05 to 0.5 were prepared by different methods and characterized by XRD and TPR techniques. Ce(0.7)Mi(0.3)O(2) sample prepared by sol-gel method shows the highest reducibility and the highest catalytic activity for methane combustion. Three kinds of Ni phases co-exist in the Ce1-XNiXO2 catalysts prepared by sol-gel method: (i) aggregated NiO on the support CeO2, (ii) highly dispersed NiO with strong interaction with CeO2 and (iii) Ni atoms incorporated into CeO2 lattice. The distribution of different Ni species strongly depends on the preparation methods. The highly dispersed NiO shows the highest activity for methane combustion. The NiO aggregated on the support CeO2 shows lower catalytic activity for methane combustion, while the least catalytic activity is found for the Ni species incorporated into CeO2. Any oxygen vacancy formed in CeO2 lattice due to the incorporating of Ni atoms adsorbs and activates the molecular oxygen to form active oxygen species. So the highest catalytic activity for methane combustion on Ce0.7Ni0.3O2 catalyst is attributed not only to the highly dispersed Ni species but also to the more active oxygen species formed. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of addition of Zn on the catalytic activity of a Co/HZSM-5 catalyst for the SCR of NOx with CH4

The selective catalytic reduction (SCR) of NOx by methane in the presence of excess oxygen was studied on a Zn-Co/HZSM-5 catalyst. It was found that the addition of Zn could improve effectively the selectivity of methane towards NOx reduction. When prepared by a coimpregnation method, the Zn-Co/HZSM-5 catalyst showed much higher catalytic activity than the two catalysts of a Zn/Co/HZSM-5 and Co/Zn/HZSM-5 prepared by the successive impregnation method. It is considered that there exists a cooperative effect among the Zn, Co and zeolite, which enhances the reduction of NO to NO2 reaction and the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

Pretreatment of polymer-supported Pd-Co and its catalytic activity

Various pretreatments of poly (N-vinyl-2-pyrrolidone) (PVP) protected palladium-cobalt system result in different catalytic activities in the hydrodechlorination of chlorobenzene.

Pyrrolide-supported lanthanide alkyl complexes. Influence of ligands on molecular structure and catalytic activity toward isoprene polymerization

The N,N- bidentate ligands 2- {( N- 2,6- R) iminomethyl)} pyrrole ( HL1, R) dimethylphenyl; HL2, R) diisopropylphenyl) have been prepared. HL1 reacted readily with 1 equiv of lanthanide tris( alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), affording lanthanide bis(alkyl) complexes L(1)Ln(CH2SiMe3)(2)(THF)(n) (1a, Ln= Lu, n = 2; 1b, Ln = Sc, n = 1) via alkane elimination. Reaction of the bulky ligand HL2 with 1 equiv of Ln(CH2SiMe3)(3)( THF)(2) gave the bis(pyrrolylaldiminato) lanthanide mono(alkyl) complexes L(2)(2)Ln- (CH2SiMe3)(THF) (2a, Ln) Lu; 2b, Ln = Sc), selectively. The N,N- bidentate ligand HL3, 2- dimethylaminomethylpyrrole, reacted with Ln( CH2SiMe3) 3( THF) 2, generating bimetallic bis( alkyl) complexes of central symmetry ( 3a, Ln = Y; 3b, Ln = Lu; 3c, Ln = Sc). Treatment of the N,N,N,N- tetradentate ligand H2L4, 2,2'-bis(2,2-dimethylpropyldiimino) methylpyrrole, with equimolar Lu(CH2SiMe3)(3)(THF)(2) afforded a C-2- symmetric binuclear complex ( 4). Complexes 3a, 3b, 3c, and 4 represent rare examples of THF- free binuclear lanthanide bis( alkyl) complexes supported by non- cyclopentadienyl ligands. All complexes have been tested as initiators for the polymerization of isoprene in the presence of AlEt3 and [ Ph3C][B(C6F5)(4)]. Complexes 1a, 1b, and 3a show activity, and 1b is the most active initiator, whereas 2a, 2b, 3b, 3c, and 4 are inert.

Rare earth metal bis(alkyl) complexes bearing amino phosphine ligands: Synthesis and catalytic activity toward ethylene polymerization

Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)(2) (HL1) and Lu(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h generated mono(alkyl) complex (L-1)(2)Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)(2) (HL2) with Lu(CH2SiMe3)(3)(THF)(2) afforded (L-2)(2)Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L-2)(3)Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)(2) (HL3) swiftly reacted with Ln(CH2SiMe3)(3)(THF)(2) at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L(3)Ln(CH2SiMC3)(2)(THF)(n) (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and [Ph3C][B(C6F5)(4)], was able to catalyze the polymerization of ethylene to afford linear polyethylene.

Yttrium bis(alkyl) and bis(amido) complexes bearing N,O multidentate ligands. Synthesis and catalytic activity towards ring-opening polymerization of L-lactide

Methoxy-modified beta-diimines HL1 and HL2 reacted with Y(CH2SiMe3)(3)(THF)(2) to afford the corresponding bis(alkyl)s [(LY)-Y-1(CH2SiMe3)(2)] (1) and [(LY)-Y-2(CH2SiMe3)(2)] (2), respectively. Amination of 1 with 2,6-diisopropyl aniline gave the bis(amido) counterpart [(LY)-Y-1{N(H)(2,6-iPr(2)-C6H3)}(2)] (3), selectively. Treatment of Y(CH2SiMe3)(3)(THF)(2) with methoxy-modified anilido imine HL3 yielded bis(alkyl) complex [(LY)-Y-3(CH2SiMe3)(2)(THF)] (4) that sequentially reacted with 2,6-diisopropyl aniline to give the bis(amido) analogue [(LY)-Y-3{N(H)(2,6-iPr(2)-C6H3)}(2)] (5). Complex 2 was "base-free" monomer, in which the tetradentate beta-diiminato ligand was meridional with the two alkyl species locating above and below it, generating tetragonal bipyramidal core about the metal center. Complex 3 was asymmetric monomer containing trigonal bipyramidal core with trans-arrangement of the amido ligands. In contrast, the two cis-located alkyl species in complex 4 were endo and exo towards the 0,N,N tridentate anilido-imido moiety. The bis(amido) complex 5 was confirmed to be structural analogue to 4 albeit without THF coordination. All these yttrium complexes are highly active initiators for the ring-opening polymerization Of L-LA at room temperature.

The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.

Synthesis and structural characterization of beta-diketiminate-lanthanide Amides and their catalytic activity for the polymerization of methyl methacrylate and epsilon-caprolactone

The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction.