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.

Post-steam-treatment of Mo/HZSM-5 catalysts: An alternative and effective approach for enhancing their catalytic performances of methane dehydroaromatization

Post-steam-treatment is a facile and effective method for improving the catalytic performances of Mo/HZSM-5 catalysts in methane dehydroaromatization under nonoxidative conditions. The treatment can enhance the stability of the catalyst and also give a higher methane conversion and a higher yield of light aromatics, as well as a decrease in the formation rate of carbonaceous deposits. (27)Al, (29)Si, and (1)H multinuclear magic angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy, and thermogravimetric analysis measurements as well as catalytic reaction evaluations were employed to conduct comparative studies on the properties of the catalysts before and after the post-steam-treatment. The results revealed that the number of free Bronsted acid sites per unit cell decreased, while more Mo species migrated into the HZSM-5 channels for the 6Mo/HZSM-5 catalysts after the post-steam-treatment. In addition, the average pore diameter was also larger for the post-steam-treated catalysts, and this was advantageous for mass transport of the reaction products. However, a severe post-steam-treatment, i.e., with longer treating time, of the 6Mo/HZSM-5 catalyst will lead to the formation of the Al(2)(MoO(4))(3) phases, which is detrimental to the reaction.

Catalytic partial oxidation of n-heptane for hydrogen production

Partial oxidation of n-heptane (POH) for hydrogen generation was studied over several catalysts between 700 and 850degreesC. Modified Ni-based/gamma-Al2O3 catalyst exhibited not only good catalytic activity but also good carbon deposition resistance ability. Under the modified reaction conditions, 100% n-heptane conversion and 93% hydrogen selectivity can be obtained.

AgBiVMo oxide catalytic membrane for selective oxidation of propane to acrolein

A metal ions (Ag, Bi, V, Mo) modified sol-gel method was used to prepare a mesoporous Ag0.01Bi0.85V0.54Mo0.45O4 catalytic membrane which was used in the selective oxidation of propane to acrolein. By optimizing the preparation parameters, a thin and perfect catalytically active membrane was successfully prepared. SEM results showed that the membrane thickness is similar to5 mum. XRD results revealed that Ag0.01Bi0.85V0.54Mo0.45O4 with a Scheelite structure, which is catalytically active for the selective oxidation of propane to acrolein, was formed in the catalytic membrane only when AgBiVMoO concentrations were higher than 40%. Catalytic reaction results demonstrated that the selective oxidation of propane could be controlled to a certain degree, such as to acrolein, in the catalytic membrane reactor (CMR) compared to the fixed bed reactor (FBR). For example, a selectivity of 54.85% for acrolein in the liquid phase was obtained in the CMR, while only 8.31% was achieved in the FBR. (C) 2003 Elsevier B.V. All rights reserved.

A Mossbauer study of In-Fe2O3/HZSM-5 catalysts for the selective catalytic reduction of NO by methane

The selective catalytic reduction of NO by CH4 was compared over In-Fe2O3/HZSM-5 catalysts prepared by impregnation and co-impregnation methods. It was found that the catalyst preparation method greatly affected the catalyst activity. The impregnated catalyst was very active, but the co-impregnated one showed poor activity. The In Fe2O3/HZSM-5 catalysts were investigated by Mossbauer spectroscopy. The results showed that indium cations entered into the iron oxide lattice in the co-impregnated catalyst, while the impregnated catalyst exhibited a more stable structure, when both of the catalysts were treated severely in the reaction atmosphere. Characterization by means of combined in situ temperature programmed reduction (TPR)- Mossbauer spectroscopy further revealed that the performances of the two catalysts were different in the TPR processes.

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.

Influence of iron promoter on catalytic properties of Rh-Mn-Li/SiO2 for CO hydrogenation

The effect of iron promoter on the catalytic properties of Rh-Mn-Li/SiO2 catalyst in the synthesis Of C-2 oxygenates from syngas was investigated by means of the following techniques: CO hydrogenation reaction, temperature-programmed reduction (TPR), temperature-programmed desorption and reaction of adsorbed CO (CO-TPD and TPSR) and pulse adsorption of CO. The results showed that the addition of iron promoter could improve the activity of the catalysts. Unexpectedly, the yield of C-2 oxygenates increased greatly from 331.6 up to 457.5 g/(kg h) when 0.05% Fe was added into Rh-Mn-Li/SiO2 catalyst, while no change in the selectivity to C-2 oxygenates was observed. However, the activity and selectivity Of C-2 oxygenates were greatly decreased if the Fe amount exceeded 1.0%. The existence of a little iron decreased the reducibility of Rh precursor, while the reduction of Fe component itself became easier. CO uptake decreased with increasing the quantity of Fe addition. This phenomenon was further confirmed by CO-TPD results. The CO-TPD and TPSR results showed that only the strongly adsorbed CO could be hydrogenated, while the weakly adsorbed CO was desorbed. We propose that Fe is highly dispersed and in close contact with Rh and Mn; such arrangements were responsible for the high yield Of C-2 oxygenates. (C) 2002 Elsevier Science B.V. All rights reserved.

Novel activity of TiO2 for catalytic conversion of CO and H2O to alcohols in the presence of K2CO3

In the presence of K2CO3, TiO2 shows good catalytic activity and stability for the alcohols synthesis from CO and H2O. CO conversion of 7.6% and the STY of MeOH (about 24 mg g(-1) h(-1)) and EtOH (about 8 mg g(-1) h(-1)) are obtained under reaction conditions of T = 573 K, P = 0.5 MPa, CO flow rate of 30 ml min(-1) and CO/H2O = 3/2 during the period of 12 h to 44 h time-on-stream.