Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts for NH3 decomposition

A series of nano-sized Ni/Al2O3 and Ni/La-Al2O3 catalysts that possess high activities for NH3 decomposition have been successfully synthesized by a coprecipitation method. The catalytic performance was investigated under the atmospheric conditions and a significant enhancement in the activity after the introduction of La was observed. Aiming to study the influence of La promoter on the physicochemical properties, we characterized the catalysts by N-2 adsorption/desorption, XRD, H-2-TPR, chemisorption and TEM techniques. Physisorption results suggested a high specific surface area and XRD spectra showed that nickel particles are in a highly dispersed state. A combination of XRD, TEM and chemisorption showed that Ni-0 particles with the average size lower, than 5.0 nm are always obtained even though the Ni loading ranged widely from 4 to 63 %. Compared with the Ni/Al2O3 catalysts, the Ni/La-Al2O3 ones with an appropriate amount of promoter enjoy a more open mesoporous structure and higher dispersion of Ni. Reduction kinetic studies of prepared catalysts were investigated by temperature-programmed reduction (TPR) method and the fact that La additive partially destroyed the metastable Ni-Al mixed oxide phase was detailed. (c) 2005 Elsevier B.V. All rights reserved.

The role of Sn in Pt-Sn/CeO2 catalysts for the complete oxidation of ethanol

The structural features and catalytic properties of Pt-Sn/CeO2 catalysts prepared by modified polyol method were extensively investigated for the complete oxidation of ethanol. CO chemisorption, TPR, DTA and XPS measurements identically indicated that the electronic configuration of Pt by Sn as well as the formation of PtSn alloy were the key factors in determining the nature of the active sites, A strong Pt/Sn atomic ratio dependence of catalytic perfortmances was observed. which was explained in terms of the change., in the Surface structure of metal phases and the electronic Pt-Sn interaction. (c) 2005 Elsevier B.V. All rights reserved.

Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.

Complete hydrodechlorination of chlorobenzene and its derivatives over supported nickel catalysts under liquid phase conditions

Liquid phase hydrodechlorination of chlorobenzene was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete hydrodechlorination of chlorobenzene was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Aryl halides, three chlorotoluenes (o-, m- and p-), three chloroanilines, three chlorobenzotrifluorides, three dichlorobenzenes and two trichlorobenzenes (1,2,3- and 1,2,4-) were also completely hydrodechlorinated under the similar conditions. Chlorobenzene derivatives having either an electron-donating group or an electron-withdrawing group decreased their reactivities with respect to the unsubstituted chlorobenzene.

Preparation and characterization of multi-walled carbon nanotubes supported PtRu catalysts for proton exchange membrane fuel cells

A series of PtRu nanocomposites supported on H2O2-oxidized multi-walled carbon nanotubes (MWCNTs) were synthesized via two chemical reduction methods - one used aqueous formaldehyde (HCHO method) and the other used ethylene glycol (EG method) as the reducing agents. The effects of the solvents (water and ethylene glycol) and the surface composition of the MWCNTs on the deposition and the dispersion of the metal particles were investigated using N-2 adsorption. TEM. ICP-AES. FTIR and TPD. The wetting heats of the MWCNTs in corresponding solvents were also measured. The characterizations suggest that combination of the surface chemistry of the MWCNTs with the solvents decides the deposition and the dispersion of the metal nanoparticles. These nanocomposites were evaluated as proton exchange membrane fuel cell anode catalyts for oxidation of 50 ppm CO contaminated hydrogen and compared with a commercial PtRu/C catalyst. The data reveal superior performances for the nanocomposites prepared by the EG method to those by the HCHO method and even to that for tile Commercial analogue. Structure performance relationship of the nanocomposites was also studied. (C) 2005 Elsevier Ltd. All rights reserved.

The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer-Tropsch reaction

The cobalt carbide (Co2C) species was formed in some activated carbon supported cobalt-based (Co/AC) catalysts during the activation of catalysts. It was found that the activity of Fischer-Tropsch reaction over Co-based catalysts decreased due to the formation of cobalt carbide species. Some promoters and pretreatment of activated carbon with steam could restrain the formation of cobalt carbide.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 Elsevier B.V. All rights reserved.

Autothermal reforming of n-octane on Ru-based catalysts

In an attempt to effectively integrate catalytic partial oxidation (CPO) and steam reforming (SR) reactions on the same catalyst, autothermal reforming (ATR) of n-octane was addressed based on thermodynamic analysis and carried out on a non-pyrophoric catalyst 0.3 wt.% Ru/K2O-CeO2/gamma-Al2O3. The ATR of n-octane was more efficient at the molar ratio Of O-2/C 0.35-0.45 and H2O/C 1.6-2.2 (independent parameters), respectively, and reforming temperature of 750-800 degrees C (dependent parameter). Among the sophisticated reaction network, the main reaction thread was deducted as: long-chain hydrocarbon -> CH4, short-chain hydrocarbon -> CO2, CO and H-2 formation by steam reforming, although the parallel CPO, decomposition and reverse water gas shift reaction took place on the same catalyst. Low temperature and high steam partial pressure had more positive effect on CH4 SR to produce CO2 other than CO. This was verified by the tendency of the outlet reformate to the equilibrium at different operation conditions. Furthermore, the loss of active components and the formation of stable but less active components in the catalyst in the harsh ATR atmosphere firstly make the CO inhibition capability suffer, then eventually aggravated the ATR performance, which was verified by the characterizations of X-ray fluorescence, BET specific surface areas and temperature programmed reduction. (c) 2005 Elsevier B.V. All rights reserved.

Butene catalytic cracking to propene and ethene over potassium modified ZSM-5 catalysts

Catalytic cracking of butene over potassium modified ZSM-5 catalysts was carried out in a fixed-bed microreactor. By increasing the K loading on the ZSM-5, butene conversion and ethene selectivity decreased almost linearly, while propene selectivity increased first, then passed through a maximum (about 50% selectivity) with the addition of ca. 0.7-1.0% K, and then decreased slowly with further increasing of the K loading. The reaction conditions were 620 degrees C, WHSV 3.5 h(-1), 0.1 MPa 1-butene partial pressure and 1 h of time on stream. Both by potassium modification of the ZSM-5 zeolite and by N(2) addition in the butene feed could enhance the selectivity towards propene effectively, but the catalyst stability did not show any improvement. On the other hand, addition of water to the butene feed could not only increase the butene conversion, but also improve the stability of the 0.7%K/ZSM-5 catalyst due to the effective removal of the coke formed, as demonstrated by the TPO spectra. XRD results indicated that the ZSM-5 structure of the 0.07% K/ZSM-5 catalyst was not destroyed even under this serious condition of adding water at 620 degrees C.

Electrode catalysts behavior during direct ethanol fuel cell life-time test

In the present paper, a 60 h life-time test of a direct ethanol fuel cell (DEFC) at a current density of 20 mA cm(-2) (the beginning 38 h) and 40 mA cm(-2) (the last 22 h) was carried out. After the life-time test, the MEA could not achieve the former performance. X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) were employed to characterize the anode and cathode catalyst before and after the life-time test. The XRD and TEM results showed that the particle size of the anode catalyst increased from 2.3 to 3.3 nm and the cathode from 3.0 to 4.6 nm. The EDX results of PtSn/C anode catalysts before and after the life-time test indicated that the content of the oxygen and tin, especially the content of the platinum, decreased prominently after the life-time test. The results suggest that the agglomeration of electrocatalysts, the destruction of the anode catalyst together with the fuel/water crossover from anode to cathode concurrently contribute to the performance degradation of the DEFC. (C) 2005 Elsevier B.V. All rights reserved.