High-throughput characterization of heterogeneous catalysts by temperature-programmed analysis method

A multistream reactor for high-throughput examining the surface acidity by NH3-TPD method by application of multistream mass spectrometer screening (MSMSS) technique has been developed. This method allows for examining the surface acidity of 10 catalyst samples in about 6 h, which is an improvement over the traditional process. The demonstration of the feasibility of high-throughput TPD can be significant in convincing the hardened traditionalists in the heterogeneous catalysis community that, combinatorial methods indeed should have an important place in scientific catalyst research and development. The developed method could also be used for almost all the temperature-programmed analysis theoretically with careful designed multistream reactors. (C) 2003 Elsevier B.V. All rights reserved.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

On the reactivity of Mo species for methane partial oxidation on Mo/HMCM-22 catalysts

By characterizing fresh and used Mo/HMCM-22 catalysts with ICP-AES, XRD, NH3-TPD technique, UV - Vis DRS and UV Raman spectroscopy, the reactivity of Mo species for methane partial oxidation into formaldehyde were directly studied with a new point of view. By comparing the fresh and used catalysts, it was found that the tetrahedral Mo species bonding chemically to the support surface were practically unchanged after the reaction, while the polymolybdate octahedral Mo species, which had a rather weak interaction with the MCM-22 zeolite, leached out during the reaction, especially when the Mo loading was high. Correspondingly, it was found from the time-on-stream reaction data that the HCHO yield remained unchanged, while COx decreased with the reaction time during the reaction. By combining the characterization results and the reaction data, it can be drawn that the isolated tetrahedral molybdenum oxo-species (T-d) is responsible for HCHO formation, while the octahedral polyoxomolybdate species (O-h) will lead to the total oxidation of methane.

Liquid-phase hydrodechlorination of chlorinated benzenes over active carbon supported nickel catalysts under mild conditions

Liquid phase hydrodechlorination of chlorinated benzenes was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete dechlorination of chlorobenzene (ClBz) was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Dichloro- and trichlorobenzenes were also hydrodechlorinated with 50-95% yields of benzene under the similar conditions, as above. The reaction follows zero-order to ClBz concentration and 1.9 order to hydrogen pressure. The reaction does not proceed in the absence of alkaline hydroxide, suggesting the complete coverage of active nickel surface with produced chlorine and the removal of the chlorine ion with hydroxide ion as a rate-limiting step. The active catalysts were characterized by H-2 chemisorption and transmission electron microscopy techniques. The apparent activity strongly depends on the active area of nickel on catalyst surface. (C) 2004 Published by Elsevier B.V.

The effect of acidity on olefin aromatization over potassium modified ZSM-5 catalysts

The transformation of olefin to aromatics over ZSM-5 catalysts with different K-loadings has been investigated both in a continuous flow fixed-bed reactor and in a pulse microreactor. Investigation of variation of olefin aromatization activity with K-loadings shows that strong acid sites are indispensable for the converting of olefin to aromatics. As intermediates of olefin aromatization process, butadiene and cyclopentene not only show much higher aromatization activity than mono-olefins, but also can be transformed into aromatics over relatively weak acid sites of K/ZSM-5. A proposal is put forward, stating that among all the steps experienced in olefins aromatization, the formation of diene or cycloolfin from mono-olefins through hydrogen transfer is the key step and can be catalyzed by strong acid sites.

Catalytic alcohols synthesis from CO and H2O on TiO2 catalysts calcined at various temperatures

The reaction performance for CO hydration on a TiO2 catalyst under different calcination temperatures was investigated. Under reaction conditions of T = 573 K, P = 0.5 MPa, CO flow rate of 30 ml min(-1), TOS = 12 h, and CO/H2O (g) = 3/2 (mol), the TiO2 catalyst with a futile content of 18% shows a maximum alcohols STY of 1.81 Mg m(-2) h(-1). In addition, the catalyst deactivation and regeneration were discussed.

Effect of support on chromium based catalysts for the oxidative dehydrogenation of C2H6 with CO2 to C2H4

The oxidative dehydrogenation of ethane (ODE) with CO2 to C2H4 has been studied over a series of Cr-based catalysts using SiO2, Al2O3, (MCM-41 zeolite) MCM-41, MgO and Silicate-2 (Si-2) as the supports. TPR, NH3-TPD, and EPR characterizations of catalysts were carried out to investigate the reduction property of Cr species on different supports, the acidities of catalysts and Cr species of 6Cr/SiO2 catalysts, respectively.