Geometric and electronic structures of Pt/V2O5/TiO2 diesel engine exhaust gas purification catalysts before and after aging

In spite of their technical use and relevance the structural properties of diesel engine exhaust gas catalysts are not yet understood on an atomic scale. This study investigates structural changes during aging of Pt/V2O5/TiO2 based catalysts in order to get insight into the mutual interaction of the active constituents. X-ray photoelectron spectrometry, secondary ion mass spectrometry and X-ray absorption fine structure measurements were used to characterize the chemical composition and the electronic and geometric structure of the catalyst's surface and bulk. In the freshly prepared catalyst the interaction among the active species turns out to be moderate, i.e. vanadium is present in a distorted 5+ state. TiO2, as expected, is present as in the precursor and Pt is found to form monometallic clusters of about 16 A diameter without any significant interaction with the other metal species. Particularly, no alloying is observed. Upon aging of the catalyst vanadium is reduced to 4+ and preferentially orders in a VO2 structure although other minor phases may also be present. This is accompanied by a partial transformation of TiO2 from the initial anatase to rutile. Like V, Pt undergoes a strong modification upon aging: Pt is partly oxidized but still forms metal particles with a slightly smaller size.

[1]  Marius Grundmann,et al.  The contribution of particle core and surface to strain, disorder and vibrations in thiolcapped CdTe nanocrystals , 1998 .

[2]  B. Weckhuysen,et al.  Structure and reactivity of surface vanadium oxide species on oxide supports , 1997 .

[3]  E. C. Alyea,et al.  Influence of Metal Oxide Modification of Alumina on the Dispersion and Activity of Vanadia Catalysts , 1997 .

[4]  S. Nunes,et al.  Structural Characterization of Catalytically Active Metal Nanoclusters in Poly(amide imide) Films with High Metal Loading , 1997 .

[5]  Jeffrey T. Miller,et al.  On the Relation Between Particle Morphology, Structure of the Metal-Support Interface and Catalytic Properties of Pt/gamma-Al2O3. , 1996 .

[6]  J. A. A. Tillaart,et al.  Effect of support oxide and noble metal precursor on the activity of automotive diesel catalysts , 1996 .

[7]  Gordon E. Brown,et al.  Coordination chemistry of Ti(IV) in silicate glasses and melts: I. XAFS study of titanium coordination in oxide model compounds , 1996 .

[8]  D. Lindner,et al.  Advanced exhaust gas aftertreatment systems for gasoline and diesel fuelled vehicles , 1996 .

[9]  M. Delamar,et al.  Chapter 7.1 X-ray photoelectron spectroscopy of TiO2/V2O5 catalysts , 1994 .

[10]  G. Bond Chapter 7.2 Investigation of the Eurocat V2O5/TiO2 catalysts and of the TiO2 support by secondary-ion mass spectrometry , 1994 .

[11]  J. Rehr,et al.  Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment. , 1993, Physical review. B, Condensed matter.

[12]  F. Parmigiani,et al.  An X-ray photoelectron spectroscopy study of the vanadia-titania catalysts , 1993 .

[13]  J. Rehr,et al.  High-order multiple-scattering calculations of x-ray-absorption fine structure. , 1992, Physical review letters.

[14]  Smith,et al.  Interaction of SO2 with nearly perfect and defect TiO2(110) surfaces. , 1987, Physical review. B, Condensed matter.

[15]  D. H. Maylotte,et al.  A Study of the K-edge Absorption Spectra of Selected Vanadium Compounds. , 1984 .

[16]  D. Sayers,et al.  Quantitative technique for the determination of the number of unoccupied d-electron states in a platinum catalyst using the L2,3 x-ray absorption edge spectra , 1984 .

[17]  W. Göpel,et al.  Intrinsic defects of Ti O 2 (110): Interaction with chemisorbed O 2 , H 2 , CO, and C O 2 , 1983 .

[18]  G. Sawatzky,et al.  X-ray photoelectron and Auger spectroscopy study of some vanadium oxides , 1979 .

[19]  R. Greegor,et al.  Effect of chemical environment on magnitude of x‐ray absorption resonance at LIII edges. Studies on metallic elements, compounds, and catalysts , 1979 .

[20]  R. Benfield Mean coordination numbers and the non-metal–metal transition in clusters , 1992 .

[21]  Satohiro Yoshida,et al.  X-ray absorption (EXAFS/XANES) study of supported vanadium oxide catalysts. Structure of surface vanadium oxide species on silica and γ-alumina at a low level of vanadium loading , 1988 .