FTIR Investigation of the H2, N2, and C2H4 Molecular Complexes Formed on the Cr(II) Sites in the Phillips Catalyst: a Preliminary Step in the understanding of a Complex System
- 15 July 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 109 (31) , 15024-15031
- https://doi.org/10.1021/jp051826w
Abstract
This work reports the first complete FTIR characterization of H2, N2 and C2H4 molecular complexes formed on the Cr(II) sites in the Phillips catalyst. The use of a silica aerogel as support for Cr(II) sites, substituting the conventional aerosil material, allowed us to obtain a remarkable increase in the signal-to-noise ratio of the IR spectra of adsorbed species. The improvement is directly related to an increase of the surface area of the support (∼700 m2g-1) and to an almost complete absence of scattering [Groppo et al., Chem. Mater. 2005, 17, 2019−2027]. The use of this support and the adoption of suitable experimental conditions results, for the first time, in the clear observation of H2 and N2 adducts formed on two different types of Cr(II) sites, thus yielding important information on the coordinative state of the Cr(II) ions, which well agrees with the evidences provided in the past by other probe molecules. Furthermore, we report the first complete characterization of the C2H4 π-complexes formed on Cr(II) sites. These results are particularly important in the view of the understanding of the polymerization mechanism, since the C2H4 coordination and the formation of π-bonded complexes are the first steps of the reaction.Keywords
This publication has 62 references indexed in Scilit:
- New Strategies in the Raman Study of the Cr/SiO2 Phillips Catalyst: Observation of Molecular Adducts on Cr(II) SitesChemistry of Materials, 2005
- Vibrational and Thermodynamic Properties of H2Adsorbed on MgO in the 300−20 K IntervalThe Journal of Physical Chemistry B, 2004
- Temperature resolved FTIR spectroscopy of Cr2+/SiO2catalysts: acetylene and methylacetylene oligomerisationPhysical Chemistry Chemical Physics, 2003
- The surface chemistry of amorphous silica. Zhuravlev modelColloids and Surfaces A: Physicochemical and Engineering Aspects, 2000
- Well-defined carbonyl and dinitrogen complexes of ruthenium supported on dealuminated Y zeolite. Analogies and differences to the homogeneous caseJournal of Molecular Catalysis A: Chemical, 1999
- Monolayers of ortho-H2, para-H2, para-D2 and normal-H2 adsorbed on NaCl(001) single crystal surfacesThe Journal of Chemical Physics, 1999
- Estimate of ionicity of zeolite NaA using the frequency shift values of physisorbed molecular hydrogenMolecular Physics, 1996
- Surface Chemistry in a Zeolite Matrix. Well-Defined Dinitrogen Complexes of Rhodium Supported on Dealuminated Y ZeoliteJournal of the American Chemical Society, 1994
- An FTIR spectroscopic view of the initiation of ethylene polymerization on Cr/SiO2 catalystJournal of Catalysis, 1992
- IR Studies of Coordinatively Unsaturated Surface Compounds on Silica Gel. IV. CO Complexes of Chromium(II) and Chromium(III)Zeitschrift für anorganische und allgemeine Chemie, 1981