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Operando Molecular Spectroscopy During Ethylene Polymerization by Supported CrO x /SiO2 Catalysts: Active Sites, Reaction Intermediates, and Structure-Activity Relationship

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Abstract

Time-resolved operando molecular spectroscopy was applied during ethylene polymerization by supported CrO x /SiO2 catalysts to investigate the structure-activity relationships for this important industrial catalytic reaction. A combination of spectroscopic techniques (Raman, UV–Vis, XAS, DRIFTS and TPSR) during ethylene polymerization allows for the first time to monitor the molecular events taking place during activation of supported CrO x /SiO2 catalysts by ethylene and establishment of the structure-activity relationships for this reaction. Based on complementary DFT computational studies, a new initiation mechanism for ethylene polymerization is proposed. During reaction, the initial surface Cr+6O x sites reduce to Cr+3 sites to form Cr–(CH2)2CH=CH2 and Cr–CH=CH2 reaction intermediates with the latter representing the catalytic active site.

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Acknowledgments

A. Chakrabarti and I. E. Wachs would like to acknowledge Professor A. I. Frenkel and Y. Li (Department of Physics, Yeshiva University) for assistance with the XAS collection and analysis. They acknowledge the facilities support provided at the National Synchrotron Light Source at Brookhaven National Laboratory (U. S. DOE BES, Contract No. DE-SC1112704) and the Synchrotron Catalysis Consortium (U. S. DOE BES, Grant No. DE-SC0012335). They would also like to acknowledge Dr. Christopher Keturakis for the use of his XAS data of the reference compounds. The computational research was supported in part by PL-Grid Infrastructure. Other computing resources from Academic Computer Centre CYFRONET AGH (grants MNiSW/IBM_BC_HS21/PK/003/2013 and MNiSW/IBM_BC_HS21/PK/037/2014) are acknowledged.

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Authors and Affiliations

  1. Operando Molecular Spectroscopy and Catalysis Laboratory, Department of Chemical and Biomolecular Engineering, Lehigh University, Bethlehem, PA, 18015, USA

    Anisha Chakrabarti & Israel E. Wachs

  2. Faculty of Chemical Engineering and Technology, Cracow University of Technology, ul. Warszawska 24, 31-155, Kraków, Poland

    Maciej Gierada & Jaroslaw Handzlik

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  1. Anisha Chakrabarti
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  2. Maciej Gierada
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  4. Israel E. Wachs
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Correspondence to Israel E. Wachs.

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Chakrabarti, A., Gierada, M., Handzlik, J. et al. Operando Molecular Spectroscopy During Ethylene Polymerization by Supported CrO x /SiO2 Catalysts: Active Sites, Reaction Intermediates, and Structure-Activity Relationship. Top Catal 59, 725–739 (2016). https://doi.org/10.1007/s11244-016-0546-6

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