Operando X-ray Absorption Spectroscopy Studies of Sintering for Supported Copper Catalysts during Liquid-phase Reaction

Authors

  • Brandon J. O'Neill,

    1. Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53705 (United States), Fax: (+1) 608-262-5434
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  • Dr. Jeffrey T. Miller,

    1. Chemical Science and Engineering, Argonne National Laboratory, Argonne, IL 60439 (United States)
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  • Dr. Paul J. Dietrich,

    1. Chemical Engineering, Purdue University, West Lafayette, IN 47907 (United States)
    2. Current Address: BP Products North America, 150 W. Warrenville Road, Naperville, IL 60563 (USA)
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  • Fred G. Sollberger,

    1. Chemical Engineering, Purdue University, West Lafayette, IN 47907 (United States)
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  • Prof. Fabio H. Ribeiro,

    1. Chemical Engineering, Purdue University, West Lafayette, IN 47907 (United States)
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  • Prof. James A. Dumesic

    Corresponding author
    1. Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53705 (United States), Fax: (+1) 608-262-5434
    • Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53705 (United States), Fax: (+1) 608-262-5434

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Abstract

Operando X-ray absorption spectroscopy is used to measure simultaneous changes in catalyst structure and changes in catalytic activity versus time during the liquid phase hydrogenation of furfural over supported copper catalysts. This approach allows the size of the copper nanoparticles to be monitored continuously versus time-on-stream, such that these changes in dispersion can be accounted for in the calculation of turnover frequency. It is shown that sintering of the copper nanoparticles is the predominant mode of catalyst deactivation for a Cu/γ-Al2O3 catalyst throughout its time-on-stream, leading to irreversible loss of catalytic activity. In contrast, this mode of deactivation is eliminated by atomic layer deposition of an alumina overcoat; however, deposition of carbonaceous deposits in the small pores of the overcoat leads to deactivation that is reversible upon calcination of the catalyst.

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