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Facile Ester Synthesis on Ag-Modified Nanoporous Au: Oxidative Coupling of Ethanol and 1-Butanol Under UHV Conditions

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Abstract

A dilute Ag alloy of nanoporous Au (npAu) has been shown to self-couple methanol with 100 % selectivity and high conversion under catalytic flow conditions. However, because prior studies in flow reactors showed difficulty in self-coupling ethanol and 1-butanol over npAu in flow reactors, the inherent capability on npAu for self-coupling of ethanol and 1-butanol was examined under ultrahigh vacuum conditions on identical npAu catalysts. This study shows that the oxygen-covered Ag-modified npAu does efficiently effect the self-coupling of ethanol and 1-butanol under UHV conditions. The coupling is initiated by adsorbed atomic oxygen formed from O2 dissociation via a chemisorbed molecular state. The amount of ester formed increases with the degree of oxygen precoverage at the expense of aldehyde production. Repeated annealing of the catalyst above 550 K for temperature programmed reaction changes the ligament and pore sizes, affecting the product distribution, but high reactivity is sustained over many heating cycles.

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Acknowledgments

We gratefully acknowledge the support of this work by the U.S. Department of Energy, Basic Energy Sciences, Catalysis Science Program (DE-FG-02-84ER13289). Work at LLNL was performed under the auspices of the U.S. Department of Energy by LLNL under Contract DE-AC52-07NA27344. Correspondence and requests for materials should be addressed to C.M.F.

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Authors and Affiliations

  1. Chemistry and Biochemistry, Brigham Young University, Provo, USA

    Kara J. Stowers

  2. School of Engineering and Applied Sciences, Harvard University, Cambridge, USA

    Robert J. Madix

  3. Lawrence Livermore National Laboratory, Livermore, USA

    Monika M. Biener & Juergen Biener

  4. Harvard University, Cambridge, USA

    Cynthia M. Friend

Authors
  1. Kara J. Stowers
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  2. Robert J. Madix
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  3. Monika M. Biener
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  4. Juergen Biener
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  5. Cynthia M. Friend
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Corresponding author

Correspondence to Cynthia M. Friend.

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Stowers, K.J., Madix, R.J., Biener, M.M. et al. Facile Ester Synthesis on Ag-Modified Nanoporous Au: Oxidative Coupling of Ethanol and 1-Butanol Under UHV Conditions. Catal Lett 145, 1217–1223 (2015). https://doi.org/10.1007/s10562-015-1525-4

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  • DOI: https://doi.org/10.1007/s10562-015-1525-4

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