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Effect of Promoter M (M = Au, Ag, Cu, Ce, Fe, Ni, Co, Zn) on the Activity of Pd–M/Al2O3 Catalysts of Ethanol Conversion into α-Alcohols

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Abstract

Pd/Al2O3 and Pd–M/Al2O3 catalysts (M = Au, Ag, Cu, Ce, Fe, Ni, Co, Zn) were obtained by ion exchange and impregnation. Pd/Al2O3 had high initial activity in the conversion of ethanol into α-alcohols, but lost 90% of its activity after 10 h of operation because of deactivation caused by the chemisorption of the by-product (CO) on Pd atoms. Modification of Pd with gold or silver led to an increase in the rate of Pd deactivation. As a result, the Pd–Au and Pd–Ag systems were less active and stable. In contrast, the Pd–Fe, Pd–Co, Pd–Ni, Pd–Cu, Pd–Zn, and Pd–Ce systems exhibited higher resistance to CO poisoning than Pd and demonstrated high activity and stability. The observed tendencies in the catalytic action of the mono- and bimetallic systems were explained within the framework of the d band model proposed by Hammer and Norskov. Pd–Cu/Al2O3 was most effective in the target process; it is not poisoned by CO and allows ethanol conversion into α-alcohols at 95% selectivity, while the time of its stable operation is at least 100 h. The structure of the Pd–Cu catalytic system was studied by TEM, EDA, XPS, TPR-H2, and TPD-NH3. A model of active catalyst sites was proposed.

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ACKNOWLEDGMENTS

We are grateful to K.I. Maslakov, S.V. Maksimov, and S.V. Dvoryak (Multiaccess Center “Nanochemistry and Nanomaterials”, Moscow State University) for help with studies of the samples using the equipment obtained under the Program of Development of Moscow State University.

Funding

This study was performed under the government contract at the Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences.

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Authors and Affiliations

  1. Faculty of Chemistry, Moscow State University, 119991, Moscow, Russia

    S. A. Nikolaev, D. I. Ezzhelenko & I. N. Krotova

  2. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia

    M. V. Tsodikov, A. V. Chistyakov & P. A. Chistyakova

Authors
  1. S. A. Nikolaev
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  2. M. V. Tsodikov
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  3. A. V. Chistyakov
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  4. P. A. Chistyakova
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  5. D. I. Ezzhelenko
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  6. I. N. Krotova
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Corresponding author

Correspondence to S. A. Nikolaev.

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Translated by L. Smolina

Abbreviations and notation: TEM, transmission electron microscopy; EDA, energy dispersive analysis; XPS, X-ray photoelectron spectroscopy; TPR-H2, temperature-programmed reduction with hydrogen; TPD-NH3, temperature-programmed desorption with ammonia; AAS, atomic absorption spectrometry.

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Nikolaev, S.A., Tsodikov, M.V., Chistyakov, A.V. et al. Effect of Promoter M (M = Au, Ag, Cu, Ce, Fe, Ni, Co, Zn) on the Activity of Pd–M/Al2O3 Catalysts of Ethanol Conversion into α-Alcohols. Kinet Catal 61, 894–902 (2020). https://doi.org/10.1134/S0023158420060117

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