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Title: Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals

Abstract

Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank themore » groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1424833
Report Number(s):
PNNL-SA-125668
Journal ID: ISSN 0021-9517
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Catalysis; Journal Volume: 359; Journal Issue: C
Country of Publication:
United States
Language:
English
Subject:
electrocatalysis; hydrogenation; benzaldehyde; aqueous phase reactions; carbon-supported metals

Citation Formats

Song, Yang, Sanyal, Udishnu, Pangotra, Dhananjai, Holladay, Jamie D., Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A. Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals. United States: N. p., 2018. Web. doi:10.1016/j.jcat.2017.12.026.
Song, Yang, Sanyal, Udishnu, Pangotra, Dhananjai, Holladay, Jamie D., Camaioni, Donald M., Gutiérrez, Oliver Y., & Lercher, Johannes A. Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals. United States. doi:10.1016/j.jcat.2017.12.026.
Song, Yang, Sanyal, Udishnu, Pangotra, Dhananjai, Holladay, Jamie D., Camaioni, Donald M., Gutiérrez, Oliver Y., and Lercher, Johannes A. Thu . "Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals". United States. doi:10.1016/j.jcat.2017.12.026.
@article{osti_1424833,
title = {Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals},
author = {Song, Yang and Sanyal, Udishnu and Pangotra, Dhananjai and Holladay, Jamie D. and Camaioni, Donald M. and Gutiérrez, Oliver Y. and Lercher, Johannes A.},
abstractNote = {Abstract Selective reduction of benzaldehyde to benzyl alcohol on C-supported Pt, Rh, Pd, and Ni in aqueous phase was conducted using either directly H2 (thermal catalytic hydrogenation, TCH) or in situ electrocatalytically generated hydrogen (electrocatalytic hydrogenation, ECH). In TCH, the intrinsic activity of the metals at room temperature and 1 bar H2 increased in the sequence Rh/C < Pt/C < Pd/C, while Ni/C is inactive at these conditions due to surface oxidation in the absence of cathodic potential. The reaction follows a Langmuir-Hinshelwood mechanism with the second hydrogen addition to the adsorbed hydrocarbon being the rate-determining step. All tested metals were active in ECH of benzaldehyde, although hydrogenation competes with the hydrogen evolution reaction (HER). The minimum cathodic potentials to obtain appreciable ECH rates were identical to the onset potentials of HER. Above this onset, the relative rates of H reacting to H2 and H addition to the hydrocarbon determines the selectivity to ECH and TCH. Accordingly, the selectivity of the metals towards ECH increases in the order Ni/C < Pt/C < Rh/C < Pd/C. Pd/C shows exceptionally high ECH selectivity due to its surprisingly low HER reactivity under the reaction conditions. Acknowledgements The authors would like to thank the groups of Hubert A. Gasteiger at the Technische Universität München of Jorge Gascon at the Delft University of Technology for advice and valuable discussions. The authors are grateful to Nirala Singh, Erika Ember, Gary Haller, and Philipp Rheinländer for fruitful discussions. We are also grateful to Marianne Hanzlik for TEM measurements and to Xaver Hecht and Martin Neukamm for technical support. Y.S. would like to thank the Chinese Scholarship Council for the financial support. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under the Laboratory Directed Research and Development Program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.},
doi = {10.1016/j.jcat.2017.12.026},
journal = {Journal of Catalysis},
number = C,
volume = 359,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2018},
month = {Thu Mar 01 00:00:00 EST 2018}
}