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Title: Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water

Abstract

Compared to the vapour phase, liquid-phase heterogeneous catalysis provides additional degrees of freedom for reaction engineering, but the multifaceted solvent effects complicate analysis of the reaction mechanism. Here, using furfural as an example, we reveal the important role of water-mediated protonation in a typical hydrogenation reaction over a supported Pd catalyst. Depending on the solvent, we have observed different reaction orders with respect to the partial pressure of H2, as well as distinct selectivity towards hydrogenation of the conjugated C=O and C=C double bonds. Free energy calculations show that H2O participates directly in the kinetically relevant reaction step and provides an additional channel for hydrogenation of the aldehyde group, in which hydrogen bypasses the direct surface reaction via a hydrogen-bonded water network. This solution-mediated reaction pathway shows the potential role of the solvent for tuning the selectivity of metal-catalysed hydrogenation when charge separation on the metal surface is feasible.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Oklahoma, Norman, OK (United States). Center fro Interfacial Reaction Engineering and School of Chemical, Biological, and Materials Engineering
  2. Univ. of Tulsa, OK (United States). Dept. of Physics and Engineering Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1527373
DOE Contract Number:  
SC0018284
Resource Type:
Journal Article
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2520-1158
Country of Publication:
United States
Language:
English

Citation Formats

Zhao, Zheng, Bababrik, Reda, Xue, Wenhua, Li, Yaping, Briggs, Nicholas M., Nguyen, Dieu-Thy, Nguyen, Umi, Crossley, Steven P., Wang, Sanwu, Wang, Bin, and Resasco, Daniel E. Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water. United States: N. p., 2019. Web. doi:10.1038/s41929-019-0257-z.
Zhao, Zheng, Bababrik, Reda, Xue, Wenhua, Li, Yaping, Briggs, Nicholas M., Nguyen, Dieu-Thy, Nguyen, Umi, Crossley, Steven P., Wang, Sanwu, Wang, Bin, & Resasco, Daniel E. Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water. United States. doi:10.1038/s41929-019-0257-z.
Zhao, Zheng, Bababrik, Reda, Xue, Wenhua, Li, Yaping, Briggs, Nicholas M., Nguyen, Dieu-Thy, Nguyen, Umi, Crossley, Steven P., Wang, Sanwu, Wang, Bin, and Resasco, Daniel E. Mon . "Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water". United States. doi:10.1038/s41929-019-0257-z.
@article{osti_1527373,
title = {Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water},
author = {Zhao, Zheng and Bababrik, Reda and Xue, Wenhua and Li, Yaping and Briggs, Nicholas M. and Nguyen, Dieu-Thy and Nguyen, Umi and Crossley, Steven P. and Wang, Sanwu and Wang, Bin and Resasco, Daniel E.},
abstractNote = {Compared to the vapour phase, liquid-phase heterogeneous catalysis provides additional degrees of freedom for reaction engineering, but the multifaceted solvent effects complicate analysis of the reaction mechanism. Here, using furfural as an example, we reveal the important role of water-mediated protonation in a typical hydrogenation reaction over a supported Pd catalyst. Depending on the solvent, we have observed different reaction orders with respect to the partial pressure of H2, as well as distinct selectivity towards hydrogenation of the conjugated C=O and C=C double bonds. Free energy calculations show that H2O participates directly in the kinetically relevant reaction step and provides an additional channel for hydrogenation of the aldehyde group, in which hydrogen bypasses the direct surface reaction via a hydrogen-bonded water network. This solution-mediated reaction pathway shows the potential role of the solvent for tuning the selectivity of metal-catalysed hydrogenation when charge separation on the metal surface is feasible.},
doi = {10.1038/s41929-019-0257-z},
journal = {Nature Catalysis},
issn = {2520-1158},
number = 5,
volume = 2,
place = {United States},
year = {2019},
month = {4}
}

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