Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase

Udishnu Sanyal; Simuck F. Yuk; Katherine Koh; Mal Soon Lee; Kelsey Stoerzinger; Difan Zhang; Laura C. Meyer; Juan A. Lopez-Ruiz; Abhi Karkamkar; Jamie D. Holladay; Donald M. Camaioni; Manh Thuong Nguyen; Vassiliki Alexandra Glezakou; Roger Rousseau; Oliver Y. Gutiérrez; Johannes A. Lercher

doi:10.1002/anie.202008178

Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase

Udishnu Sanyal, Simuck F. Yuk, Katherine Koh, Mal Soon Lee, Kelsey Stoerzinger, Difan Zhang, Laura C. Meyer, Juan A. Lopez-Ruiz, Abhi Karkamkar, Jamie D. Holladay, Donald M. Camaioni, Manh Thuong Nguyen, Vassiliki Alexandra Glezakou, Roger Rousseau, Oliver Y. Gutiérrez, Johannes A. Lercher

Chemical Sciences Division

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58 Scopus citations

Abstract

The hydrogenation of benzaldehyde to benzyl alcohol on carbon-supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co-adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co-adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction.

Original language	English
Pages (from-to)	290-296
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	1
DOIs	https://doi.org/10.1002/anie.202008178
State	Published - Jan 4 2021

Funding

The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under PNNL's Laboratory Directed Research and Development Program. D.M.C. and J.A.L. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers, FWP 47319). Computational resources were provided by PNNL's Research Computing facility and the National Energy Research Scientific Computing Center (NERSC), which is a DOE Office of Science User Facility. Open access funding enabled and organized by Projekt DEAL. The research described in this paper is part of the Chemical Transformation Initiative at Pacific Northwest National Laboratory (PNNL), conducted under PNNL's Laboratory Directed Research and Development Program. D.M.C. and J.A.L. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers, FWP 47319). Computational resources were provided by PNNL's Research Computing facility and the National Energy Research Scientific Computing Center (NERSC), which is a DOE Office of Science User Facility. Open access funding enabled and organized by Projekt DEAL.

Keywords

electrochemistry
electron transfer
hydrogen bonding
reduction
supported catalysts

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10.1002/anie.202008178

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Sanyal, U., Yuk, S. F., Koh, K., Lee, M. S., Stoerzinger, K., Zhang, D., Meyer, L. C., Lopez-Ruiz, J. A., Karkamkar, A., Holladay, J. D., Camaioni, D. M., Nguyen, M. T., Glezakou, V. A., Rousseau, R., Gutiérrez, O. Y., & Lercher, J. A. (2021). Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase. Angewandte Chemie - International Edition, 60(1), 290-296. https://doi.org/10.1002/anie.202008178

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title = "Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase",

abstract = "The hydrogenation of benzaldehyde to benzyl alcohol on carbon-supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co-adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co-adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction.",

keywords = "electrochemistry, electron transfer, hydrogen bonding, reduction, supported catalysts",

author = "Udishnu Sanyal and Yuk, {Simuck F.} and Katherine Koh and Lee, {Mal Soon} and Kelsey Stoerzinger and Difan Zhang and Meyer, {Laura C.} and Lopez-Ruiz, {Juan A.} and Abhi Karkamkar and Holladay, {Jamie D.} and Camaioni, {Donald M.} and Nguyen, {Manh Thuong} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau and Guti{\'e}rrez, {Oliver Y.} and Lercher, {Johannes A.}",

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Sanyal, U, Yuk, SF, Koh, K, Lee, MS, Stoerzinger, K, Zhang, D, Meyer, LC, Lopez-Ruiz, JA, Karkamkar, A, Holladay, JD, Camaioni, DM, Nguyen, MT, Glezakou, VA , Rousseau, R, Gutiérrez, OY & Lercher, JA 2021, 'Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase', Angewandte Chemie - International Edition, vol. 60, no. 1, pp. 290-296. https://doi.org/10.1002/anie.202008178

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T1 - Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase

AU - Sanyal, Udishnu

AU - Yuk, Simuck F.

AU - Koh, Katherine

AU - Lee, Mal Soon

AU - Stoerzinger, Kelsey

AU - Zhang, Difan

AU - Meyer, Laura C.

AU - Lopez-Ruiz, Juan A.

AU - Karkamkar, Abhi

AU - Holladay, Jamie D.

AU - Camaioni, Donald M.

AU - Nguyen, Manh Thuong

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Gutiérrez, Oliver Y.

AU - Lercher, Johannes A.

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N2 - The hydrogenation of benzaldehyde to benzyl alcohol on carbon-supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co-adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co-adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction.

AB - The hydrogenation of benzaldehyde to benzyl alcohol on carbon-supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co-adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co-adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction.

KW - electrochemistry

KW - electron transfer

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Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase

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