TY - JOUR
T1 - Electrochemically Tunable Proton-Coupled Electron Transfer in Pd-Catalyzed Benzaldehyde Hydrogenation
AU - Koh, Katherine
AU - Sanyal, Udishnu
AU - Lee, Mal Soon
AU - Cheng, Guanhua
AU - Song, Miao
AU - Glezakou, Vassiliki Alexandra
AU - Liu, Yue
AU - Li, Dongsheng
AU - Rousseau, Roger
AU - Gutiérrez, Oliver Y.
AU - Karkamkar, Abhijeet
AU - Derewinski, Miroslaw
AU - Lercher, Johannes A.
N1 - Funding Information:
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 multi-program national laboratory operated by Battelle for the U.S. Department of Energy. Computational resources were provided by PNNL Research Computing. O.Y.G. and M.D. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers, FWP 47319). J.A.L. was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy?EXC 2089/1-390776260.
Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
PY - 2020/1/20
Y1 - 2020/1/20
N2 - Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted-acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2-induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support-generated hydronium ions in the proximity of the metal particles.
AB - Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted-acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2-induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support-generated hydronium ions in the proximity of the metal particles.
KW - acidity of support
KW - biomass conversion
KW - carbon modification
KW - electrocatalytic hydrogenation
KW - nanocatalysis
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U2 - 10.1002/anie.201912241
DO - 10.1002/anie.201912241
M3 - Article
C2 - 31634416
AN - SCOPUS:85076411293
VL - 59
SP - 1501
EP - 1505
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 4
ER -