TY - JOUR
T1 - The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase
AU - Yang, Guoju
AU - Akhade, Sneha A.
AU - Chen, Xi
AU - Liu, Yue
AU - Lee, Mal Soon
AU - Glezakou, Vassiliki Alexandra
AU - Rousseau, Roger
AU - Lercher, Johannes A.
N1 - Funding Information:
G.J.Y. is grateful for the support by the 111Project (B17020) of China and the postdoctoral international exchange program of China. S.A.A., M.S.L., V.A.G., and J.A.L. were supported by 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. R.R. was supported by the United States Department of Energy (U.S. DOE), the Bioenergy Technologies Office. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe. Computational resources were provided by PNNL's Platform for Institutional Computing (PIC) and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231.
Funding Information:
G.J.Y. is grateful for the support by the 111Project (B17020) of China and the postdoctoral international exchange program of China. S.A.A., M.S.L., V.A.G., and J.A.L. were supported by 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. R.R. was supported by the United States Department of Energy (U.S. DOE), the Bioenergy Technologies Office. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe. Computational resources were provided by PNNL≫s Platform for Institutional Computing (PIC) and the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/3/11
Y1 - 2019/3/11
N2 - The thermodynamic state of H2 adsorbed on Pt in the aqueous phase was determined by kinetic analysis of H2 reacting with D2O to HDO, HD, and D2, and by DFT-based ab initio molecular dynamics simulations of H2 adsorption on Pt(111), Pt(110), and Pt nanoparticles. Dissociative adsorption of H2 on Pt is significantly weakened in the aqueous phase compared to adsorption at gas–solid interfaces. Water destabilizes the adsorbed H atoms, decreasing the heat of adsorption by 19–22 kJ (Formula presented.) while inducing an additional entropy loss of 50–70 J (Formula presented.) K−1. Upon dissociative adsorption of H2, the average distance of water from the Pt surface increases and the liquid adopts a structure that is more ordered than before close to the Pt surface, which limits the translation mobility of the adsorbed H atoms. The presence of hydrated hydronium ions next to the Pt surface further lowers the H−Pt bond strength.
AB - The thermodynamic state of H2 adsorbed on Pt in the aqueous phase was determined by kinetic analysis of H2 reacting with D2O to HDO, HD, and D2, and by DFT-based ab initio molecular dynamics simulations of H2 adsorption on Pt(111), Pt(110), and Pt nanoparticles. Dissociative adsorption of H2 on Pt is significantly weakened in the aqueous phase compared to adsorption at gas–solid interfaces. Water destabilizes the adsorbed H atoms, decreasing the heat of adsorption by 19–22 kJ (Formula presented.) while inducing an additional entropy loss of 50–70 J (Formula presented.) K−1. Upon dissociative adsorption of H2, the average distance of water from the Pt surface increases and the liquid adopts a structure that is more ordered than before close to the Pt surface, which limits the translation mobility of the adsorbed H atoms. The presence of hydrated hydronium ions next to the Pt surface further lowers the H−Pt bond strength.
KW - adsorption
KW - hydrogen
KW - hydrogen binding energy
KW - platinum
KW - water phase
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U2 - 10.1002/anie.201813958
DO - 10.1002/anie.201813958
M3 - Article
C2 - 30556940
AN - SCOPUS:85060807109
VL - 58
SP - 3527
EP - 3532
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 11
ER -