The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

Guoju Yang; Sneha A. Akhade; Xi Chen; Yue Liu; Mal Soon Lee; Vassiliki Alexandra Glezakou; Roger Rousseau; Johannes A. Lercher

doi:10.1002/anie.201813958

The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

Guoju Yang, Sneha A. Akhade, Xi Chen, Yue Liu, Mal Soon Lee, Vassiliki Alexandra Glezakou, Roger Rousseau, Johannes A. Lercher

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70 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	3527-3532
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	11
DOIs	https://doi.org/10.1002/anie.201813958
State	Published - Mar 11 2019
Externally published	Yes

Funding

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.

Funders	Funder number
U.S. Department of Energy
Office of Science	DE-AC02-05CH11231
Pacific Northwest National Laboratory
Bioenergy Technologies Office
National Energy Research Scientific Computing Center

Keywords

adsorption
hydrogen
hydrogen binding energy
platinum
water phase

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title = "The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase",

abstract = "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.",

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AU - Lee, Mal Soon

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Lercher, Johannes A.

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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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The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

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