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Title: The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase

Abstract

H2 adsorption properties on Pt in aqueous phase was determined by a reaction kinetic measurement of gas H2 reacting with liquid D2O into liquid HDO, gas HD and D2, and a DFT based ab inito molecular dynamic simulation of H2 adsorption on Pt (111) in the presence and absence of water. Both approaches show that the H2 adsorption on Pt in water is much weaker than that in the gas phase. The presence of interfacial water destabilizes the adsorbed H on Pt via decreasing the adsorption heat (hydrogen binding energy) by 19 - 22 kJ·molH2-1 and inducing an extra entropy loss of 50 - 70 J·mol H2-1·K-1. Upon H adsorption on Pt, the closest water layer near Pt surface shifts to a larger distance from the surface and re-orientates to a more ordered structure; in turn, the water layer limits the translation mobility of adsorbed H on Pt. The influence of interfacial water property on H2 adsorption is also reflected by the decrease of adsorption heat with the decrease of local pH provided by the support. Research was funded by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [4]
  1. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4 85747 Garching Germany; College of Chemistry and International Center of Future Science, Jilin University, Qianjin Str. 2699 130012 Changchun P. R. China
  2. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA
  3. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4 85747 Garching Germany
  4. Department of Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstrasse 4 85747 Garching Germany; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1501940
Report Number(s):
PNNL-SA-134839
Journal ID: ISSN 1433-7851
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 58; Journal Issue: 11; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

Citation Formats

Yang, Guoju, Akhade, Sneha A., Chen, Xi, Liu, Yue, Lee, Mal-Soon, Glezakou, Vassiliki-Alexandra, Rousseau, Roger, and Lercher, Johannes A. The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase. United States: N. p., 2019. Web. doi:10.1002/anie.201813958.
Yang, Guoju, Akhade, Sneha A., Chen, Xi, Liu, Yue, Lee, Mal-Soon, Glezakou, Vassiliki-Alexandra, Rousseau, Roger, & Lercher, Johannes A. The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase. United States. doi:10.1002/anie.201813958.
Yang, Guoju, Akhade, Sneha A., Chen, Xi, Liu, Yue, Lee, Mal-Soon, Glezakou, Vassiliki-Alexandra, Rousseau, Roger, and Lercher, Johannes A. Tue . "The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase". United States. doi:10.1002/anie.201813958.
@article{osti_1501940,
title = {The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase},
author = {Yang, Guoju and Akhade, Sneha A. and Chen, Xi and Liu, Yue and Lee, Mal-Soon and Glezakou, Vassiliki-Alexandra and Rousseau, Roger and Lercher, Johannes A.},
abstractNote = {H2 adsorption properties on Pt in aqueous phase was determined by a reaction kinetic measurement of gas H2 reacting with liquid D2O into liquid HDO, gas HD and D2, and a DFT based ab inito molecular dynamic simulation of H2 adsorption on Pt (111) in the presence and absence of water. Both approaches show that the H2 adsorption on Pt in water is much weaker than that in the gas phase. The presence of interfacial water destabilizes the adsorbed H on Pt via decreasing the adsorption heat (hydrogen binding energy) by 19 - 22 kJ·molH2-1 and inducing an extra entropy loss of 50 - 70 J·mol H2-1·K-1. Upon H adsorption on Pt, the closest water layer near Pt surface shifts to a larger distance from the surface and re-orientates to a more ordered structure; in turn, the water layer limits the translation mobility of adsorbed H on Pt. The influence of interfacial water property on H2 adsorption is also reflected by the decrease of adsorption heat with the decrease of local pH provided by the support. Research was funded by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory.},
doi = {10.1002/anie.201813958},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 11,
volume = 58,
place = {United States},
year = {2019},
month = {1}
}

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