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Title: Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates

Abstract

Adsorbed hydrogen and phenol on Pt nanoparticles during (electro)catalytic hydrogenation are explored by combining x-ray absorption spectroscopy and ab initio simulations. Direct evidence for two types of Pt-C bonds at the surface of the metal particles detected by X-ray absorption spectroscopy suggest strong bonding between metal and the carbon support as well as adsorption of phenol nearly parallel to the surface. Hydrogen and phenol compete for accessible Pt sites. The surface concentrations are compatible with the proposal that atomic hydrogen and chemisorbed phenol are the species reacting in the rate-determining step of hydrogenation in the presence and absence of an external cathodic potential. During electrocatalytic hydrogenation the external electric potential controls the concentration of species on the surface, but doesnot impose structural or electronic property changes of the Pt compared to Pt particles in presence of hydrogen gas. Increasing reaction rates with increasing cathodic potential are attributed to the increase in chemical potential of adsorbed H.

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [3];  [2];  [2];  [4]; ORCiD logo [2];  [2];  [2];  [2];  [2]; ORCiD logo [5];  [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of Liverpool (United Kingdom)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
  5. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1476648
Alternate Identifier(s):
OSTI ID: 1496789
Report Number(s):
PNNL-SA-136451
Journal ID: ISSN 0021-9517; 145410
Grant/Contract Number:  
AC02-06CH11357; AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 368; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; hydrogenation; x-ray Absorption Spectroscopy; Hydrogenation, Electrocatalysis, X-ray Absorption Spectroscopy

Citation Formats

Singh, Nirala, Nguyen, Manh-Thuong, Cantu, David C., Mehdi, B. Layla, Browning, Nigel D., Fulton, John L., Zheng, Jian, Balasubramanian, Mahalingam, Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Govind, Niranjan, Camaioni, Donald M., Campbell, Charles T., and Lercher, Johannes A. Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates. United States: N. p., 2018. Web. doi:10.1016/j.jcat.2018.09.021.
Singh, Nirala, Nguyen, Manh-Thuong, Cantu, David C., Mehdi, B. Layla, Browning, Nigel D., Fulton, John L., Zheng, Jian, Balasubramanian, Mahalingam, Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Govind, Niranjan, Camaioni, Donald M., Campbell, Charles T., & Lercher, Johannes A. Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates. United States. doi:10.1016/j.jcat.2018.09.021.
Singh, Nirala, Nguyen, Manh-Thuong, Cantu, David C., Mehdi, B. Layla, Browning, Nigel D., Fulton, John L., Zheng, Jian, Balasubramanian, Mahalingam, Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Govind, Niranjan, Camaioni, Donald M., Campbell, Charles T., and Lercher, Johannes A. Sat . "Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates". United States. doi:10.1016/j.jcat.2018.09.021.
@article{osti_1476648,
title = {Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates},
author = {Singh, Nirala and Nguyen, Manh-Thuong and Cantu, David C. and Mehdi, B. Layla and Browning, Nigel D. and Fulton, John L. and Zheng, Jian and Balasubramanian, Mahalingam and Gutiérrez, Oliver Y. and Glezakou, Vassiliki-Alexandra and Rousseau, Roger and Govind, Niranjan and Camaioni, Donald M. and Campbell, Charles T. and Lercher, Johannes A.},
abstractNote = {Adsorbed hydrogen and phenol on Pt nanoparticles during (electro)catalytic hydrogenation are explored by combining x-ray absorption spectroscopy and ab initio simulations. Direct evidence for two types of Pt-C bonds at the surface of the metal particles detected by X-ray absorption spectroscopy suggest strong bonding between metal and the carbon support as well as adsorption of phenol nearly parallel to the surface. Hydrogen and phenol compete for accessible Pt sites. The surface concentrations are compatible with the proposal that atomic hydrogen and chemisorbed phenol are the species reacting in the rate-determining step of hydrogenation in the presence and absence of an external cathodic potential. During electrocatalytic hydrogenation the external electric potential controls the concentration of species on the surface, but doesnot impose structural or electronic property changes of the Pt compared to Pt particles in presence of hydrogen gas. Increasing reaction rates with increasing cathodic potential are attributed to the increase in chemical potential of adsorbed H.},
doi = {10.1016/j.jcat.2018.09.021},
journal = {Journal of Catalysis},
issn = {0021-9517},
number = C,
volume = 368,
place = {United States},
year = {2018},
month = {10}
}

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