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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 does not 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. N.S. is funded by the WRF Innovation Fellowship in Clean Energy Institute. 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, amore » multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. Computational resources used by M.-T.N., D.C., V.-A.G., and R.R., were provided by DOE’s National Energy Research Scientific Computing Center located at Lawrence Berkeley National Laboratory and PNNL institutional computing. N.G. acknowledges computational resources for the XANES calculations provided by the Environmental Molecular Sciences Laboratory (EMSL), which is a DOE Office of Science User Facility located at PNNL. This research used resources of the Advanced Photon Source Sector 20, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors would like to thank Kamlesh Suthar and Scott Russell for help in designing the cell.« less

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 Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1476648
Alternate Identifier(s):
OSTI ID: 1496789; OSTI ID: 1775842
Report Number(s):
PNNL-SA-136451
Journal ID: ISSN 0021-9517; 145410
Grant/Contract Number:  
AC02-06CH11357; AC05-76RL01830
Resource Type:
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. https://doi.org/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. https://doi.org/10.1016/j.jcat.2018.09.021. https://www.osti.gov/servlets/purl/1476648.
@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 does not 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. N.S. is funded by the WRF Innovation Fellowship in Clean Energy Institute. 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 multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. Computational resources used by M.-T.N., D.C., V.-A.G., and R.R., were provided by DOE’s National Energy Research Scientific Computing Center located at Lawrence Berkeley National Laboratory and PNNL institutional computing. N.G. acknowledges computational resources for the XANES calculations provided by the Environmental Molecular Sciences Laboratory (EMSL), which is a DOE Office of Science User Facility located at PNNL. This research used resources of the Advanced Photon Source Sector 20, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors would like to thank Kamlesh Suthar and Scott Russell for help in designing the cell.},
doi = {10.1016/j.jcat.2018.09.021},
journal = {Journal of Catalysis},
number = C,
volume = 368,
place = {United States},
year = {Sat Oct 06 00:00:00 EDT 2018},
month = {Sat Oct 06 00:00:00 EDT 2018}
}

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Cited by: 40 works
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Figures / Tables:

Figure 1 Figure 1: a) Particle size distribution of the Pt/C 2 nm sample and atomic resolution HAADF STEM images showing typical particle morphology including presence of facets. Frequency axis maximum is 70 particles. b) Particle size distribution of the Pt/C 1.5 nm sample and STEM images showing crystalline Pt nanoparticles coexistingmore » with atomically-dispersed Pt species. Frequency axis maximum is 100 particles. In both cases, the catalyst is in the as-prepared condition. Arrows highlight single Pt atoms both in the nanocrystal and on the carbon support surface. Scale bar in all images is 2 nm.« less

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