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Title: Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh

Abstract

In aqueous phase, the rates of hydrogenation of aromatic substrates such as phenol on Pt/C and Rh/C are influenced by varying activity of hydronium ions. Decreasing the pH from 8 to 1 increases the rate of hydrogenation of phenol on Pt at 20 bar H2 and 80 °C by 15-fold. This increase is attributed to weakening of the hydrogen binding energy (HBE) on the metal surface with decreasing pH. A weaker HBE at lower pH is also predicted by ab initio molecular dynamics simulations, providing atomistic insight into the impact of electrolyte ion distribution and interfacial solvent reorganization on HBE. The lower HBE results in a decrease in the activation energy for addition of adsorbed H from the metal to the adsorbed organic (with a Brønsted–Evans–Polanyi slope of ~1). In conclusion, the kinetic model derived accounts also for the lack of pH dependence at low hydrogen coverages (at 1 bar H2 on Pt or up to 70 bar H2 on Rh), when the weakening of the HBE decreases the hydrogen coverage.

Authors:
 [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [4]; ORCiD logo [5]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
  3. Technische Univ. Munchen, Garching (Germany). Dept. Chemistry and Catalysis Research Center
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Technische Univ. Munchen, Garching (Germany). Dept. Chemistry and Catalysis Research Center
  5. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1557264
Grant/Contract Number:  
FG02-96ER14630
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogenation; phenol; platinum; Brønsted−Evans−Polanyi; aqueous phase; hydrogen adsorption; pH effects; molecular dynamics simulations

Citation Formats

Singh, Nirala, Lee, Mal-Soon, Akhade, Sneha A., Cheng, Guanhua, Camaioni, Donald M., Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Lercher, Johannes A., and Campbell, Charles T. Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b04039.
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Singh, Nirala, Lee, Mal-Soon, Akhade, Sneha A., Cheng, Guanhua, Camaioni, Donald M., Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Lercher, Johannes A., & Campbell, Charles T. Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh. United States. https://doi.org/10.1021/acscatal.8b04039
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Singh, Nirala, Lee, Mal-Soon, Akhade, Sneha A., Cheng, Guanhua, Camaioni, Donald M., Gutiérrez, Oliver Y., Glezakou, Vassiliki-Alexandra, Rousseau, Roger, Lercher, Johannes A., and Campbell, Charles T. Wed . "Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh". United States. https://doi.org/10.1021/acscatal.8b04039. https://www.osti.gov/servlets/purl/1557264.
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@article{osti_1557264,
title = {Impact of pH on Aqueous-Phase Phenol Hydrogenation Catalyzed by Carbon-Supported Pt and Rh},
author = {Singh, Nirala and Lee, Mal-Soon and Akhade, Sneha A. and Cheng, Guanhua and Camaioni, Donald M. and Gutiérrez, Oliver Y. and Glezakou, Vassiliki-Alexandra and Rousseau, Roger and Lercher, Johannes A. and Campbell, Charles T.},
abstractNote = {In aqueous phase, the rates of hydrogenation of aromatic substrates such as phenol on Pt/C and Rh/C are influenced by varying activity of hydronium ions. Decreasing the pH from 8 to 1 increases the rate of hydrogenation of phenol on Pt at 20 bar H2 and 80 °C by 15-fold. This increase is attributed to weakening of the hydrogen binding energy (HBE) on the metal surface with decreasing pH. A weaker HBE at lower pH is also predicted by ab initio molecular dynamics simulations, providing atomistic insight into the impact of electrolyte ion distribution and interfacial solvent reorganization on HBE. The lower HBE results in a decrease in the activation energy for addition of adsorbed H from the metal to the adsorbed organic (with a Brønsted–Evans–Polanyi slope of ~1). In conclusion, the kinetic model derived accounts also for the lack of pH dependence at low hydrogen coverages (at 1 bar H2 on Pt or up to 70 bar H2 on Rh), when the weakening of the HBE decreases the hydrogen coverage.},
doi = {10.1021/acscatal.8b04039},
journal = {ACS Catalysis},
number = 2,
volume = 9,
place = {United States},
year = {Wed Dec 19 00:00:00 EST 2018},
month = {Wed Dec 19 00:00:00 EST 2018}
}
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Works referenced in this record:

Integrated catalytic and electrocatalytic conversion of substituted phenols and diaryl ethers
journal, December 2016

Hydrogenation of benzaldehyde via electrocatalysis and thermal catalysis on carbon-supported metals
journal, March 2018

Electrocatalytic Hydrogenation of Phenol over Platinum and Rhodium: Unexpected Temperature Effects Resolved
journal, October 2016

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010

  • Sheng, Wenchao; Gasteiger, Hubert A.; Shao-Horn, Yang
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3483106

Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy
journal, March 2016

New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014

  • Durst, J.; Siebel, A.; Simon, C.
  • Energy Environ. Sci., Vol. 7, Issue 7
  • DOI: 10.1039/C4EE00440J

Size-Dependent Hydrogen Oxidation and Evolution Activities on Supported Palladium Nanoparticles in Acid and Base
journal, January 2016

  • Zheng, Jie; Zhou, Shuyuan; Gu, Shuang
  • Journal of The Electrochemical Society, Vol. 163, Issue 6
  • DOI: 10.1149/2.0661606jes

Temperature-Dependent Hydrogen Electrochemistry on Platinum Low-Index Single-Crystal Surfaces in Acid Solutions
journal, July 1997

  • Marković, N. M.; Grgur, B. N.; Ross, P. N.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 27
  • DOI: 10.1021/jp970930d

Hydrogen electrochemistry on platinum low-index single-crystal surfaces in alkaline solution
journal, January 1996

  • Markovića, Nenad M.; Sarraf, Stella T.; Gasteiger, Hubert A.
  • J. Chem. Soc., Faraday Trans., Vol. 92, Issue 20
  • DOI: 10.1039/FT9969203719

Design principles for hydrogen evolution reaction catalyst materials
journal, November 2016

The role of non-covalent interactions in electrocatalytic fuel-cell reactions on platinum
journal, August 2009

  • Strmcnik, D.; Kodama, K.; van der Vliet, D.
  • Nature Chemistry, Vol. 1, Issue 6
  • DOI: 10.1038/nchem.330

Co-adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single-Crystal Electrode
journal, October 2017

  • Chen, Xiaoting; McCrum, Ian T.; Schwarz, Kathleen A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 47
  • DOI: 10.1002/anie.201709455

Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces
journal, January 2013

  • Sheng, Wenchao; Myint, MyatNoeZin; Chen, Jingguang G.
  • Energy & Environmental Science, Vol. 6, Issue 5
  • DOI: 10.1039/c3ee00045a

Perspective—Towards Establishing Apparent Hydrogen Binding Energy as the Descriptor for Hydrogen Oxidation/Evolution Reactions
journal, January 2018

  • Zheng, Jie; Nash, Jared; Xu, Bingjun
  • Journal of The Electrochemical Society, Vol. 165, Issue 2
  • DOI: 10.1149/2.0881802jes

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015

  • Sheng, Wenchao; Zhuang, Zhongbin; Gao, Minrui
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6848

Water dissociation on well-defined platinum surfaces: The electrochemical perspective
journal, March 2013

The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen
journal, January 1958

  • Parsons, Roger
  • Transactions of the Faraday Society, Vol. 54, p. 1053-1063
  • DOI: 10.1039/tf9585401053

Explanation of Dramatic pH-Dependence of Hydrogen Binding on Noble Metal Electrode: Greatly Weakened Water Adsorption at High pH
journal, May 2018

  • Cheng, Tao; Wang, Lu; Merinov, Boris V.
  • Journal of the American Chemical Society, Vol. 140, Issue 25
  • DOI: 10.1021/jacs.8b04006

The Hydrogen Evolution Reaction in Alkaline Solution: From Theory, Single Crystal Models, to Practical Electrocatalysts
journal, May 2018

  • Zheng, Yao; Jiao, Yan; Vasileff, Anthony
  • Angewandte Chemie International Edition, Vol. 57, Issue 26
  • DOI: 10.1002/anie.201710556

pH effect on acetate adsorption at Pt(111) electrode
journal, April 2018

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces
journal, July 2018

  • McCrum, Ian T.; Chen, Xiaoting; Schwarz, Kathleen A.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 29
  • DOI: 10.1021/acs.jpcc.8b03660

Importance of Solvation for the Accurate Prediction of Oxygen Reduction Activities of Pt-Based Electrocatalysts
journal, May 2017

  • He, Zheng-Da; Hanselman, Selwyn; Chen, Yan-Xia
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
  • DOI: 10.1021/acs.jpclett.7b01018

Recent developments in electrochemical hydrogen evolution reaction
journal, January 2018

pH and Alkali Cation Effects on the Pt Cyclic Voltammogram Explained Using Density Functional Theory
journal, December 2015

  • McCrum, Ian T.; Janik, Michael J.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 1
  • DOI: 10.1021/acs.jpcc.5b10979

Influence of Alkali Metal Cations on the Hydrogen Evolution Reaction Activity of Pt, Ir, Au, and Ag Electrodes in Alkaline Electrolytes
journal, June 2018

  • Xue, Song; Garlyyev, Batyr; Watzele, Sebastian
  • ChemElectroChem, Vol. 5, Issue 17
  • DOI: 10.1002/celc.201800690

Influence of the Nature of the Alkali Metal Cations on the Electrical Double-Layer Capacitance of Model Pt(111) and Au(111) Electrodes
journal, March 2018

  • Garlyyev, Batyr; Xue, Song; Watzele, Sebastian
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 8
  • DOI: 10.1021/acs.jpclett.8b00610

Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

Gas-Phase Chemistry to Understand Electrochemical Hydrogen Evolution and Oxidation on Doped Transition Metal Sulfides
journal, January 2013

  • Singh, Nirala; Upham, David Chester; Metiu, Horia
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.002311jes

Probing ensemble effects in surface reactions. 1. Site-size requirements for the dehydrogenation of cyclic hydrocarbons on platinum(111) revealed by bismuth site blocking
journal, January 1989

  • Campbell, Charles T.; Campbell, J. M.; Dalton, P. J.
  • The Journal of Physical Chemistry, Vol. 93, Issue 2
  • DOI: 10.1021/j100339a056

Surface science studies of model fuel cell electrocatalysts
journal, April 2002

Co-adsorption of O and H2O on Nanostructured Platinum Surfaces: Does OH Form at Steps?
journal, July 2010

  • van der Niet, Maria J. T. C.; den Dunnen, Angela; Juurlink, Ludo B. F.
  • Angewandte Chemie International Edition, Vol. 49, Issue 37
  • DOI: 10.1002/anie.201002124

In situ infrared spectroscopy at single-crystal metal electrodes: an emerging link between electrochemical and ultrahigh-vacuum surface science
journal, July 1991

  • Chang, Si Chung; Weaver, Michael J.
  • The Journal of Physical Chemistry, Vol. 95, Issue 14
  • DOI: 10.1021/j100167a010

Finite Bias Calculations to Model Interface Dipoles in Electrochemical Cells at the Atomic Scale
journal, June 2016

  • Hansen, Martin Hangaard; Jin, Chengjun; Thygesen, Kristian Sommer
  • The Journal of Physical Chemistry C, Vol. 120, Issue 25
  • DOI: 10.1021/acs.jpcc.6b00721

System-Size Dependence of Diffusion Coefficients and Viscosities from Molecular Dynamics Simulations with Periodic Boundary Conditions
journal, October 2004

  • Yeh, In-Chul; Hummer, Gerhard
  • The Journal of Physical Chemistry B, Vol. 108, Issue 40
  • DOI: 10.1021/jp0477147

First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase
journal, July 2014

  • Yoon, Yeohoon; Rousseau, Roger; Weber, Robert S.
  • Journal of the American Chemical Society, Vol. 136, Issue 29
  • DOI: 10.1021/ja501592y

Energies of Formation Reactions Measured for Adsorbates on Late Transition Metal Surfaces
journal, October 2016

  • Silbaugh, Trent L.; Campbell, Charles T.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 44
  • DOI: 10.1021/acs.jpcc.6b06154

Computational study of the adsorption and dissociation of phenol on Pt and Rh surfaces
journal, January 2012

  • Honkela, Maija L.; Björk, Jonas; Persson, Mats
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 16
  • DOI: 10.1039/c2cp24064e

Chemisorption of Benzene on Pt(111), Pd(111), and Rh(111) Metal Surfaces:  A Structural and Vibrational Comparison from First Principles
journal, May 2004

  • Morin, C.; Simon, D.; Sautet, P.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 18
  • DOI: 10.1021/jp0373503

Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces
journal, February 2014

  • Carrasco, Javier; Liu, Wei; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4866175

Aqueous phase electrocatalysis and thermal catalysis for the hydrogenation of phenol at mild conditions
journal, March 2016

Benzene hydrogenation over supported and unsupported palladium II. Reaction model
journal, September 1987

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte
journal, November 2017

  • Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 2
  • DOI: 10.1021/acs.jpcb.7b06953

First Principles Simulations of Cyclic Voltammograms on Stepped Pt(553) and Pt(533) Electrode Surfaces
journal, August 2016

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media
journal, November 2017

  • Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.
  • Angewandte Chemie International Edition, Vol. 56, Issue 49
  • DOI: 10.1002/anie.201708484

On the pH dependence of electrochemical proton transfer barriers
journal, March 2016

The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy
journal, October 2014

Potential Dependent Organization of Water at the Electrified Metal−Liquid Interface
journal, November 2005

  • Schultz, Zachary D.; Shaw, Scott K.; Gewirth, Andrew A.
  • Journal of the American Chemical Society, Vol. 127, Issue 45
  • DOI: 10.1021/ja0543393

Interaction of hydrogen with solid surfaces
journal, July 1988

Structure Sensitivity in Hydrogenation Reactions on Pt/C in Aqueous‐phase
journal, October 2018

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

A hybrid Gaussian and plane wave density functional scheme
journal, October 1997

Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Separable dual-space Gaussian pseudopotentials
journal, July 1996

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Enthalpic and Entropic Effects on Hydrogen and OH Adsorption on Pt(111), Pt(100), and Pt(110) Electrodes As Evaluated by Gibbs Thermodynamics
journal, December 2010

  • Garcia-Araez, Nuria
  • The Journal of Physical Chemistry C, Vol. 115, Issue 2
  • DOI: 10.1021/jp1088146
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