Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt-Based Electrocatalysts

Journal Article · · ChemPhysChem
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Leiden Univ. (Netherlands)
  2. Univ. EAFIT, Medellín (Colombia)
  3. Univ. de Barcelona (Spain)
+ Show Author Affiliations

Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid-phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near-surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE-D3 and RPBE-D3. On average, *OH solvation energies are less negative by ~0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid-phase catalysis.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC); Ramón y Cajal; Units of Excellence María de Maeztu; Netherlands Organization for Scientific Research (NWO); European Union (EU)
Grant/Contract Number:
SC0012704; RYC-2015-18996; MDM-2017-0767
OSTI ID:
1623518
Journal Information:
ChemPhysChem, Vol. 20, Issue 22; ISSN 1439-4235
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (88)

Generalized Gradient Approximation Made Simple journal October 1996
Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations journal April 2018
Alkali cation specific adsorption onto fcc(111) transition metal electrodes journal January 2014
Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO 2 over Ag and Cu journal September 2016
A New Type of Scaling Relations to Assess the Accuracy of Computational Predictions of Catalytic Activities Applied to the Oxygen Evolution Reaction journal March 2017
Near-surface alloys for hydrogen fuel cell applications journal January 2006
Chemically Accurate Simulation of a Prototypical Surface Reaction: H2 Dissociation on Cu(111) journal November 2009
Establishing the Accuracy of Broadly Used Density Functionals in Describing Bulk Properties of Transition Metals journal February 2013
Initial stages of water solvation of stepped platinum surfaces journal January 2016
Self-consistent continuum solvation (SCCS): The case of charged systems journal December 2013
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Structure and Bonding of Water on Pt(111) journal December 2002
Accounting for Bifurcating Pathways in the Screening for CO 2 Reduction Catalysts journal September 2017
Chemical accuracy for the van der Waals density functional journal December 2009
Elucidation of the Electrochemical Activation of Water over Pd by First Principles journal January 2006
Solvation Effects for Oxygen Evolution Reaction Catalysis on IrO 2 (110) journal May 2017
Molecular and solid-state tests of density functional approximations: LSD, GGAs, and meta-GGAs journal January 1999
Tailoring the catalytic activity of electrodes with monolayer amounts of foreign metals journal January 2013
Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement journal February 2017
Nonequivalence of the generalized gradient approximations PBE and PW91 journal May 2006
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation journal June 2012
High-precision sampling for Brillouin-zone integration in metals journal August 1989
The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations journal November 2010
Hybrid solvation models for bulk, interface, and membrane: Reference interaction site methods coupled with density functional theory journal September 2017
Grand-canonical approach to density functional theory of electrocatalytic systems: Thermodynamics of solid-liquid interfaces at constant ion and electrode potentials journal January 2019
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Parallel Nanoimprint Forming of One-Dimensional Chiral Semiconductor for Strain-Engineered Optical Properties journal August 2020
Product Selectivity Affected by Cationic Species in Electrochemical Reduction of CO 2 and CO at a Cu Electrode journal January 1991
How covalence breaks adsorption-energy scaling relations and solvation restores them journal January 2017
Multigrid-Based Methodology for Implicit Solvation Models in Periodic DFT journal February 2016
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways journal February 2014
Elucidation of the Electrochemical Activation of Water over Pd by First Principles journal January 2006
Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes journal March 2017
Adsorption trends for water, hydroxyl, oxygen, and hydrogen on transition-metal and platinum-skin surfaces journal October 2006
Generalized gradient approximation for the exchange-correlation hole of a many-electron system journal December 1996
Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster journal March 2016
Oxygen Electroreduction at High-Index Pt Electrodes in Alkaline Electrolytes: A Decisive Role of the Alkali Metal Cations journal November 2018
Importance of Solvation for the Accurate Prediction of Oxygen Reduction Activities of Pt-Based Electrocatalysts journal May 2017
Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface journal February 2019
Computational Screening of Near-Surface Alloys for CO 2 Electroreduction journal March 2018
Thermodynamic assessment of the oxygen reduction activity in aqueous solutions journal January 2017
pH and Alkali Cation Effects on the Pt Cyclic Voltammogram Explained Using Density Functional Theory journal December 2015
Catalytic Water Formation on Platinum:  A First-Principles Study journal May 2001
Structure- and Potential-Dependent Cation Effects on CO Reduction at Copper Single-Crystal Electrodes journal November 2017
Capturing Solvation Effects at a Liquid/Nanoparticle Interface by Ab Initio Molecular Dynamics: Pt 201 Immersed in Water journal August 2016
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals journal March 1999
Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics journal February 2019
Understanding the electrocatalysis of oxygen reduction on platinum and its alloys journal January 2012
Formic acid oxidation on platinum: a simple mechanistic study journal January 2015
Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles journal February 2019
Enabling Generalized Coordination Numbers to Describe Strain Effects journal May 2018
Density functional theory study of the electrochemical interface between a Pt electrode and an aqueous electrolyte using an implicit solvent method journal June 2015
Influence of Alkali Metal Cations on the Hydrogen Evolution Reaction Activity of Pt, Ir, Au, and Ag Electrodes in Alkaline Electrolytes journal June 2018
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Mechanism of Oxygen Reduction Reaction on Pt(111) in Alkaline Solution: Importance of Chemisorbed Water on Surface journal July 2016
Implanting Ni-O-VOx sites into Cu-doped Ni for low-overpotential alkaline hydrogen evolution journal June 2020
Quantifying solvation energies at solid/liquid interfaces using continuum solvation methods journal January 2017
The role of van der Waals forces in water adsorption on metals journal January 2013
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode journal November 2004
Number of outer electrons as descriptor for adsorption processes on transition metals and their oxides journal January 2013
Density functional theory simulations of water–metal interfaces: waltzing waters, a novel 2D ice phase, and more journal September 2006
Properties of metal–water interfaces studied from first principles journal December 2009
Joint density functional theory of the electrode-electrolyte interface: Application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge journal August 2012
Are Mixed Explicit/Implicit Solvation Models Reliable for Studying Phosphate Hydrolysis? A Comparative Study of Continuum, Explicit and Mixed Solvation Models journal May 2009
General Model for Water Monomer Adsorption on Close-Packed Transition and Noble Metal Surfaces journal May 2003
Establishing and Understanding Adsorption–Energy Scaling Relations with Negative Slopes journal November 2016
Tuning the Catalytic Activity and Selectivity of Cu for CO 2 Electroreduction in the Presence of Halides journal February 2016
Chemical accuracy for the van der Waals density functional preprint January 2009
The role of van der Waals forces in water adsorption on metals text January 2013
Are Mixed Explicit/Implicit Solvation Models Reliable for Studying Phosphate Hydrolysis? A Comparative Study of Continuum, Explicit and Mixed Solvation Models journal May 2009
Enabling Generalized Coordination Numbers to Describe Strain Effects journal May 2018
Multigrid-Based Methodology for Implicit Solvation Models in Periodic DFT journal February 2016
Establishing and Understanding Adsorption–Energy Scaling Relations with Negative Slopes journal November 2016
Importance of Solvation for the Accurate Prediction of Oxygen Reduction Activities of Pt-Based Electrocatalysts journal May 2017
Establishing the Accuracy of Broadly Used Density Functionals in Describing Bulk Properties of Transition Metals journal February 2013
Catalytic Water Formation on Platinum:  A First-Principles Study journal May 2001
Structure- and Potential-Dependent Cation Effects on CO Reduction at Copper Single-Crystal Electrodes journal November 2017
Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics journal February 2019
Making the hydrogen evolution reaction in polymer electrolyte membrane electrolysers even faster journal March 2016
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Self-consistent continuum solvation (SCCS): The case of charged systems journal December 2013
Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations journal April 2018
Chemical accuracy for the van der Waals density functional journal December 2009
Physical and Chemical Nature of the Scaling Relations between Adsorption Energies of Atoms on Metal Surfaces journal March 2012
The role of van der Waals forces in water adsorption on metals text January 2013
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways text January 2013
Evaluating continuum solvation models for the electrode-electrolyte interface: challenges and strategies for improvement text January 2016

Cited By (1)

Adsorption processes on a Pd monolayer-modified Pt(111) electrode journal January 2020

Figures / Tables (3)

Figure 1(p. 2)figure Figure 1
Table 1(p. 3)table Table 1
Figure 2(p. 4)figure Figure 2

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
chemistry
physics
adsorbate solvation
density functional theory
near-surface alloys
oxygen reduction reaction
platinum