Theory of Solid/Electrolyte Interfaces

Groß, Axel

doi:10.1002/9783527680603.ch56

Cited by 20 publications

(16 citation statements)

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“…This, however, requires computationally expensive ab initio molecular dynamics (AIMD) simulations (Kenmoe et al, 2018;Sakong and Groß, 2020). The cell sizes that can be treated by AIMD (Groß, 2020) so far are too small to simulate the dependency of binding energies on electrolyte concentrations (Groß, 2020). Although a steep increase in the computational power is needed to accurately determine the binding energies as a function of electrolyte composition, the effect of the electrolyte solution on the binding energy of an intermediate is significant, nonetheless.…”

Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

“…Currently, continuum solvation models such as Vaspsol (Mathew et al, 2014(Mathew et al, , 2019, COSMO (Klamt and Schüürmann, 1993), or Jaguar (Bochevarov et al, 2013) are commonly used to describe solvation at the electrode/electrolyte interface (Abidi et al, 2020;Basdogan et al, 2020b;Groß, 2020). However at least in the case of the intermediates relevant to the ORR and CO 2 reduction reactions on Cu, Au, and Pt, the widely used continuum solvation models did not improve the accuracy of binding energies compared to the respective calculations in vacuum (Heenen et al, 2020).…”

Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

“…Experimental conditions, however, correspond to a grand canonical ensemble where the electrode potential is fixed instead of the charge. Recent progress in this field put forth grand canonical models beyond the CHE method (Hansen and Rossmeisl, 2016;Hörmann et al, 2019Hörmann et al, , 2020Abidi et al, 2020), allowing the electrode potential to be explicitly included into the DFT calculations (Govind Rajan et al, 2020;Groß, 2020). Yet, a limitation of this approach is that the outcome may severely depend on the chosen value for the proton/hydrogen work function, for which values between 3.9 eV and 4.7 eV have been reported in the literature (Busch et al, 2020;Bhattacharyya et al, 2021).…”

Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

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The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

2021

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The Sabatier principle, which states that the binding energy between the catalyst and the reactant should be neither too strong nor too weak, has been widely used as the key criterion in designing and screening electrocatalytic materials necessary to promote the sustainability of our society. The widespread success of density functional theory (DFT) has made binding energy calculations a routine practice, turning the Sabatier principle from an empirical principle into a quantitative predictive tool. Given its importance in electrocatalysis, we have attempted to introduce the reader to the fundamental concepts of the Sabatier principle with a highlight on the limitations and challenges in its current thermodynamic context. The Sabatier principle is situated at the heart of catalyst development, and moving beyond its current thermodynamic framework is expected to promote the identification of next-generation electrocatalysts.

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Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

Section: Influence Of the Electrolyte: Beyond The Che Modelmentioning

confidence: 99%

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The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

2021

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“…1a ) 10 . We also have multiple ways to obtain the potential and the potential dependence of the reaction energetics 11 . While continuum approximations give us huge reductions in computational cost, we see significant deviations in solvation energies determined with implicit vs. dynamic explicit water models 12 .…”

Section: What Computational Electrocatalysis Can and Cannot Domentioning

confidence: 99%

A few basic concepts in electrochemical carbon dioxide reduction

Chan

2020

Nat Commun

103

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In this perspective, I discuss a few basic concepts in fundamental mechanistic studies of electrochemical carbon dioxide reduction. With the looming global environmental crisis, electrochemical CO 2 reduction (CO 2 R) is a hot topic. Excellent perspectives on mechanistic studies 1-3 , practical vapor-fed devices 4 , and technoeconomic and system-level analyses 5-7 have come out in the past few years, all with compelling visions for the future. We can also harken back to Hori's timeless review of his work over several decades 8 , which seeded many of the impressive advances today. But as the French maxim says: parfois, il faut reculer pour mieux sauter. Here, I showcase a few basic concepts in the fundamental mechanistic studies of CO 2 R. What computational electrocatalysis can and cannot do In heterogeneous catalysis, periodic density functional theory (DFT) simulations have really enabled us to computationally explore reaction mechanisms. For electrocatalysis, the "computational hydrogen electrode" model is our standard method to determine reaction thermodynamics 9. This method trivially translates simulations in vacuum to potential-dependent energetics, without requiring we simulate explicitly the ions or potential. Our models of the electrolyte and electrochemical reaction barriers, in contrast, are far from convergent. Our field abounds with different approaches towards the electrolyte: implicit continuum models, explicit ab initio ones, or a hybrid of the two (Fig. 1a) 10. We also have multiple ways to obtain the potential and the potential dependence of the reaction energetics 11. While continuum approximations give us huge reductions in computational cost, we see significant deviations in solvation energies determined with implicit vs. dynamic explicit water models 12. Furthermore, different ways to set up the applied potential result in differences in the computed reaction energetics 13. All these challenges could contribute to the wide range in the computed energetics and mechanisms towards the various C 2 products 1. Despite the difficulties in an ab initio treatment of electrochemical reaction barriers, we do need kinetics for mechanistic understanding. Case in point: our evolving understanding of CO (2) R to CH 4 on Cu 14. A thermodynamic analysis showed a proton-electron transfer to *CO to form *CHO to be the rate-limiting step. Considering the corresponding barriers across different materials, we suggested the transition state of this process to be the descriptor of activity. But when we simply consider the kinetics of electrochemical reactions with multiple proton-electron transfers, we see that this step cannot be rate limiting on Cu. The corresponding Tafel plots have defining features that depend on the symmetry factor β (0 < β < 1) for the rate-limiting step, as well as the number of proton-electron transfers preceding it, n. Figure 1b shows the Tafel slopes and the effect of pH on the overpotential for alkaline solutions, where H 2 O as the proton donor. Experiments show

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“…On this account, the interaction of electrolytes with catalytic surfaces was studied intensively in the last decades (Groß, 2020 ; Nowicki and Wandelt, 2020 ). One of the best studied systems is sulfate adsorption on platinum (Shingaya and Ito, 1996 ; Kolics and Wieckowski, 2001 ; Herrero et al, 2002 ; Braunschweig et al, 2010 ; Garcia-Araez et al, 2010 ; Santana et al, 2010 ; Comas-Vives et al, 2013 ), but despite various investigations the surface structure of the ad-layer is still controversially discussed.…”

Section: Introductionmentioning

confidence: 99%

Sulfate, Bisulfate, and Hydrogen Co-adsorption on Pt(111) and Au(111) in an Electrochemical Environment

2020

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The co-adsorption of sulfate, bisulfate and hydrogen on Pt(111) and Au(111) electrodes was studied based on periodic density functional calculations with the aqueous electrolyte represented by both explicit and implicit solvent models. The influence of the electrochemical control parameters such as the electrode potential and pH was taken into account in a grand-canonical approach. Thus, phase diagrams of the stable coadsorption phases as a function of the electrochemical potential and Pourbaix diagrams have been derived which well reproduce experimental findings. We demonstrate that it is necessary to include explicit water molecules in order to determine the stable adsorbate phases as the (bi)sulfate adsorbates rows become significantly stabilized by bridging water molecules.

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Theory of Solid/Electrolyte Interfaces

Cited by 20 publications

References 159 publications

The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

A few basic concepts in electrochemical carbon dioxide reduction

Sulfate, Bisulfate, and Hydrogen Co-adsorption on Pt(111) and Au(111) in an Electrochemical Environment

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