Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

Sundararaman, Ravishankar; Schwarz, Kathleen

doi:10.1063/1.4976971

Cited by 97 publications

(111 citation statements)

References 37 publications

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“…All the calculations include the long-range dispersion correction approach by Grimme [56,57], which is an improvement on pure DFT when considering large polarizable atoms [58][59][60][61][62][63]. We included a self-consistent aqueous implicit solvation model [64,65]. The optimisation thresholds were 10 −5 eV and 0.03 eV/Å for electronic and ionic relaxation, respectively.…”

Section: Methodsmentioning

confidence: 99%

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

et al. 2018

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Safe and efficient hydrogen generation and storage has received much attention in recent years. Herein, a commercial 5 wt% Pd/C catalyst has been investigated for the catalytic, additive-free decomposition of formic acid at mild conditions, and the experimental parameters affecting the process systematically have been investigated and optimised. The 5 wt% Pd/C catalyst exhibited a remarkable 99.9% H 2 selectivity and a high catalytic activity (TOF = 1136 h −1 ) at 30 °C toward the selective dehydrogenation of formic acid to H 2 and CO 2 . The present commercial catalyst demonstrates to be a promising candidate for the efficient in-situ hydrogen generation at mild conditions possibiliting practical applications of formic acid systems on fuel cells. Finally DFT studies have been carried out to provide insights into the reactivity and decomposition of formic acid along with the two-reaction pathways on the Pd (111) surface.

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Section: Methodsmentioning

confidence: 99%

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

et al. 2018

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“…In computational electrocatalysis adsorbate‐solvent and adsorbate‐electrolyte interactions at the interface can be evaluated implicitly (where the solvent is modelled as a continuum with certain dielectric constant), explicitly, or through combinations of the two . Furthermore, efforts have been devoted to determine the minimal number of explicit water molecules needed to stabilize a given adsorbate .…”

Section: Computational Detailsmentioning

confidence: 99%

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

et al. 2019

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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.

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“…However, the calculation of reaction barriers and the associated kinetics requires the treatment of electrolyte at the interface. To this end, a great deal of effort has been invested to effectively treat charged species at the interface using DFT, ranging from a variety of continuum approximations to a fully ab initio approach …”

Section: Introductionmentioning

confidence: 99%

Practical Considerations for Continuum Models Applied to Surface Electrochemistry

et al. 2019

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Modelling the electrolyte at the electrochemical interface remains a major challenge in ab initio simulations of charge transfer processes at surfaces. Recently, the development of hybrid polarizable continuum models/ab initio models have allowed for the treatment of solvation and electrolyte charge in a computationally efficient way. However, challenges remain in its application. Recent literature has reported that large cell heights are required to reach convergence, which presents a serious computational cost. Furthermore, calculations of reaction energetics require costly iterations to tune the surface charge to the desired potential. In this work, we present a simple capacitor model of the interface that illuminates how to circumvent both of these challenges. We derive a correction to the energy for finite cell heights to obtain the large cell energies at no additional computational expense. We furthermore demonstrate that the reaction energetics determined at constant charge are easily mapped to those at constant potential, which eliminates the need to apply iterative schemes to tune the system to a constant potential. These developments together represent more than an order of magnitude reduction of the computational overhead required for the application of polarizable continuum models to surface electrochemistry.

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Evaluating continuum solvation models for the electrode-electrolyte interface: Challenges and strategies for improvement

Cited by 97 publications

References 37 publications

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

Practical Considerations for Continuum Models Applied to Surface Electrochemistry

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