Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles

Calle‐Vallejo, Federico; Morais, Rodrigo Ferreira de; Illas, Francesc; Loffreda, David; Sautet, Philippe

doi:10.1021/acs.jpcc.9b01211

Cited by 62 publications

(83 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…where * represents an active site at the NSAs surface. Recent works have shown that three *H 2 O molecules are required to solvate *OH, as the O atom in *OH can make two hydrogen bonds with surrounding water molecules and the H atom can make one . This is also the case for the periodic water bilayers considered here, as shown in Figure a.…”

Section: Resultssupporting

confidence: 52%

“…Following previous works, to obtain the free energy of solvation (Ω OH ) for *OH on the √3×√3 R30° slab, we determined: (i) the free energy of formation of 1/3 ML *OH coadsorbed with 1/3 ML *H 2 O with respect to an ice‐like water bilayer with 2/3 ML *H 2 O (

Δ G_{O H}^{H_{2} O}

), as shown in Equation (1) and in Figure a; and (ii) The free energy of formation of 1/3 ML *OH in vacuum with respect to H 2 O(l) (

Δ G_{O H}^{v a c}

) using Equation (2), as depicted in Figure b.

true 2^{*} normalH_{2} normalO \to^{*} OH +^{*} normalH_{2} normalO + normalH^{+} + normale^{-}

true^{*} + H_{2} O (l) \to^{*} OH + normalH^{+} + normale^{-}

…”

Section: Resultsmentioning

confidence: 99%

“…Once Ω OH is known, it can be added to other adsorption energies calculated in vacuum

((), Δ G_{O H}^{v a c #})

to obtain a first assessment of the adsorption energies in solution (

Δ G_{O H}^{H_{2} O #}

), which are usually burdensome to calculate:

true Δ G_{O H}^{H_{2} O #} \approx Δ G_{O H}^{v a c #} + Ω_{O H}

…”

Section: Resultsmentioning

confidence: 99%

“…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 . Such “micro‐solvation” approaches are specifically devised to save computational resources and speedup electrocatalysis modelling.…”

Section: Computational Detailsmentioning

confidence: 99%

See 3 more Smart Citations

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

et al. 2019

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 52%

Δ G_{O H}^{H_{2} O}

), as shown in Equation (1) and in Figure a; and (ii) The free energy of formation of 1/3 ML *OH in vacuum with respect to H 2 O(l) (

Δ G_{O H}^{v a c}

) using Equation (2), as depicted in Figure b.

true 2^{*} normalH_{2} normalO \to^{*} OH +^{*} normalH_{2} normalO + normalH^{+} + normale^{-}

true^{*} + H_{2} O (l) \to^{*} OH + normalH^{+} + normale^{-}

…”

Section: Resultsmentioning

confidence: 99%

“…Once Ω OH is known, it can be added to other adsorption energies calculated in vacuum

((), Δ G_{O H}^{v a c #})

to obtain a first assessment of the adsorption energies in solution (

Δ G_{O H}^{H_{2} O #}

), which are usually burdensome to calculate:

true Δ G_{O H}^{H_{2} O #} \approx Δ G_{O H}^{v a c #} + Ω_{O H}

…”

Section: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…111 Here it is worth mentioning that generalized coordination numbers in conjunction with micro-solvation can also be used to calculate average water stabilization values for extended surfaces and nanoparticles. 112 Additionally, solvation is a crucial factor in studies aimed at breaking scaling relations in solution. As seen in the recent literature, 111 adsorption-energy scaling relations broken under vacuum conditions can, in some cases, be restored in solution by virtue of solvation.…”

Section: Solvent and Electrolyte Effectsmentioning

confidence: 99%

Revealing the nature of active sites in electrocatalysis

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

Modeling Single‐Atom Catalysis

Di Liberto,

Pacchioni

2023

Advanced Materials

View full text Add to dashboard Cite

Electronic structure calculations represent an essential complement of experiments to characterize single‐atom catalysts (SACs), consisting of isolated metal atoms stabilized on a support, but also to predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple as often assumed. In this work, the essential factors that characterize a reliable simulation of SACs activity are examined. The Perspective focuses on the importance of precise atomistic characterization of the active site, since even small changes in the metal atom's surroundings can result in large changes in reactivity. The dynamical behavior and stability of SACs under working conditions, as well as the importance of adopting appropriate methods to solve the Schrödinger equation for a quantitative evaluation of reaction energies are addressed. The Perspective also focuses on the relevance of the model adopted. For electrocatalysis this must include the effects of the solvent, the presence of electrolytes, the pH, and the external potential. Finally, it is discussed how the similarities between SACs and coordination compounds may result in reaction intermediates that usually are not observed on metal electrodes. When these aspects are not adequately considered, the predictive power of electronic structure calculations is quite limited.

show abstract

Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles

Cited by 62 publications

References 41 publications

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

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

Revealing the nature of active sites in electrocatalysis

Modeling Single‐Atom Catalysis

Contact Info

Product

Resources

About