New Implicit Solvation Scheme for Solid Surfaces

Faheem, Muhammad; Suthirakun, Suwit; Heyden, Andreas

doi:10.1021/jp308212h

Cited by 47 publications

(66 citation statements)

References 49 publications

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“…Moreover, Heyden et al have proposed a simple but highly efficient approach for modeling reactions at solid–liquid interfaces with implicit solvation models, by which they found that water can stabilize the dehydrogenated derivatives of propionic acid and propionate and thus affect the reaction mechanism of propanoic acid hydrodeoxygenation over a model Pd(211) catalyst …”

Section: Mechanistic Insightsmentioning

confidence: 99%

The promotional role of water in heterogeneous catalysis: mechanism insights from computational modeling

Chang

Huang

2016

WIREs Comput Mol Sci

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Water is the key to life in our planet. As one of the most abundant resources on the earth, water may play important roles in chemical reactions in addition to being a reaction medium. In this review, we highlight recent advances in experimental observations and mechanistic understanding of the promotional role of water in chemical reactions, with an emphasis on the essential effects of water in heterogeneous catalysis. As water may exist in molecular state or dissociate to hydroxyl (OH) and hydrogen (H) species on catalyst surfaces, we have outlined the roles of water from three aspects: (1) the promotional role of molecular water including the solvation-like effect and water-mediated H-transfer, (2) the promotional role of OH/OH − and H/H + species, and (3) some miscellaneous effects of water, such as water-assisted carbon removal, surface reconstruction, and active sites blocking. The results discussed here provide a fundamental understanding of the promotional role of water in heterogeneous reactions and may inspire the theoretical studies of water effects on other fields of chemistry and atmospheric science as well.

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Section: Mechanistic Insightsmentioning

confidence: 99%

The promotional role of water in heterogeneous catalysis: mechanism insights from computational modeling

Chang

Huang

2016

WIREs Comput Mol Sci

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“…12 In their implicit solvation model for surfaces (iSMS), reaction energies are computed with DFT applying periodic boundary conditions and solvation effects are estimated separately on large metallic clusters using a polarizable continuum model (PCM) for the solvent description. 12 PCM, which accounts for the electrostatic interaction between the solute and the solvent, is well-established in molecular chemistry 13 but less common for metal/liquid interfaces 14,15 since it has only recently become available to the public for periodic boundary conditions. 16 PCM can not describe any direct solvent effects and might be inaccurate for specific hydrogen bonds, 17 which makes the combination of micro-solvation with PCM particularly attractive.…”

Section: Introductionmentioning

confidence: 99%

Solvation free energies for periodic surfaces: comparison of implicit and explicit solvation models

Steinmann

Sautet

Michel

2016

Phys. Chem. Chem. Phys.

101

112

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The evaluation of solvation energies is a great challenge. We focus here on an organic molecule chemisorbed at a metal-liquid interface, as a prototypical system, essential in tribology, electrochemistry and heterogeneous catalysis. We compare an established implicit solvation scheme with a strategy based on molecular mechanics (MM) free energy perturbation (FEP) seeded by QM computations. First, we benchmark the approaches against experimental hydration energies of standard (organic) molecules and find acceptable errors in the order of 0.06 eV (1.3 kcal/mol). Then, the impact of various parameters on the solvation energy of an adsorbate have been assessed on a typical system of interest, levulinic acid adsorbed at a Ru(0001)/water interface. We identify the need for dipole corrections or symmetric slabs when including solvation effects on metallic surfaces. The MM-FEP scheme is revealed to be as reliable as the implicit solvent for water. In the case of levulinic acid, both PCM and MM-FEP agree that the bulk solvation effect is not sufficient to change the adsorption mode from bidentate to mono-dentate, despite the fact that the COOH group is desolvated in the bidentate case. MM-FEP has the great advantage of being more easily generalized to other solvents and to be further improved which will be particularly useful to study solvent and (counter-)ion effects on interfacial reactions.

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“…23 Therefore, different approximations have been proposed: inclusion of only a couple of solvent molecules (called micro-solvation) 24,25 , adsorption of ice-like water layers on metallic surfaces 26,27 , the use of a combination of optimization and AIMD, 11,18,19 the classical treatment of solvent interactions 16,28 or the application of implicit solvent models. [29][30][31] In terms of accessible and interpretable differences between gas-phase and solution-phase reactivity, the advantage of implicit solvents is that solvation energies are directly accessible, which is not the case for AIMD simulations. On the other hand, the main limitation of implicit solvents is that no direct participation of the solvent can be described, in contrast to micro-solvation approaches.…”

Section: Introductionmentioning

confidence: 99%

Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

Schweitzer

Michel

et al. 2017

J. Phys. Chem. C

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International audienceDespite progress in theoretical tools, the influence of solvation in heterogeneous catalysis remains poorly understood and predicted due to the large computational burden. In this work, we show that the inclusion of the solvation by water using a continuum model thermodynamically inhibits the O–H bond scissions involved in the ethanol aqueous phase reforming reaction over Pt(111), while it tends to favor the C–H, C–C, and C–O scissions. Then, we present a novel group additivity scheme for the free energy of adsorbates at the Pt/water interface that is able to capture this solvent effect. The mean absolute error (MeanAE) for the Gibbs free energy of formation is 3.3 kcal/mol over the investigated set of 200 species at the interface and the MeanAE for the 151 reaction free energies of ethanol aqueous phase reforming is 2.8 kcal/mol. Regarding the effect of solvation, our scheme is able to predict it with a MeanAE of about 1 kcal/mol. Together, the scheme promises to be accurate enough for narrowing down the most important reaction pathways in complex reaction networks as encountered in biomass conversion

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New Implicit Solvation Scheme for Solid Surfaces

Cited by 47 publications

References 49 publications

The promotional role of water in heterogeneous catalysis: mechanism insights from computational modeling

The promotional role of water in heterogeneous catalysis: mechanism insights from computational modeling

Solvation free energies for periodic surfaces: comparison of implicit and explicit solvation models

Group Additivity for Aqueous Phase Thermochemical Properties of Alcohols on Pt(111)

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