New insights in self-assembled monolayer of imidazolines on iron oxide investigated by DFT

Gouron, Aurélie; Mapihan, Katell Le; Camperos, Sheyla; Farra, Ahmad Al; Lair, Virginie; Ringuedé, Armelle; Cassir, Michel; Diawara, Boubakar

doi:10.1016/j.apsusc.2018.06.119

Cited by 20 publications

(10 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The (0001) surface of α-Fe 2 O 3 is widely used both as a catalyst , and as a model for steel surfaces. , It is described here using a p (3 ×3) cell. The primitive cell is represented in Figure a, showing that only one type of iron atom is exposed at the surface.…”

Section: Methodsmentioning

confidence: 99%

Transferable Gaussian Attractive Potentials for Organic/Oxide Interfaces

et al. 2021

View full text Add to dashboard Cite

Organic/oxide interfaces play an important role in many areas of chemistry, and in particular for lubrication and corrosion. Molecular dynamics simulations are the method of choice for providing complementary insight to experiments. However, the force fields used to simulate the interaction between molecules and oxide surfaces tend to capture only weak physisorption interactions, discarding the stabilizing Lewis acid/base interactions. We here propose a simple complement to the straightforward molecular mechanics description based on "out-of-the-box" Lennard-Jones potentials and electrostatic interactions: the addition of an attractive Gaussian potential between reactive sites of the surface and heteroatoms of adsorbed organic molecules, leading to the GLJ potential. The interactions of four oxygenated and four amine molecules with the typical and widespread hematite and γ-alumina surfaces are investigated. The total RMSD for all probed molecules is only 5.7 kcal/mol, and the corresponding percentage 23% over hematite, while on γ-alumina the RMSD is 11.2 kcal/mol, despite using a single parameter for all five chemically inequivalent surface aluminum atoms. Applying GLJ to the simulation of organic films on oxide surfaces demonstrates that mobility of the surfactants is overestimated by the simplistic LJ potential, while GLJ and other qualitatively correct potentials show a strong structuration and slow dynamics of the surface films, as could be expected from the first-principles adsorption energies for model head-groups.

show abstract

Section: Methodsmentioning

confidence: 99%

Transferable Gaussian Attractive Potentials for Organic/Oxide Interfaces

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Hematite, α-Fe2O3, is the most abundant iron oxide on earth 49 and is of interest in a wide range of applications including energy storage 52,62 and catalysis 52,63,64 . In this paper, we chose the representative hematite (0001) surface as a model for the oxidized steel surface, in agreement with several previous studies [65][66][67] .…”

Section: Hematitementioning

confidence: 98%

(Dis)Similarities of adsorption of diverse functional groups over alumina and hematite depending on the surface state

Blanck

Martí

Loehlé

et al. 2021

The Journal of Chemical Physics

View full text Add to dashboard Cite

To accelerate the conversion to more sustainable lubricants, there is a need for an improved understanding of the adsorption at the solid/liquid interface. As a first step, the DFT computed adsorption energies can be used to screen the ability of additives to cover a surface. Analogously to what has been found in catalysis with the universal scaling relations, we investigate here if a general universal ranking of additives can be found, independently of the surface considered. We divided our set of 25 diverse representative molecules into aprotic and protic molecules. We compared their adsorption over alumina and hematite, which are models of surface oxidized aluminum and steel, respectively. The adsorption energy ranking of our set is not strongly affected by alumina hydration.In contrast, adsorption on hematite is more strongly affected by hydration since all exposed Fe Lewis acid sites are converted into hydroxylated Brønsted basic sites. However, the ranking obtained on hydrated hematite is close to the one obtained on dry alumina, paving the road to a fast screening of additives. In our library, protic molecules are more strongly adsorbed than non-protic molecules. In particular, methyl and dimethyl phosphates are the most strongly adsorbed ones, followed by Nmethyldiethanolamine, succinimide and ethanoic acid. Additives combining these functional groups are expected to strongly adsorb at the solid/liquid interface and, therefore, likely to be relevant components of lubricant formulations.

show abstract

“…The (0001) surface of α-Fe2O3 is widely used both as a catalyst 17,77 and as a model for steel surfaces. 78,79 It is described here using a p(3 × 3) cell. The primitive cell is represented in Figure 1.a showing that only one type of iron atom is exposed at the surface.…”

Section: Surface Slab Models and Molecule Adsorption At The Dft Levelmentioning

confidence: 99%

Transferable Gaussian Attractive Potentials for Organic/oxide Interfaces

Rey¹,

Blanck²,

Clabaut³

et al. 2021

Preprint

View full text Add to dashboard Cite

Organic/oxide interfaces play an important role in many areas of chemistry, and in particular for lubrication and corrosion. Molecular dynamics simulations are the method of choice for providing complementary insight to experiments. However, the force fields used to simulate the interaction between molecules and oxide surfaces tend to capture only weak physisorption interactions, discarding the stabilizing Lewis acid/base interactions. We here propose an improvement of the usual molecular mechanics description (based on Lennard-Jones and electrostatic interactions) by addition of an attractive Gaussian potential between reactive sites of the surface and heteroatoms of adsorbed organic molecules, leading to the GLJ potential. The interactions of four oxygenated and four amine molecules with the typical and widespread hematite and γ-alumina surfaces are investigated. The total RMSD for all probed molecules decreases from 29.2 to 5.7 kcal/mol, and the corresponding percentage from 107.4 to 22.6% over hematite, while on γ-alumina the RMSD decreases from 21.5 to 7.6 kcal/mol, despite using a single parameter for all five chemically inequivalent surface aluminum atoms. Applying GLJ to the simulation of n-octadecanamine and N-tetradecyldiethanolamine adsorbed films on hematite and alumina respectively demonstrates that mobility of the surfactants is overestimated by the common LJ potential, while GLJ shows a strong structuration and slow dynamics of the surface films, as could be expected from the first-principles adsorption energies for model head-groups.

show abstract

New insights in self-assembled monolayer of imidazolines on iron oxide investigated by DFT

Cited by 20 publications

References 38 publications

Transferable Gaussian Attractive Potentials for Organic/Oxide Interfaces

Transferable Gaussian Attractive Potentials for Organic/Oxide Interfaces

(Dis)Similarities of adsorption of diverse functional groups over alumina and hematite depending on the surface state

Transferable Gaussian Attractive Potentials for Organic/oxide Interfaces

Contact Info

Product

Resources

About