Computational Simulations of Adsorption Behavior of Anionic Surfactants at the Portlandite–Water Interface under Sulfate and Calcium Ions

Zhao, Hongxia; Yang, Yong; Shu, Xin; Qiao, Min; Dong, Lei; Ran, Qianping

doi:10.1021/acs.langmuir.3c03914

Cited by 1 publication

(1 citation statement)

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“…Acetonitrile was modeled using a flexible six-site potential model introduced by Kowsari and Tohidifar . The LJ parameters for BnBr, TBA + , and I – were taken from the literature. − The van der Waals interactions of the solute with Au (111) were represented by Lennard-Jones potential described by Heinz et al Several studies have demonstrated that these parameters can qualitatively replicate interactions between the metal surface and the solution interface, ,− while the Lennard-Jones parameters for interactions in solution effectively capture physical phenomena in the bulk.…”

Section: Methodsmentioning

confidence: 99%

Electric Double Layer Effect on the Outer-Sphere Benzyl Halides Electro-Reduction Mechanism

Kramarenko,

Chernyshov,

Pidko

2024

J. Phys. Chem. C

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Electrocatalytic reduction of organic halides and subsequent carboxylation are promising methods for the valorization of CO 2 as a C1 source in synthetic organic chemistry. The reaction mechanism underlying the selectivity and reduction mechanism of benzyl halides is highly dependent on the nature of the electrode material as well as the processes, composition, and structure of the liquid phase at the electrode−solution interface. Herein, we present a computational study on the influence of the electric double layer (EDL) on the activation of benzyl halides at different applied potentials over the Au (111) cathode. Using a multiscale modeling approach, we demonstrate that, under realistic electrocatalytic conditions, the formation of a dense EDL over the cathode hampers the diffusion of benzyl halides toward the electrode surface. A combination of classical molecular dynamics simulations and density functional theory calculations reveals the most favorable benzyl halide electro-carboxylation pathway over the EDL that does not require direct substrate adsorption to the cathode surface. The dense EDL promotes the dissociative reduction of the benzyl halides via the outer-sphere electron transfer from the cathode surface to the electrolyte. Such a reduction mechanism results in a benzyl radical intermediate, which is then converted to benzyl anions in the EDL via an additional electron transfer step.

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