Some Unexpected Behavior of the Adsorption of Alkali Metal Ions onto the Graphene Surface under the Effect of External Electric Field

Peles‐Lemli, Beáta; Kánnár, Dániel; Nie, Jundan; Li, Heng; Kunsági‐Máté, Sándor

doi:10.1021/jp403856e

Cited by 42 publications

(28 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Optimized structures of benzene interacting with halide ions indicate that the π‐electron clouds of benzene show strong repulsion with incoming halide ions and cause them to be associated mainly with the terminal H atoms instead of being situated on top of the benzene ring as in the case of graphene (Figure ) . This also validates the present graphene models, which have been widely used before …”

Section: Resultssupporting

confidence: 82%

See 1 more Smart Citation

Insights from the Adsorption of Halide Ions on Graphene Materials

Zhu

Yang

2016

ChemPhysChem

View full text Add to dashboard Cite

Graphene has recently found applications in a wide range of fields. Density functional calculations show that halide ions can be adsorbed on pristine graphene, but only F(-) has an appreciable binding energy (-97.0 kJ mol(-1) ). Graphene materials, which are mainly electron donors, can be made strong electron acceptors by edge functionalization with F atoms. The binding strengths of halide ions are greatly enhanced by edge functionalization and show direct proportionality with the degree of functionalization Θ and increased charge transfer. In contrast, the adsorption strengths of metal ions on pristine graphene are clearly superior to those of halide ions but decline substantially with increasing degree of edge functionalization, and for Θ=100 %, the binding energies of -95.7, -44.8, and -25.9 kJ mol(-1) that are calculated for Li(+) , Na(+) , and K(+) , respectively, are obviously inferior to that of F(-) (-186.3 kJ mol(-1) ). Thus, the electronic properties of graphene are fundamentally regulated by edge functionalization, and the preferential adsorption of certain metal ions or anions can be facilely realized by choice of an appropriate degree of functionalization. Adsorbed metal ions and anions behave differently on gradual addition of water molecules, and their binding strengths remain substantial when graphene materials are in the pristine and highly edge functionalized states, respectively.

show abstract

Section: Resultssupporting

confidence: 82%

“…In line with previous studies, a graphene monolayer with 19 aromatic rings (Figure a) was used for adsorption of halide ions (X − ) and metal ions (M + ). The graphene structure has the chemical formula of C 54 H 18 when passivated with H atoms.…”

Section: Computational Detailsmentioning

confidence: 86%

Insights from the Adsorption of Halide Ions on Graphene Materials

Zhu

Yang

2016

ChemPhysChem

View full text Add to dashboard Cite

show abstract

“…Aside from the substituents on a π-framework, it has been shown that an external electric field (EEF) can modulate the bonding properties of the ion-π systems. 26,27,28,29 In the following after a brief introduction to the effect of an EEF on electronic energy of our model systems in Section 1.2, and describing the computational methods (Section 2) we study the effect of substituents and an EEF on the bonding between a number of singly charged ions and substituted coronenes. Variations of the binding energy, electronic properties, and electric response properties of the substituted coronenes are investigated in the absence and presence of an EEF in Section 3.…”

Section: Ion-π Interactionmentioning

confidence: 99%

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Novák

Foroutan‐Nejad

Marek

2016

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Substituted coronenes, a family of ion-π receptors whose ion-affinities can be explained exclusively neither via ion-quadrupole nor induction/polarization mechanisms, are studied. The best descriptors of ion-affinity among these species are those characterizing charge-transfer between ions and the π-systems, e.g. vertical ionization potential, electron affinity, and the relative energies of charge-transfer excited-states (CTESs). The variation of the electric multipole moments, polarizability, binding energy, and relative energy of CTESs in the presence of an external electric field (EEF) is evaluated. The results indicate that the EEF has a negligible effect on the polarizability and quadrupole moment of the systems. However, it significantly affects the binding energies, CTES energies, and the dipole moments of the receptors. Contrary to the changes in the dipole moment, the variation pattern of the binding energy is more consistent with the pattern observed for the CTES energy changes. Finally, by analyzing the exchange-correlation component of the binding energy we demonstrate that the increased binding energy, i.e. bond strengthening, originates from enhanced electron sharing and multicenter covalency between the ions and the π-systems as a result of the state-mixing between the ground-state and the CTESs. According to our findings, we hypothesize that the electron sharing and in extreme cases the multicenter covalency are the main driving forces for complexation of ions with extended π-receptors such as carbon nanostructures.

show abstract

“…Colherinhas et al [56] conduct DFT calculations and indicate that the adsorption strength of metal ions on grapheme is closely associated with the radius and charge of metal ions. The adsorption configurations with the highest stability correspond to the hollow site (H-site) where metal ions are situated at the center of an aromatic ring, as a result of maximizing the cation-π interactions [57]. As indicated by Addition of water molecules may significantly weaken the binding between metal ions on grapheme [58].…”

Section: +mentioning

confidence: 99%

Adsorption of Ions at the Interface of Clay Minerals and Aqueous Solutions

Jia¹,

Wang²,

Zhu³

et al. 2016

Advances in Colloid Science

View full text Add to dashboard Cite

Adsorption of ions at the interface of clay minerals and aqueous solutions plays a critical role in a wide spectrum of colloidal, chemical, physical, and geological processes. Owing to the particular complexity of related systems and the femtosecond scale of related processes, the direct experimental observations often become a challenging task. As a contrast, computer simulations have proven to be a competent and powerful approach therein and already realized fruitful and significant contributions. In this chapter, we attempt to draw a relatively comprehensive picture of the interfacial adsorption of ions mainly within the context of computer simulations. As elaborated, quantum mechanics (QM) and molecular dynamics (MD), two popular simulation techniques currently used, have respective advantages, and with their collaborative efforts, we are striding toward the in-depth and systematic understanding of adsorption configuration, distribution, stability, reaction thermodynamics and mechanism, dynamics, diffusivity as well as electric double layer and other fundamental issues that are closely associated with the adsorption of ions at the interface of clay minerals and aqueous solutions. In addition, we demonstrate that investigation of the interfacial adsorption of ions greatly helps to unravel the origin and mechanism of ion-specific effects, whose importance has been explicitly suggested to be no less than Gregor Mendel's work to genetics.

show abstract

Some Unexpected Behavior of the Adsorption of Alkali Metal Ions onto the Graphene Surface under the Effect of External Electric Field

Cited by 42 publications

References 28 publications

Insights from the Adsorption of Halide Ions on Graphene Materials

Insights from the Adsorption of Halide Ions on Graphene Materials

Modulating Electron Sharing in Ion-π-Receptors via Substitution and External Electric Field: A Route toward Bond Strengthening

Adsorption of Ions at the Interface of Clay Minerals and Aqueous Solutions

Contact Info

Product

Resources

About