title: Insights from the Adsorption of Halide Ions on Graphene Materials.
abstract: 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.
authors.affiliation: College of Resources and Environment & Chongqing Key Laboratory of Soil Multi-scale Interfacial Process, Southwest University, Chongqing, 400715, P. R. China.
authors.forename: Chang
authors.initials: C
authors.lastname: Zhu
authors.affiliation: College of Resources and Environment & Chongqing Key Laboratory of Soil Multi-scale Interfacial Process, Southwest University, Chongqing, 400715, P. R. China. theobiochem@gmail.com.
authors.forename: Gang
authors.initials: G
authors.lastname: Yang
keywords: adsorption; anions; density functional calculations; graphene; halogenation