DFT study of common anions adsorption at graphene surface due to anion-π interaction

Fan Xiaozhen; Liu Xing; He Zhenglin; Zhu Kaiyuan; Shi Guosheng

doi:10.1007/s00894-022-05218-4

DFT study of common anions adsorption at graphene surface due to anion-π interaction

J Mol Model. 2022 Jul 20;28(8):225. doi: 10.1007/s00894-022-05218-4.

Authors

Fan Xiaozhen¹, Liu Xing², He Zhenglin¹, Zhu Kaiyuan³, Shi Guosheng^{1

4}

Affiliations

¹ State Key Lab. Advanced Special Steel, Shanghai Applied Radiation Institute, Shanghai University, Shanghai, 200444, China.
² State Key Lab. Advanced Special Steel, Shanghai Applied Radiation Institute, Shanghai University, Shanghai, 200444, China. liuxing0215@shu.edu.cn.
³ School of Science, East China University of Science and Technology, Shanghai, 200237, China.
⁴ Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China.

PMID: 35857141
DOI: 10.1007/s00894-022-05218-4

Abstract

Using density functional theory (DFT) calculations, we researched the different anions adsorption on the graphene and found that anions can be stably adsorbed on the graphene surface due to the anion-π interaction. The adsorption energy decreased as the order of HPO₄^2- > SO₄^2- > F^- > CH₃COO^- > ClO₃^- > NO₃^- > ClO₄^- > SCN^- > Cl^- > Br^-. The adsorption energy markedly increased as the valence of anion increased from negative monovalence (< -20 kcal/mol) to negative bivalence (> -40 kcal/mol). The energy decomposition analysis (EDA) showed that anion-π interaction is mainly induced by orbital effect. This work provides new insights for understanding Hofmeister effect at graphene interface from the molecular level and indicates that the anion-π interaction cannot be ignored at the interface, especially for the substrate with π-electron-rich carbon-based nanomaterials.

Keywords: Anion-π interaction; DFT; Graphene.

Abstract

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