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The effect of sulfur and nitrogen/sulfur co-doping in graphene surface on the adsorption of toxic heavy metals (Cd, Hg, Pb)

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Abstract

The adsorption of toxic heavy metals (THMs), including cadmium (Cd), mercury (Hg), and lead (Pb), on the graphene (G) and six sulfur- and nitrogen/sulfur-co-doped graphene surfaces (G@1N@1S, G@1N@2S, G@2N@1S, G@1S, G@2S, G@3S) has been studied using electronic structure methods. The doping of graphene surface with the nitrogen and sulfur atoms increases the adsorption energies of THMs. The strongest interaction is seen with adsorption of Pb atom on the surfaces, following the order Pb > Cd > Hg and is confirmed by the atoms in molecules analysis, noncovalent interaction plots, and frontier molecular orbitals. The free energy of adsorption calculation shows that the adsorption process of Pb atoms on the surfaces is exothermic and proceeds spontaneously, while the nature of adsorption of Cd and Hg atoms is endothermic. Significant changes in the electronic structure of the surfaces are seen with adsorption of THMs. A significant change in the HOMO–LUMO energy gap (Eg) and electrical conductivity (σ) of the surfaces is observed with adsorption of Pb atoms, in contrast to Cd and Hg atoms counterparts. Moreover, the calculated optical properties of the surfaces and their complexes with THMs using time-dependent density functional theory reveal that the absorption spectra of the surfaces undergo appreciable changes after adsorption of THMs. These studies indicate the potential use of defect engineering and decoration of vacant sites by chalcogens/pnictogens for sensing of toxic heavy metals.

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Acknowledgements

We gratefully acknowledge financial support from the Research Council of Jahrom University and Birjand University of Technology.

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Authors and Affiliations

  1. Department of Physics, Jahrom University, Jahrom, P.O. Box 74135-111, Iran

    Hamid Reza Ghenaatian

  2. Department of Chemical Engineering, Birjand University of Technology, Birjand, P.O. Box 97175/569, Iran

    Mehdi Shakourian-Fard

  3. Dalzierfiver LLC, 3500 Carlfied St, EL Sobrante, CA, 94803, USA

    Ganesh Kamath

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  1. Hamid Reza Ghenaatian
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  2. Mehdi Shakourian-Fard
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Correspondence to Hamid Reza Ghenaatian or Mehdi Shakourian-Fard.

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10853_2019_3791_MOESM1_ESM.docx

This material contains the optimized geometries of G@3C and G@4C surfaces and their complexes with THMs, the adsorption energies (Eads) for interaction of G@3C(b) and G@4C(b) surfaces with THMs, the results of AIM analysis, correlation between the sum of electron density (∑ρ(r)) and the sum of Wiberg bond indices (∑Wbi) values in the surface–THM complexes, noncovalent interaction (NCI) plots, and TD–DFT results of the surfaces and their complexes with Cd, Hg, and Pb atoms (DOCX 9285 kb)

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Ghenaatian, H.R., Shakourian-Fard, M. & Kamath, G. The effect of sulfur and nitrogen/sulfur co-doping in graphene surface on the adsorption of toxic heavy metals (Cd, Hg, Pb). J Mater Sci 54, 13175–13189 (2019). https://doi.org/10.1007/s10853-019-03791-3

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