Transition metal (X = Mn, Fe, Co, Ni, Cu, Zn)-doped graphene as gas sensor for CO2 and NO2 detection: a molecular modeling framework by DFT perspective

Fatemeh Mollaamin; Majid Monajjemi

doi:10.1007/s00894-023-05526-3

Transition metal (X = Mn, Fe, Co, Ni, Cu, Zn)-doped graphene as gas sensor for CO₂ and NO₂ detection: a molecular modeling framework by DFT perspective

J Mol Model. 2023 Mar 29;29(4):119. doi: 10.1007/s00894-023-05526-3.

Authors

Fatemeh Mollaamin¹, Majid Monajjemi²

Affiliations

¹ Department of Biomedical Engineering, Faculty of Engineering and Architecture, Kastamonu University, Kastamonu, Turkey. smollaamin@gmail.com.
² Department of Chemical Engineering, Central Tehran Branch, Islamic Azad University, Tehran, Iran.

PMID: 36988725
DOI: 10.1007/s00894-023-05526-3

Abstract

Context: In this research, CO₂ and NO₂ adsorption on doped nanographene (NG) sheets with transition metals (Fe, Ni, Zn) and (Mn, Co, Cu), respectively, have been applied for scavenging of these toxic gases as the environmental pollutants. The values of changes of atomic charge density have illustrated a more significant charge transfer for Ni-doped C-NG through CO₂ adsorption and a more remarkable charge transfer for Co-doped C-NG through NO₂ adsorption. The data of NMR spectroscopy has depicted several fluctuations around the graph of Zn-doped on the nanographene surface. The thermodynamic results from IR spectroscopy have indicated that [Formula: see text] values are almost similar for doped metal transitions of Mn, Co, and Cu on the C-NG nanosheet, while [Formula: see text] has the largest gap of Gibbs free energy adsorption with dipole moment.

Methods: The Langmuir adsorption model with a three-layered ONIOM using CAM-B3LYP functional accompanying LANL2DZ, EPR-III and 6-31 + G (d,p) basis sets due to Gaussian 16 revision C.01 program on the complexes of CO₂ → (Fe, Ni, Zn) and NO₂ → (Mn, Co, Cu) doped on the C-NG has been accomplished. Then, NMR and IR spectroscopy, nuclear quadrupole resonance, and natural bond orbital analysis have been accomplished for evaluating chemical shielding tensors, thermodynamic properties, electric potential, and occupancy fluctuation through bond orbitals, respectively. In addition, frontier orbitals of LUMO, HOMO, and also a series of chemical reactivity parameters have been calculated. Finally, time-dependent-DFT method due to UV-VIS spectrums has been accomplished to discern the low-lying excited states of CO₂ and NO₂ adsorption on the (Fe, Ni, Zn) and (Mn, Co, Cu), respectively, doped C-NG sheet.

Keywords: (Fe, Ni, Zn) @C-NG; (Mn, Co, Cu) @C-NG; CO2; Gas sensor; Langmuir adsorption; NO2; ONIOM/CAM.