Examining O₂ adsorption on pristine and defective popgraphene sheets: A DFT study

Resumo

Context Popgraphene (PopG) is a two-dimensional carbon-based material with fused pentagonal and octagonal rings. Like graphene, it exhibits a metallic band gap and exceptional thermal, dynamic, and mechanical stability. Here, we theoretically study the electronic and structural properties of PopG monolayers, including their doped and vacancy-endowed versions, as O2 adsorbers. Our findings show that pristine and vacancy-endowed PopG sheets have a comparable ability to adsorb O2 molecules, with adsorption energies ranging from −0.57 to −0.59 eV (physisorption). In these cases, octagonal rings play a dominant role in the adsorption mechanism. Platinum and Silicon doping enhance the O2 adsorption in areas close to the octagonal rings, resulting in adsorption energies ranging from −1.13 to −2.56 eV (chemisorption). Furthermore, we computed the recovery time for the adsorbed O2 molecules. The results suggest that PopG/O2 interaction in pristine and vacancy-endowed cases can change the PopG electronic properties before O2 diffusion. Methods Density Functional Theory (DFT) simulations, with Van der Waals corrections (DFT-D, within the Grimme scheme), were performed to study the structural and electronic properties of PopG/O2 systems using the DMol3 code within the Biovia Materials Studio software. The exchange and correlation functions are treated within the generalized gradient approximation (GGA) as parameterized by Perdew-Burke-Ernzerhof (PBE) functional. We used the double-zeta plus polarization (DZP) for the basis set in these cases. We also considered the BSSE correction through the counterpoise method and the nuclei-valence electron interactions by including semi-core DFT pseudopotentials.

JOURNAL OF MOLECULAR MODELING, 2023 · Fator de impacto 2,9.

DOI 10.1007/s00894-023-05692-4