Screening for the adsorption-activated H2O2 and peroxymonosulfate for high-performance heteroatom-doped graphene: Molecular dynamics simulation and DFT.

[Display omitted] • The MD + DFT complementarity method is used. • The adsorption activation behavior of activated molecules on the surfaces of the six catalysts occurs in the first adsorption layer. • The electrostatic interaction between catalyst and activated molecules and van der Waals interaction have significant effects on the adsorption process of both, and the electrostatic interaction is greater than the van der Waals interaction. • Compared with other heteroatom-doped graphene, BGR and NGR have better catalytic properties, in which BGR has better catalytic activation properties for H 2 O 2 , while NGR has better catalytic activation properties for PMS. • It is speculated that -BC 2 O and -NC 2 functional groups are the main functional regions of H 2 O 2 activation by BGR and PMS activation by NGR, respectively. As an green and efficient metal-free catalyst, heteroatom-doped graphene has gradually become a research topic in the catalytic field, but the active sites and mechanisms of the catalytic reactions are still not thorough enough. In this paper, the adsorption-activation properties of two activated molecules, H 2 O 2 and peroxymonosulfate (PMS), on graphene (GR) and heteroatom (N, P, B, Si, F) doped graphene were investigated by means of computational methods. Molecular dynamics (MD) simulation results showed that the adsorption activation process of activated molecules on the surface of the six catalysts occurs in their first adsorption layer, in which B-doped graphene (BGR) has better catalytic activation performance for H 2 O 2 , while N -doped graphene (NGR) has better catalytic activation performance for PMS. Density function theory (DFT) revealed that the lowest molecular orbital gap of H 2 O 2 at -BCO 2 (0.691 eV), PMS at -NC 2 has the lowest gap (0.432 eV). It is inferred that -BCO 2 and -NC 2 functional groups are the main functional regions of H 2 O 2 activation by BGR and PMS activation by NGR, respectively. This work provides useful guidance for the design and optimization of high-performance metal-free catalysts, and the realization of green remediation for wastewater in the electrocatalytic oxidation process. [ABSTRACT FROM AUTHOR]