Density functional theory prediction of pKa for carboxylated single-wall carbon nanotubes and graphene

•pKas for carboxylated SWCNT and graphene are predicted by SMD/M05-2X method.•pKa of the COOH functionalized nanotubes mainly depends on the solvation energy.•Decarboxylation occurs when Cs is sp3 hybridization in the deprotonated state.

Density functional calculations have been performed to investigate the acidities for the carboxylated single-wall carbon nanotubes and graphene. The pKa values for different COOH-functionalized models with varying lengths, diameters and chirality of nanotubes and with different edges of graphene were predicted using the SMD/M05-2X/6-31G* method combined with two universal thermodynamic cycles. The effects of following factors, such as, the functionalized position of carboxyl group, the Stone-Wales and single vacancy defects, on the acidity of the functionalized nanotube and graphene have also been evaluated. The deprotonated species have undergone decarboxylation when the hybridization mode of the carbon atom at the functionalization site changed from sp2 to sp3 both for the tube and graphene. The knowledge of the pKa values of the carboxylated nanotube and graphene could be of great help for the understanding of the nanocarbon materials in many diverse areas, including environmental protection, catalysis, electrochemistry and biochemistry.

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