Nitrogen-doped carbon nanotubes enhanced Fenton chemistry: Role of near-free iron(III) for sustainable iron(III)/iron(II) cycles

Abstract

The sluggish kinetics of Fe(II) recovery strongly impedes the scientific progress of Fenton reaction (Fe(II)/H₂O₂) towards practical application. Here, we propose a novel mechanism that metal-free nitrogen-doped carbon nanotubes (NCNT) can enhance Fenton chemistry with H₂O₂ as electron donors by elevating the oxidation potential of Fe(III). NCNT remarkably promotes the circulation of Fe(III)/Fe(II) to produce hydroxyl radical (^•OH) with excellent stability for multiple usages (more than 10 cycles) in the NCNT/Fe(III)/H₂O₂ system. Although carbonyl on NCNT can act as the electron supplier for Fe(III) reduction, the behavior of NCNT is distinct from common reductants such as hydroxylamine and boron. Electrochemical analysis and density functional theory calculation unveil that nitrogen sites of NCNT can weakly bind with Fe(III) to elevate the oxidation potential of Fe(III) (named near-free Fe(III), primarily FeOH²⁺) at pH ranging from 2.0 to 4.0. Without inputs of external stimulations or electron sacrificers, near-free Fe(III) can promote H₂O₂ induced reduction of Fe(III) to initiate Fenton chain reactions for long-lasting generation of ^•OH. To our delight, it is a common property of N-doped carbon materials (e.g., graphene, carbon nanofibers, and acetylene black), our research thus provides a novel, sustainable, and green strategy for promoting Fenton chemistry.

Keywords: Density functional theory; Fenton chemistry; Hydroxyl radicals; N-doped carbon nanotubes; Near-free Fe(III).