Structure and catalytic activities of ferrous centers confined on the interface between carbon nanotubes and humic acid

Abstract

Preparation of heterogeneous catalysts with active ferrous centers is of great significance for industrial and environmental catalytic processes. Nanostructured carbon materials (NCM), which possess free-flowing π electrons, can coordinate with transition metals, provide a confinement environment for catalysis, and act as potential supports or ligands to construct analogous complexes. However, designing such catalysts using NCM is still seldom studied to date. Herein, we synthesized a sandwich structured ternary complex via the coordination of Fe-loaded humic acid (HA) with CC bonds in the aromatic rings of carbon nanotubes (CNTs), in which the O/N–Fe–C interface configuration provides the confinement environment for the ferrous sites. The experimental and theoretical results revealed octahedrally/tetrahedrally coordinated geometry at Fe centers, and the strong hybridization between CNT C π* and Fe 3d orbitals induces discretization of the atomic charges on aromatic rings of CNTs, which facilitates O₂ adsorption and electron transfer from carbon to O₂, which enhances O₂ activation. The O₂ activation by the novel HA/Fe-CNT complex can be applied in the oxidative degradation of phenol red (PR) and bisphenol A (BPA) in aqueous media.