Key role of carbon as an efficient electron bridge in CuO@C@Fe2O3 for enhancing H2O2 activation during photo-assisted Fenton-like reaction

Abstract

The Fe3+/Fe2+ cycle has been identified as the rate-limiting step in the Fenton system, and many efforts have been made to promote the Fe3+ reduction via external electrons provided by various electron donors. However, how to design an efficient electron transport pathway and then inhibit the invalid electron shuttle has been largely underestimated. In this study, two kinds of heterogeneous Fenton catalysts of CuO@Fe2O3 and CuO@C@Fe2O3 were prepared. The key role of carbon in transporting electrons as an electron bridge and its enhancement mechanism in photo-assisted Fenton-like performances were explored in detail. Compared with CuO@Fe2O3, the removal efficiency of tetracycline (TC) and the corresponding pseudo-first order reaction rate constants over CuO@C@Fe2O3 increased significantly from 88.6% and 0.1054min-1 to 99.7% and 0.2058min-1, respectively. Based on a series of probe experiments, visible light irradiation can promote the reduction of Cu2+ to Cu+, then the carbon in CuO@C@Fe2O3 can effectively transfer electrons from Cu+ to Fe3+, enhancing the Fe3+/Fe2+ cycle and the following Fenton-like efficiency. Since more ·OH while less ∙O2- was produced over CuO@C@Fe2O3, which further supports the fact that the enhanced Fe3+/Fe2+ cycle was due to the transfer electron from Cu+ to Fe3+ instead of the Haber-Wiss mechanism. Hence, this study provides new insight for effectively improving the transfer efficiency and effective utilization of electrons in Fenton systems.