Revealing the synergistic mechanism of the generation, migration and nearby utilization of reactive oxygen species in FeOCl-MOF yolk-shell reactors

Abstract

Fenton-like reactions is attractive for environmental pollutant control, but there is an urgent need to improve the utilisation of hydroxyl radicals (·OH) in practical applications. Here, for the first time, FeOCl is encapsulated within a Metal Organic Framework (MOF) (Materials of Institut Lavoisier-101 (MIL-101(Fe))) as a yolk-shell reactor (FeOCl-MOF) by in situ growth. The interaction between FeOCl and the MOF not only increases the electron density of FeOCl, but also shifts down the d-band centre. The increase of electron density could promote the efficient conversion of H₂O₂ to ·OH catalysed by FeOCl. And the shift of the d-band centre to the lower energy level facilitates the desorption of ·OH. Experimental and theoretical calculations showed that the high catalytic performance was attributed to the unique yolk-shell structure that concentrates the catalytic and adsorption sites in a confinement space, as well as the improved electron density and d-band centre for efficient generation, rapid desorption and utilized nearby of ·OH. Which is utilized nearby by the organic pollutants adsorbed by the surface MOF, thus greatly improving the effective conversion of H₂O₂ and the ·OH utilisation (from 25.5% (Fe²⁺/H₂O₂) to 77.1% (FeOCl-MOF/H₂O₂)). In addition, a catalytic reactor was constructed to achieve continuous efficient treatment of organic pollutants. This work provides a Fenton-like microreactor for efficient generation, rapid desorption, and nearby utilization of ·OH to improve future technologies for deep water purification in complex environments.

Keywords: Efficient utilization; Fenton-like; Microreactor; d-band centre; ·OH.