Uniform Mesoporous Amorphous Cobalt-Inherent Silicon Oxide as a Highly Active Heterogeneous Catalyst in the Activation of Peroxymonosulfate for Rapid Oxidation of 2,4-Dichlorophenol: The Important Role of Inherent Cobalt in the Catalytic Mechanism

Abstract

Amorphous cobalt-inherent silicon oxide (Co-SiOx) was synthesized for the first time and employed as a highly active catalyst in the activation of peroxymonosulfate (PMS) for the rapid oxidation of 2,4-dichlorophenol (2,4-DCP). The characterization results revealed that the 0.15Co-SiOx possessed a high specific surface area of 607.95 m²/g with a uniform mesoporous structure (24.33 nm). The X-ray diffraction patterns indicate that the substituted cobalt atoms enlarge the unit cell parameter of the original SiO₂, and the selected area electron diffraction pattern confirmed the amorphous nature of Co-SiOx. More bulk oxygen vacancies (O_v) existing in the Co-SiOx were identified to be one of the primary contributors to the significantly enhanced catalytic activation of PMS. The cobalt substitution both creates and stabilizes the surficial O_v and forms the adequately active Co(II)-O_v pairs which engine the electron transfer process during the catalytic activities. The active Co(II)-O_v pairs weaken the average electronegativity of Co/Si and Co/O sites, resulting in the prevalent changes in final state energy, which is the main driving cause of the binding energy shifts in the X-ray photoelectron spectroscopy (XPS) spectra of Si and O among all samples. The increase of the relative proportion of Co(III) in the spent Co-SiOx probably causes the binding energy shifts of the Co XPS spectrum compared to that of the Co-SiOx. The amorphous Co-SiOx outperforms stable and quick 2,4-DCP degradation, achieving a much higher kinetic rate of 0.7139 min^-1 at pH = 7.02 than others via sulfate radical advanced oxidation processes (AOPs), photo-Fenton AOPs, H₂O₂ reagent AOPs, and other AOP approaches. The efficient degradation performance makes the amorphous Co-SiOx as a promising catalyst in removing 2,4-DCP or organic-rich pollutants.