Contribution of 1O2 in the efficient degradation of organic pollutants with Cu0/Cu2O/CuO@N-C activated peroxymonosulfate: A Case study with tetracycline

Peroxymonosulfate-mediated advanced oxidation processes (PMS-AOPs) degrading organic pollutants (Tetracycline (TC) as an example) in water with singlet oxygen (1O2) as the main reactive oxygen has received more and more attention. However, the generation mechanism of 1O2 is still unclear. Consequently, this study investigates the 1O2 formation mechanism during the activated PMS process using a nitrogen-copper-loaded carbon-based material (Cu0/Cu2O/CuO@N-C), synthesized by thermally decomposing organobase-modified HKUST-1 via a one-pot method. It was discovered that incorporating an organobase (Benzylamine) into the metal organic framework (MOF) precursor directs the MOF's self-assembly process and supplements its nitrogen content. This modification modulates the Nx-Cu-Oy active site formation in the material, selectively producing 1O2. Additionally, 1O2 was identified as the dominant reactive oxygen species in the Cu0/Cu2O/CuO@N-C-PMS system, contributing to TC degradation with a rate of 70.82%. The TC degradation efficiency remained high in the pH range of 3-11 and sustained its efficacy after five consecutive uses. Finally, based on the intermediates of TC degradation, three possible degradation pathways were postulated, and a reduction in the ecotoxicity of the degradation products was predicted. This work presents a novel and general strategy for constructing nitrogen copper-loaded carbon-based materials for use in PMS-AOPs.