Accelerated photodegradation (minute range) of the commercial azo-dye Orange II mediated by Co3O4/Raschig rings in the presence of oxone

The accelerated discoloration of Orange II by an innovative Co3O4/Raschig ring photocatalyst (from now on Co3O4/RR) is feasible and proceeds to completion using oxone as an oxidant within the surprisingly short time of ∼5 min. The preparation of Co3O4 small clusters (2–10 nm in size) on RR is reported. The discoloration/mineralization of the azo-dye Orange II was carried out in a concentric coaxial photo-reactor and was a function of the Orange II and oxone concentrations, the solution pH and the recirculation rate. At bio-compatible pH-values, the concentration of Co-ions in solution after photocatalysis (15 min) was found to be between 0.5 and 2 ppm, within the limits allowed for treated waters. The generation of peroxide was observed as long as Orange II was still available in solution. By elemental analysis (EA), the amount of Co of the Raschig rings was determined to be ∼65% (w/w) before and after the photocatalysis. This confirms the stability observed during long-term operation of the Co3O4/RR catalyst. The sizes of the Co3O4 clusters on the RR surface were determined by transmission electron spectroscopy (TEM). A non-uniform distribution of Co3O4 particles on RR with sizes between 2 and 10 nm was found. The presence of Co-clusters on the RR-surface was confirmed by electron dispersive spectroscopy (EDS) showing 12.6% surface Co-enrichment before the photocatalysis and 18.8% surface enrichment after the photocatalysis. By confocal microscopy the irregularly thick shaped Co3O4 on the Raschig rings was analyzed. The most striking observation is very large shift of Co2p3/2 line from 779.6 eV at time zero to 782.2 eV within 10 min after due to the photocatalysis taking place. This indicates a strong reduction of electron density on the cobalt atoms of Co3O4/RR and providing the evidence for the strong oxidation properties of this catalyst.