Oxygen doped graphite carbon nitride as efficient metal-free catalyst for peroxymonosulfate activation: Performance, mechanism and theoretical calculation.

In this study, oxygen-doped graphitic carbon nitride (g-C3N4), named O-g-C3N4, was successfully fabricated and characterized, and its performance in activating peroxymonosulfate (PMS, HSO5-) for the removal of phenol, 2,4-dichlorophenol (2,4-DCP), bisphenol A (BPA), rhodamine B (RhB), reactive brilliant blue (RBB) and acid orange 7 (AO7) was evaluated. The catalytic performance of O-g-C3N4 for AO7 removal increased by 14 times compared to g-C3N4. In the presence of 0.2 g L-1 O-g-C3N4, 3.5 mM PMS at natural pH 5.8, 96.4% of AO7 could be removed in 60 min, reduced toxicity of the treated AO7 solution was obtained, and the mineralization efficiency was 47.2% within 120 min. Density functional theory (DFT) calculations showed that the charge distribution changed after oxygen doping, and PMS was more readily adsorbed by O-g-C3N4 with the adsorption energy (Eads) of -0.855 kcal/mol than that of the pristine g-C3N4 (Eads: -0.305 kcal/mol). Mechanism investigation implied that AO7 was primarily removed by the sulfate radicals (SO4•-) and hydroxyl radicals (•OH) on the surface of O-g-C3N4, but the role of singlet oxygen (1O2) to AO7 elimination was negligible. The results of cyclic experiments and catalyst characterization after reaction confirmed the favorable catalytic activity and structural stability of O-g-C3N4 particles. Furthermore, the O-g-C3N4/PMS system was very resistant to most of the environmental impacts, and AO7 removal was still acceptable in natural water environment. This study may provide an efficient metal-free carbonaceous activator with low dosage for PMS activation to remove recalcitrant organic pollutants (ROPs).

Efficient degradation of clofibric acid by heterogeneous catalytic ozonation using CoFe2O4 catalyst in water.

CoFe2O4 (Cobalt ferrite, CF) nanoparticles were prepared, well characterized and applied as efficient solid catalyst in catalytic ozonation, named CF/O3 process, for the removal of emerging organic contaminants (EOCs). The degradation and mineralization of clofibric acid (CA) in CF/O3 process were dramatically enhanced in comparison with those under the O3 system. Surface hydroxyl groups (HGs) were considered as an important factor for ozone decomposition and the reactive oxygen species (ROS) on the catalyst surface were mainly responsible for CA elimination. The contribution and formation of ROS, including hydroxyl radicals (•OH), especially superoxide radicals (O2•-), singlet oxygen (1O2), and hydrogen peroxide (H2O2) were evaluated, and a rational mechanism was elucidated accordingly. Probable degradation pathway of CA was proposed according to the organic intermediates identified. The acute toxicity of the treated solution increased during the first 15 min and then declined rapidly and nearly disappeared as the reaction proceeded. In addition, acceptable catalytic performance of CF/O3 can be obtained for the treatment of other EOCs and the treatment of natural surface water spiked with CA. This work presents an efficient and promising catalytic ozonation technique for the elimination of EOCs in complex water matrices.