Catalytic ozonation performance of graphene quantum dot doped MnOOH nanorod for effective treatment of ciprofloxacin and bromate formation control in water

[Display omitted] •GQDs@MnOOH could enhance the CIP degradation and inhibit the formation of bromate.•GQDs@MnOOH exhibited excellent electron transport capability for catalytic ozonation.•GQDs@MnOOH + O3 system exhibits good efficiency of CIP removal over different water conditions.•Radicals and non-radicals were involved in CIP degradation by catalytic ozonation process. A catalyst GQDs@MnOOH was successfully synthesized by attaching graphene quantum dots (GQDs) on the surface of MnOOH nanorods to boost catalytic ozonation of antibiotic, exemplified by ciprofloxacin (CIP). The result demonstrated that the GQDs@MnOOH/O3 system had the greatest CIP removal effectiveness, followed by that of MnOOH/O3 and O3 only. The 0.02 mM CIP was degraded with 99.9% efficiency in 30 min in the presence 9.6 mg L-1 of O3 catalyzed by 12.5 mg L-1 of GQDs@MnOOH. The kinetic rate constants ​​were in the order: GQDs@MnOOH/O3 (0.161 min−1) > MnOOH/O3 (0.079 min−1) > O3 (0.055 min−1). The GQDs@MnOOH could enhance CIP degradation and inhibit BrO3- formation in different water sources. Results of scavenger and electron paramagnetic resonance (EPR) experiments demonstrated that oxygen radical (O2•-), singlet oxygen (1O2), and hydroxyl radicals (•OH) were involved in CIP degradation by the GQDs@MnOOH/O3 system. Accordingly, the degradation pathways of CIP and mechanism of catalytic ozonation over GQDs@MnOOH were investigated and proposed. This research is expected to shed light on the connection between carbonaceous material and metal hydroxide in catalytic ozonation.