Energy-efficient electrochemical degradation of ciprofloxacin by a Ti-foam/PbO2-GN composite electrode: Electrode characteristics, parameter optimization, and reaction mechanism

Reducing energy comsuption is crucial to commercialize electrochemical oxidation technologies. In this study, a novel PbO₂ composite electrode (Ti-foam/PbO₂-GN) was successfully fabricated based on a porous titanium (Ti) foam substrate and a β-PbO₂ active layer embedded with multiple graphene (GN) interlayers, and applied as an anode for energy-efficient pulse electrochemical oxidation of ciprofloxacin (CIP). In contrast to PbO₂ and Ti-foam/PbO₂ electrodes, the Ti-foam/PbO₂-GN electrode surface exhibited a more compact structure, smaller crystal grain size, and greater electrochemical active surface area. CIP removal of 89.7% was obtained with a low energy consumption (EE/O) of 6.17 kWh m^-3 under pulse electrolysis conditions with a current density of 25.00 mA cm^-2, pulse frequency of 5000 Hz, and pulse duty cycle of 50.0%. Up to 70.7% of the energy was saved in the pulse current mode compared to the direct current mode. Narrowing the electrode spacing to 2 cm facilitated the mass transfer process and enhanced oxidation efficiency. According to the intermediates identified, the pulse electrolysis of CIP primarily involved hydroxylation of the quinolone ring, breaking of the piperazine ring, defluorination, and decarboxylation processes, and a possible degradation mechanism of CIP was proposed. The continuous oxidation performance of CIP and the relatively low leaching of Pb²⁺ suggested that the Ti-foam/PbO₂-GN electrode exhibited excellent stability, repeatability, and safety. The degradation results of CIP in real water also exhibits the great potential of environmental application. As a result, pulse electrochemical oxidation using a Ti-foam/PbO₂-GN electrode has proven to be an energy-efficient and promising alternative for antibiotic wastewater treatment.