Freestanding 3-dimensional macro-porous SnO2 electrodes for efficient electrochemical degradation of antibiotics in wastewater

Abstract

• A novel freestanding 3-dimensional SnO 2 -Sb anodes with macro-pores were fabricated; • The 3D MP SnO 2 -Sb anode featured a 140-fold increase in the electro-active surface area; • 3D MP SnO 2 -Sb was much more effective than 2D SnO 2 -Sb for the antibiotic removal; • The novel 3D anode exhibited a high stability after more than 200 test cycles; • The 3D MP SnO 2 -Sb anode performed efficiently in actual wastewater effluent. Electrochemical (EC) oxidation is an effective technology for treating wastewaters with emerging and persistent organic pollutants. However, conventional 2-dimensional (2D) film-type anodes have a low efficiency and short service life due to a limited electro-active surface area (EASA) and poor stability. In this study, novel freestanding and highly-stable 3-dimensional SnO 2 -Sb anodes with macro-pores (3D MP SnO 2 -Sb) were fabricated without the Ti base substrate by simply compressing the precursor of SnO 2 -Sb and carbon fibers followed by one-step sintering. Compared with the conventional 2D SnO 2 -Sb/Ti anode, the 3D MP SnO 2 -Sb anode featured a more than 100-fold increase in EASA, which greatly improved the EC efficiency for antibiotic oxidation and mineralization. Nearly 100% of ciprofloxacin (CIP, 20 mg L -1 ) in the synthetic wastewater was degraded by the 3D MP SnO 2 -Sb anode at a very low current density of 5 mA cm −2 within 120 min, which was significantly more effective than that by the 2D SnO 2 -Sb (74%) and a state-of-the-art boron-doped diamond anode (69%). The 3D MP SnO 2 -Sb anode exhibited a high stability (>200 cycles) and performed well in treating actual wastewater. The combined reaction kinetics analysis and porosimetry characterization indicated the importance of macro-pores to the excellent EC oxidation capacity and performance of the anode. The mechanism and pathways of electrocatalytic CIP degradation on the 3D anode were also elucidated from the density functional theory (DFT) calculations, molecular probe-based EC reaction analysis, and intermediate product detection.