2D MXene nanosheet dispersed Mn, Ru NPs loaded Ti composite electrodes for electrocatalytic synergistic degradation of antibiotics in high-salt mariculture wastewater

Abstract

In this study, a composite electrode based on etched TiO₂ nanotube arrays and two-dimensional (2D) MXene nanosheets was successfully designed for efficient degradation of antibiotics in mariculture wastewater. The composite electrode effectively dispersed Mn and Ru nanoparticles (NPs) by introducing 2D MXene nanosheets as an intermediate layer, which significantly enhanced the catalytic performance. The bifunctional properties of Mn and Ru NPs in catalysis and the contribution of d-orbital electrons to the formation of metal‑hydrogen bonds were revealed in depth by analyzing the electron transfer mechanism at the electrodes. The experimental results demonstrated a synergistic catalytic effect between Mn and Ru bimetals and MXene, resulting in an effective increase in the degradation rate. Under the optimal conditions, the degradation rate of Tetracycline (TC) by Mn/Ru/MXene/Ti composite electrode could reach 90.69 % in 60 min. In addition, it still shows excellent stability after 45 days of air exposure, 10 cycling experiments, and 10,000 s of timed current testing. Mechanistic studies have demonstrated that anode hydroxyl radical (·OH), HClO, and cathode activated hydrogen atoms (H*) all play catalytic roles in the degradation process. The degradation pathways were analyzed using density-functional theory (DFT) calculations and liquid-liquid-mass spectrometry (LC-MS) techniques, with further experiments confirming that this degradation process effectively reduces the biotoxicity of intermediate products, improving the safety of wastewater discharge. Finally, we designed the reactor and calculated the energy consumption to verify the feasibility and economy of the system in practical applications. This research proposes a novel multi-metal co-catalysis and cathode and anode co-catalysis system for the efficient degradation of antibiotics in mariculture wastewater, with potential applications in the electrocatalytic degradation of antibiotics.