Unlocking amorphous metal alloy induced electronic metal-support interactions for efficient electro-oxidation of...

Electrochemical oxidation offers a sustainable route for decentralized wastewater treatment, yet its efficiency remains constrained by the sluggish interfacial electron transfer and inefficient generation of reactive oxygen species (ROS) via single-electron pathways. Herein, we report an amorphous PdNi alloy-modified Magnéli-phase titanium suboxide (Ti₄O₇) anode (denoted A-PdNi@Ti₄O₇) engineered via electronic metal-support interactions (EMSI) to facilitate electron transfer and unlock the concurrent generation of multiple ROS (•OH, •O₂^-, ¹O₂). The amorphous PdNi clusters provide abundant unsaturated Pd-Ni sites and induce interfacial electron redistribution, enhancing both water oxidation and oxygen reduction processes. In-situ Raman spectroscopy, quenching experiments, and electron spin resonance (EPR) measurements confirm the simultaneous formation of •OH and •O₂^-, with ¹O₂ arising from their subsequent interaction. Density functional theory (DFT) calculations reveal that EMSI optimizes the adsorption of H₂O and O₂, and lowers the energy barriers for ROS evolution. Consequently, A-PdNi@Ti₄O₇ achieves a 2.73-fold enhancement in levofloxacin degradation kinetics and over 95 % mineralization efficiency, outperforming both monometallic and crystalline analogs. The electrode also demonstrates high durability and defluorination performance across varied water matrices. This work highlights the potential of amorphous bimetallic systems in EMSI modulation and offers a versatile platform for efficient electrochemical water treatment.