Boosting hydroxyl radical generation for highly efficient electrooxidation of sulfamethazine via facile doping strategy

Abstract

The one-electron water oxidation reaction (WOR) to generates hydroxyl radicals (^•OH) plays a pivotal role in electrochemical advanced oxidation processes (EAOPs). In this study, we present a novel and facile strategy involving Ho-doping to regulate the electronic configuration of the conventionally nonactive PbO₂ electrode. Experimental findings demonstrate that PbO₂ doped with 2.4% Ho achieves the highest degradation performance of sulfamethazine (SMZ) (∼100%; k_obs = 0.093 min⁻¹) and highest ^•OH generation efficiency with a relatively concentration of ^•OH = 1.9 × 10⁷. The doped electrodes exhibit a notable enhancement compare to the undoped electrode, which elevating SMZ degradation efficiency and ^•OH generation by factors of 1.45 and 3.8, respectively. Electrochemical characterization and degradation results elucidate that the modulation of electron transfer rate and oxygen evolution potential are crucial factors governing the performance of the Ho-doped PbO₂ anode. Specifically, maintaining a suitably high oxygen evolution potential (OEP) enables the thermodynamically feasible production of ^•OH, while a relatively fast electron transfer rate ensures the generation of H₂O⁺ (the oxidation precursor of ^•OH) with kinetic feasibility. Furthermore, a degradation pathway for SMZ is proposed based on the identification of transformation mechanism using density functional calculation (DFT) and the detection of intermediates via LC-MS/MS. This study provides an universal strategy for simultaneously enhancing the OEP and optimizing the electron transfer rate of an EAOP anode through the modulation of anodic electronic configuration, thereby advancing the field of efficient water treatment applications.