Titanium Oxide Electrocatalytic Membrane Filtration: “Two Faces” of Oxygen Vacancies in Generation and Transformation of Reactive Oxygen Species

Oxygen vacancies are crucial to the production of reactive oxygen species (ROS) in the metal oxide electrocatalytic membrane (MO_x EM) process. Here, using cathodic TiO_x EM as a model, we thoroughly reveal the roles of oxygen vacancies in ROS generation and transformation. Oxygen vacancies significantly promote H₂O₂ and ^•OH production at low concentrations (increment <35%) but inhibit their production at high concentrations (increment >35%). Electrochemical analysis discloses that the enhancement of ROS production profits from the acceleration of charge transfer kinetics by both bulk and surface oxygen vacancies, whereas we attribute the decline in ROS production to the strong adsorption of ROS by surface oxygen vacancies. It is strongly supported by theoretical calculations that reveal the promoted adsorption of *OOH and *OH by oxygen vacancies, which intensifies the capture and scavenging of H₂O₂ and ^•OH. Moreover, the gradual increase of interaction time between ROS and oxygen vacancies (from ∼1 to ∼5 s) notably reduces the generation and transformation efficiency of ROS, further highlighting the detrimental impact of oxygen vacancies. In summary, oxygen vacancies show "two faces" toward ROS generation and transformation, acting as ROS promoters at low concentrations but inhibitors at high concentrations. A medium oxygen vacancy concentration is preferred for ROS production, thus causing impressive pollutant removal (>95% removal of bisphenol A within 1.2-1.5 s at 360-440 LMH). This study provides guidance on regulating ROS generation and transformation by manipulating the oxygen vacancy concentration to enhance the decontamination efficiency of MO_x EMs.