Periodate-based advanced oxidation processes: A review focusing on the overlooked role of high-valent iron and manganese species

Periodate-based advanced oxidation processes (AOPs) have received mounting attention in scientific research in the past two decades due to their fair oxidizing capability for satisfactory decontamination performance. Unlike iodyl (IO3•) and hydroxyl (•OH) radicals are widely recognized as the predominant species generated from periodate activation, the role of high-valent metal as a dominant reactive oxidant has been proposed recently. Although several excellent reviews concerning periodate-based AOPs have been reported, there are still prevalent knowledge roadblocks to high-valent metals' formation and reaction mechanisms. Therefore, this work aims to provide a comprehensive overview of high-valent metals, especially concerning the identification methods (e.g., direct and indirect strategies), formation mechanisms (e.g., formation pathways and interpretation based on density functional theory calculation), reaction mechanisms (e.g., nucleophilic attack, electron transfer, oxygen-atom transfer, electrophilic addition, and hydride and hydrogen-atom transfer), and reactivity performance (e.g., chemical properties, influencing factors, and practical applications). Furthermore, points for critical thinking and further prospects for high-valent metal-mediated oxidation processes are suggested, emphasizing the need for parallel efforts to enhance the stability and reproducibility of high-valent metal-mediated oxidation processes in real world applications.