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High-valent metals in advanced oxidation processes: A critical review of their identification methods, formation mechanisms, and reactivity performance

期刊

CHEMICAL ENGINEERING JOURNAL
卷 460, 期 -, 页码 -

出版社

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2023.141796

关键词

High-valent metal; Advanced oxidation process; Fe(IV)-oxo complex; Selective reactivity; Reaction kinetics

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The role of high-valent metals in advanced oxidation processes (AOPs) is discussed in this study. The identification methods, formation mechanisms, and reactivity performance of high-valent metals are comprehensively reviewed. Density functional theory calculations show that high-valent metals are more favorable compared to radicals. High-valent metals exhibit strong selectivity towards electrophilic functional groups due to their moderate oxidation performance. The study also proposes points for critical thinking and future prospects for high-valent metal-mediated oxidation processes.
The role of high-valent metals as dominant reactive oxidants in advanced oxidation processes (AOPs) has not been systematically reviewed. The aim of this study was to provide an in-depth and comprehensive overview of high-valent metals in AOPs with respect to the identification methods, formation mechanisms, and reactivity performance. First, we discuss current identification methods for high-valent metals including their drawbacks. Subsequently, theoretical formation pathways and key influencing factors (e.g., pH and ligands) of high-valent metals are summarized. Based on density functional theory calculations, high-valent metals are more favor-able than radicals. We then compare high-valent metals with radicals with respect to their redox potential and reaction rate constant and observed that high-valent metals have a strong selectivity towards the electrophilic functional group due to their moderate oxidation performance. Finally, points for critical thinking and further prospects for high-valent metal-mediated oxidation processes are proposed.

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