基于新型三电子氧还原反应形成羟基自由基的机理研究

氧气还原（ORR）在生物代谢、化学转化、生物与环境电化学等过程中代表了一类重要的反应，是由多电子引发的，有多种中间态产物生成和参与的复杂异相催化反应，目前反应机理尚不明确。经典理论认为ORR主要通过二电子和四电子还原两种途径完成。本项目从ORR过程产生的重要活性氧组分（ROS）出发，以反应热力学自发性准则为理论依据，提出一类以oOH自由基为特征产物的三电子ORR新模式。课题围绕"氧气如何还原为oOH自由基"这一关键科学问题，开展ORR形成oOH自由基的机理、关键影响因子和影响机制三方面的研究，并以此为基础构建以ROS中间产物为核心的ORR研究模式。该课题不仅对进一步揭示ORR机理具有重要的科学意义，同时也为发展新型可持续性高级氧化技术处理难降解有机废水和削减持久性有机物提供了新的思路和策略，具有重要的学术价值和环境意义。

The oxygen reduction constitutes an important reaction in biological metabolisms, chemical conversion, biological and environmental electrochemistry. Due to complex heterogeneous multielectron-induced electrocatalytic reaction involving many kinds of intermediates, the mechanisms of oxygen reduction reaction (ORR) are not well understood yet. The classical ORR theory considers the ORR to proceed through two- or four-electron pathways. Starting from the significant reactive oxygen species (ROS) formed during ORR and thermodynamics, this project tries to propose a new kind of three-electron ORR mode characterized by the formation of oOH free radicals intermediate. To answer the key scientific problem "How does oxygen reduction produce oOH free radicals?", the project will carry out the studies on mechanisms of oOH free radicals during ORR, the key environmental influencing factors and corresponding influencing mechanisms, as well as the construction of new mode for investigating the ORR based on ROS intermediates. This study not only suggests the scientific importance to uncover the ORR mechanisms, but also provides a new strategy to develop sustainable advanced oxidation process for wastewater treatment and reduction of persistent organic pollutants during environmental remediation.