Beijing Engineering Research Center of Process Pollution Control, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology , Institute of Process Engineering, Chinese Academy of Science , Beijing 100190 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
J Am Chem Soc. 2019 Jul 31;141(30):12005-12010. doi: 10.1021/jacs.9b04569. Epub 2019 Jul 17.
The peroxone reaction between O and HO has been deemed a promising technology to resolve the increasingly serious water pollution problem by virtue of the generation of superactive hydroxyl radicals (OH), but it suffers greatly from an extremely limited reaction rate constant under acidic conditions (ca. less than 0.1 M s at pH 3). This article describes a heterogeneous catalyst composed of single Mn atoms anchored on graphitic carbon nitride, which effectively overcomes such a drawback by altering the reaction pathway and thus dramatically promotes OH generation in acid solution. Combined experimental and theoretical studies demonstrate Mn-N as the catalytically active sites. A distinctive catalytic pathway involving HO formation by the activation of HO is found, which gets rid of the restriction of HO as the essential initiator in the conventional peroxone reaction. This work offers a new pathway of using a low-cost and easily accessible single-atom catalyst (SAC) and could inspire more catalytic oxidation strategies.
过氧单键反应（peroxone reaction）是一种在 O 和 HO 之间发生的反应，被认为是解决日益严重的水污染问题的一种有前途的技术，因为它可以生成超活性羟基自由基（OH）。但在酸性条件下，其反应速率常数非常有限（在 pH 值为 3 时约小于 0.1 M s）。本文描述了一种由单原子锰锚定在石墨相氮化碳上组成的非均相催化剂，通过改变反应途径有效地克服了这一缺点，从而在酸性溶液中显著促进了 OH 的生成。实验和理论研究的结合表明，Mn-N 是催化活性位点。发现了一种独特的催化途径，涉及通过 HO 的激活形成 HO，从而摆脱了在传统过氧单键反应中 HO 作为必需引发剂的限制。这项工作为使用低成本且易于获得的单原子催化剂（SAC）提供了一种新途径，并可能激发更多的催化氧化策略。
