Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Applied & Environmental Chemistry , College of Chemistry, Central China Normal University , Wuhan 430079 , P. R. China.
Environ Sci Technol. 2018 Aug 7;52(15):8659-8665. doi: 10.1021/acs.est.8b01849. Epub 2018 Jul 17.
It is of a great challenge to seek for semiconductor photocatalysts with prominent reactivity to remove kinetically inert dilute NO without NO emission. In this study, complete visible light NO oxidation mediated by O is achieved over a defect-engineered BiOCl with selectivity exceeding 99%. Well-designed oxygen vacancies on the prototypical (001) surface of BiOCl favored the possible formation of geometric-favorable superoxide radicals (•O) in a side-on bridging mode under ambient condition, which thermodynamically suppressed the terminal end-on •O associated NO emission in case of higher temperatures, and thus selectively oxidized NO to nitrate. These findings can help us to understand the intriguing surface chemistry of photocatalytic NO oxidation and design highly efficient NO removal systems.
寻求具有高反应活性、可在无 NO 排放的情况下有效去除动力学惰性稀 NO 的半导体光催化剂极具挑战性。在这项研究中，通过缺陷工程化 BiOCl 实现了完全可见光介导的 NO 氧化，选择性超过 99%。在 BiOCl 的典型（001）表面上设计良好的氧空位有利于在环境条件下以侧桥模式形成具有几何优势的超氧自由基（•O），这在较高温度下热力学上抑制了末端过氧自由基（•O）相关的 NO 排放，从而选择性地将 NO 氧化为硝酸盐。这些发现有助于我们理解光催化 NO 氧化的有趣表面化学，并设计高效的 NO 去除系统。
