Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China.
J Colloid Interface Sci. 2011 May 15;357(2):447-52. doi: 10.1016/j.jcis.2011.01.099. Epub 2011 Feb 3.
Liquid phase catalytic oxidation of chlorophenols (CPs) was carried out over Cu-Al hydrotalcite/clay composite at ambient temperature and pressure using hydrogen peroxide as oxidant. The results showed that the catalyst had high catalytic activity, with complete oxidation of 4-CP within 40 min at 40 °C. The content and position of chlorine on the aromatic ring had significantly different effects on the oxidation rate of CPs, with the rate sequence of phenol > monochlorophenol (MCP) > dichlorophenol (DCP) > trichlorophenol (TCP), 3-CP > 2-CP > 4-CP, and 3,5-DCP > 3,4-DCP > 2,5-DCP > 2,4-DCP > 2,6-DCP. This was ascribed to the interactions among σ-electron withdrawing conductive effect, π-electron donating conjugative effect, and steric hindrance effect of chlorine. It was evidenced that the catalytic peroxide oxidation of CPs in the first step was selective and rate-limiting, where chlorinated 1,4-benzoquinones formed.
在环境温度和压力下,用过氧化氢作为氧化剂,在 Cu-Al 水滑石/粘土复合材料上进行了氯酚(CPs)的液相催化氧化。结果表明,该催化剂具有很高的催化活性,在 40°C 下 40 分钟内即可完全氧化 4-CP。芳环上氯的含量和位置对 CPs 的氧化速率有显著不同的影响,速率顺序为苯酚>单氯酚(MCP)>二氯酚(DCP)>三氯酚(TCP),3-CP>2-CP>4-CP,以及 3,5-DCP>3,4-DCP>2,5-DCP>2,4-DCP>2,6-DCP。这归因于氯的σ-电子吸电子导电效应、π-电子给体共轭效应和空间位阻效应之间的相互作用。有证据表明,CPs 的催化过氧化物氧化在第一步是选择性的和速率限制的,其中形成了氯化 1,4-苯醌。