Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH

作     者：Jing Zhang Ying Zhang Hui Wang Xiaohong Guan 

作者机构：State Key Lab of Urban Water Resource and Environment Harbin Institute of Technology Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes Ministry of Education College of Environment Hohai University CSCEC AECOM Consultants Co. Ltd. Waters Co. State Key Laboratory of Pollution Control and Resources Reuse College of Environmental Science and Engineering Tongji University 

出 版 物：《Journal of Environmental Sciences》 (环境科学学报（英文版）)

年 卷 期：2014年第26卷第7期

页      面：1395-1402页

核心收录：

学科分类：083002[工学-环境工程] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 

基　　金：supported by the National Natural Foundation of China (No. 21077029) the Shanghai Rising-Star Program (No. 12QA1403500) the Fundamental Research Funds for the Central Universities (No. 0040219206) 

主　　题：RutheniumCatalysisAnilineByproductElectron shuttle 

摘      要：Ru（Ⅲ） was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru（Ⅲ） could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru（Ⅲ） catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru（Ⅲ）, respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru（Ⅲ） catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant （ktapp） decreased from 643.20 to 2.67 （mol/L）^-1 sec^-1 with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru（Ⅲ）, as an electron shuttle, was oxidized by permanganate to Ru（Ⅵ） and Ru（Ⅶ）, which acted the co-oxidants for decomposition of aniline. Although Ru（Ⅲ） could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru（Ⅲ） into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru（Ⅲ） toward permanganate oxidation in our future study.