• 关键词：δ-MnO₂  苯酚  氧化降解  机理

• 基金项目：中央级公益性科研院所基本科研业务专项课题(No.2010KYYW03);国家自然科学基金(No.20977051)

• 徐建
• 中国环境科学研究院环境基准与风险评估国家重点实验室,流域水生态保护技术研究室,北京 100012

• 张莹
• 中国环境科学研究院环境基准与风险评估国家重点实验室,流域水生态保护技术研究室,北京 100012

• 李蕾
• 中国环境科学研究院环境基准与风险评估国家重点实验室,流域水生态保护技术研究室,北京 100012

• 郭昌胜
• 中国环境科学研究院环境基准与风险评估国家重点实验室,流域水生态保护技术研究室,北京 100012

• 张远
• 中国环境科学研究院环境基准与风险评估国家重点实验室,流域水生态保护技术研究室,北京 100012

• 摘要：δ-MnO₂以水羟锰矿和水钠锰矿的形式普遍存在于陆地和海洋环境中,是酚类等有机污染物发生非生物转化的重要氧化剂.本文研究了实验室制备的δ-MnO₂悬浮液对苯酚的去除作用,同时讨论了pH、二氧化锰投加量、离子强度、共存金属离子和腐殖酸等不同影响因素对苯酚去除效率的影响.结果表明,苯酚氧化降解的最佳pH和δ-MnO₂投加量分别为3.62和0.13 mg·L^-1.溶液中共存的Na⁺和Mn²⁺会对苯酚氧化降解产生抑制作用,而Mg²⁺和Ca²⁺对反应过程没有明显的影响.溶液中共存的腐殖酸也对苯酚的降解过程产生了抑制作用,随着腐殖酸的浓度由1 mg·L^-1增加到5 mg·L^-1,苯酚的去除率从96.9%降为78.9%.GC-MS分析发现,对苯二酚为该过程的主要中间产物,同时给出了苯酚在δ-MnO₂存在时的可能降解机制.

• Abstract：Manganese dioxides (δ-MnO₂) mainly exist in the form of vernadite and birnessite in the natural environment, which are considered to be important oxidants during the abiotic transformation of phenolic compounds. In this study, δ-MnO₂ was synthesized by a facile method, and its ability for the degradation of aqueous phenol was investigated. Impacts of solution pH, δ-MnO₂ loading, ionic strength, coexistence metal ions, and humic acid on the degradation of aqueous phenol were studied. The optimum solution pH and δ-MnO₂ loading were determined to be 3.62 and 0.13 mg·L^-1, respectively. The coexistence of Na⁺ and Mn²⁺ showed inhibition effect on the oxidative degradation process, while Mg²⁺ and Ca²⁺ did not show any obvious effect during the experimental process. The removal efficiency of phenol decreased from 96.9% to 78.9% when the concentration of humic acid in the reaction solution increased from 1 mg·L^-1 to 5 mg·L^-1. GC-MS was applied to identity the reaction intermediates, and hydroquinone was found to be the main reaction intermediate in the degradation system. Based on the above observations, the possible degradation pathway of phenol by δ-MnO₂ was proposed.

• Key words：δ-MnO₂  phenol  oxidative degradation  mechanism

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