Oxidative removal of 4-nitrophenol using activated carbon fiber and hydrogen peroxide to enhance reactivity of metallophthalocyanine
Oxidative removal of 4-nitrophenol using activated carbon fiber and hydrogen peroxide to enhance reactivity of metallophthalocyanine
复制标题
使用活性炭纤维和过氧化氢氧化去除4-硝基苯酚以增强金属酞菁的反应活性
DOI：
10.1016/j.apcatb.2008.08.024
复制
发表时间：
2009-04-07
影响因子：
22.1
通讯作者：
Yao, Yuyuan
中科院分区：
文献类型：
--
作者：
Lu, Wangyang;Chen, Wenxing;Yao, Yuyuan
通过将四（2，4-二氯-1，3，5-三嗪）氨基酞菁钴（Co-TDTAPc）共价固定在活性炭纤维（ACF）上，制备了一种新型多相金属酞菁催化剂Co-TDTAPc-ACF。采用超高效液相色谱法（UPLC）研究了Co-TDTAPc-ACF/H2 O2体系对4-硝基苯酚（4-NP）的相转移催化氧化去除效果。结果表明，Co-TDTAPc-ACF和H2 O2催化氧化可有效去除废水中的4-NP。在300 min内，4-NP对总有机碳的去除率约为90%。气相色谱/质谱（GC-MS）分析表明，残留产物主要为马来酸、丁二酸等小分子化合物，该体系在较宽的pH和温度范围内均表现出较高的催化活性。重要的是，与单独使用的均质Co-TDTAPc相比，ACF的引入特别有助于Co-TDTAPc的活性增强。对照实验表明，作为羟基自由基清除剂的2-丙醇的存在对4-NP氧化的影响很小。电子顺磁共振（EPR）自旋阱实验进一步表明，在我们的体系中，自由基并不占主导地位。本文探讨了Co-TDTAPc-ACF/H_2O_2体系的催化氧化机理。重复性试验表明，Co-TDTAPc-ACF在多次循环后仍能保持较高的催化活性，且在温和条件下具有较好的再生能力。我们的结论是，相转移催化氧化已被证明是一种可行的方法，可能会被应用到消除广泛存在的污染物。(C)2008 Elsevier B. V.保留所有权利。
We have developed a novel heterogeneous metallophthalocyanine catalyst, Co-TDTAPc-ACF, by immobilizing cobalt tetra(2,4-dichloro-1,3,5-triazine)aminophthalocyanine (Co-TDTAPc) on activated carbon fiber (ACF) covalently. The oxidative removal of 4-nitrophenol (4-NP) in the Co-TDTAPc-ACF/H2O2 system, based on phase transfer catalytic oxidation, was investigated in aqueous solution by ultra-performance liquid chromatography (UPLC). The results indicated that 4-NP could be removed efficiently by catalytic oxidation in the presence of Co-TDTAPc-ACF and H2O2. In addition, the removal of total organic carbon of 4-NP accounted for about 90% in 300 min of reaction. Gas chromatography/mass spectrometry (GC-MS) analysis showed that the residue products were mainly small molecular compounds such as malefic acid and succinic acid, etc. This system exhibited high catalytic activity across a wide pH and temperature range. Importantly, compared with homogeneous Co-TDTAPc used alone, the introduction of ACF contributed specifically to the activity enhancement of Co-TDTAPc. Controlled experiments showed that the presence of 2-propanol, as hydroxyl radicals scavenger, has little influence on 4-NP oxidation. The further result of electron paramagnetic resonance (EPR) spin-trap experiments indicated that free radicals did not dominate the reaction in our system. This paper discusses a possible catalytic oxidation mechanism of the Co-TDTAPc-ACF/H2O2 system. Repetitive tests showed that Co-TDTAPc-ACF can maintain high catalytic activity over several cycles, and it has a better regeneration capability under mild conditions. We conclude that phase transfer catalytic oxidation has proven itself to be a feasible approach which may be potentially applied to the elimination of widely existing pollutants. (C) 2008 Elsevier B.V. All rights reserved.