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纤维负载酞菁钴用于水-纤维相转移及原位催化氧化高效分解有机染料

Highly efficient decomposition of organic dyes by aqueous-fiber phase transfer and in situ catalytic oxidation using fiber-supported cobalt phthalocyanine.

作者信息

Chen Wenxing, Lu Wangyang, Yao Yuyuan, Xu Minhong

机构信息

Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education of China, Zhejiang Sci-Tech University, Hangzhou 310018, China.

出版信息

Environ Sci Technol. 2007 Sep 1;41(17):6240-5. doi: 10.1021/es070002k.

Abstract

A novel metallophthalocyanine derivative, cobalt tetra (2,4-dichloro-1,3,5-triazine) aminophthalocyanine (Co-TDTAPc), was prepared and immobilized on cellulosic fiber by covalent bond to obtain a supported oxidation catalyst (Co-TDTAPc-F). Co-TDTAPc-F/H202 system based on phase-transfer catalytic oxidation for decomposing dyes, including acid, reactive, and direct dyes, has been investigated thoroughly. Compared to traditional adsorption technologies and advanced oxidation processes (AOPs) for dye treatment, Co-TDTAPc-F/H202 combines the advantages of both and is more efficient and more effective. Azo dyes such as C. I. Acid Red 1 (AR1) can be quickly adsorbed onto/into the fiber from aqueous solution and decomposed in situ simultaneously in the presence of Co-TDTAPc-F and H2O2. It has been found that the reaction process is not affected by the visible light. Furthermore, it turns the negative effect of NaCl normally observed in homogeneous catalysis into positive one. The catalytic reaction can proceed at a wide pH range from acidic to alkaline. In 60 min, more than 98% of AR1 was eliminated at initial pH 2. In 90 min, about 40% of the carbon was found mineralized as determined by the analysis of the residual total organic carbon. The high-performance liquid chromatography result indicated that a substantial amount of the starting AR1 was converted to other organic products, while gas chromatography/mass spectrometry analysis showed the rest of the carbon existed mainly as small molecular biodegradable aliphatic carboxylic compounds such as oxalic acid, malonic acid, and maleic acid, etc. Co-TDTAPc-F is stable, causes no secondary pollution, and remains efficient in repetitive test cycles with no obvious degradation of catalytic activity.

摘要

制备了一种新型金属酞菁衍生物,四(2,4 - 二氯 - 1,3,5 - 三嗪)氨基钴酞菁(Co - TDTAPc),并通过共价键将其固定在纤维素纤维上,得到负载型氧化催化剂(Co - TDTAPc - F)。对基于相转移催化氧化的Co - TDTAPc - F/H₂O₂体系用于分解酸性、活性和直接染料等染料进行了深入研究。与传统的染料吸附技术和高级氧化工艺(AOPs)相比,Co - TDTAPc - F/H₂O₂兼具两者的优点,效率更高且效果更好。偶氮染料如C.I.酸性红1(AR1)可从水溶液中快速吸附到纤维上/进入纤维内部,并在Co - TDTAPc - F和H₂O₂存在下同时原位分解。研究发现该反应过程不受可见光影响。此外,它将均相催化中通常观察到的NaCl的负面影响转化为正面影响。催化反应可在从酸性到碱性的较宽pH范围内进行。在初始pH为2时,60分钟内AR1的去除率超过98%。在90分钟时,通过分析残留总有机碳发现约40%的碳被矿化。高效液相色谱结果表明大量起始AR1转化为其他有机产物,而气相色谱/质谱分析表明其余碳主要以小分子可生物降解的脂肪族羧酸化合物如草酸、丙二酸和马来酸等形式存在。Co - TDTAPc - F稳定,不会造成二次污染,并且在重复测试循环中保持高效,催化活性无明显下降。

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