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Catalytic Degradation of Dyes and Detection of Hydrogen Peroxide Based on Metallophthalocyanine

Author: BaoShuangYu
Tutor: ChenWenXing
School: Zhejiang University of Technology
Course: Materials Science
Keywords: Metallophthalocyanine nylon catalytic oxidation dye electrochemicaltechniques determination hydroperoxide
CLC: X791
Type: Master's thesis
Year: 2012
Downloads: 100
Quote: 1
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Abstract


Synthetic dyes are widely used in textile printing and dyeing, paper making, food andcosmetics industries. Lots of dye wastewater not only destructed the ecological environmentand ecological balance, but also have strong toxic effects on aquatic life and human. As theproblem of dye wastewater pollution become increasingly serious, it is necessary to degradatethe dye wastewater before discharge immediately. The dye wastewater is characterized withhigh value of COD, high colority, complication of organic components and more difficultremediation. Increasing attention has focused on the degradation of dye wastewater. Recently,the advanced oxidation processes（AOPs） of the wastewater treatments, which have hightreatment efficiency, be able to degradate many structural stability and difficult biodegradationcontaminants. Currently, AOPs is one of the most effective methods on the treatment of dyewastewater. Therefore, we take AOPs to deal with the dyeing wastewate in this paper. However,AOPs need to use excess H2O2oxidant. Residual concentration of H2O2is generally severaltimes more than the original concentration of dye. A large number of residual H2O2willcontinue to pollute water resources and destruct ecosystem. Therefore, it is important to developthe excellent detection method of H2O2, which can effectively avoid the rates of exceeding limitof hydrogen peroxide and guide to add the optimal amount of hydrogen peroxide in AOPs.Phthalocyanine （Pc） is a beautifully symmetrical18p-electron aromatic macrocycle withquite even of electron density and stable molecule stucture, so Phthalocyanine is a typicalcatalyst. Cobalt tetra（2,4-dichloro-1,3,5-triazine）aminophthalocyanine（CoTDTAPc）, wasprepared and immobilized on nylon fiber to obtain a supported catalyst（F-CoTDTAPc）.F-CoTDTAPc combine with H2O2to formate F-CoTDTAPc/H2O2catalytic system. In thisthesis，we use F-CoTDTAPc/H2O2system to catalytic degradate various dyes. Secondly, wealso used cobalt phthalocyanine to modify graphite electrodes, and obtained phthalocyaninemodified electrode （GE-poly-CoTAPc）. Electrochemical method has benefits of simpleoperation, high sensitivity and rapid determination, So we take GE-poly-CoTAPc modifiedelectrode to detect the concentration of H2O2. The below contents and conclusions are obtained:1. Degradation of AR1aqueous solution by F-CoTDTAPc/H2O2system was studied. The results showed that the removel ratio of AR1reached at92%with the F-CoTDTAPc/H2O2system after240min reaction, while the AR1removal ratio was63%under the adsorption ofF-CoTDTAPc fiber. The results showed that the CoTDTAPc can catalytic degradate AR1.Moreover, the influence of amount of catalytic fiber, amount of H2O2, reaction temperature, pHvalue,,,, were investigated to optimize the operating parameters for the catalytic oxidation ofAR1. The research suggested that F-CoTDTAPc/H2O2exhibited the best catalytic activity at pH2,0.2g catalytic fiber, concentration of H2O2is more100times of dye concentration.2. The CoTDTAPc-F/H2O2system can also decompose other dyes, including Weak AcidBlack BR and Direct Pink5B. It was found that the degradation rate of Weak Acid Black BRwas nearly92%after120min, while the Direct Pink5B was63%after180min at the samereaction condition. A possible pathway for AR1oxidation by the CoTDTAPc-F/H2O2catalyticsystem was proposed by monitoring the reaction products with analytic techniques includingUltra-Performance Liquid Chromatography （UPLC） and Gas Chromatography&MassSpectrometry （GC/MS）. It can be assumed that the decolorization of AR1characterized bydegradation of azo linkage. The next stage was that benzene and naphthalene rings weredestroyed with the reaction of CoTDTAPc, and AR1was oxidized to organic acids, such as laticacid, maleic acid, ethane diacid, malonic acid, acrylic acid and other ring opening products.3. The graphite electrode（GE） modified with CoTAPc（GE-poly-CoTAPc） was obtainedform electrodeposition in the DMSO solution of CoTAPc. Compared with the bare GEelectrode, the GE-poly-CoTAPc electrode showed a very strong anodic wave with a peakpotential lowered about0.12V and a peak current increased about150.5μA for the H2O2oxidation. So, GE-poly-CoTAPc electrode can be used as the sensitive electrode for hydrogenH2O2. Using chronoamperometry（E=+1.0V versus SCE）technique, the peak current is linear tothe concentration of H2O2in the range of19.48μM to194.8μM. The detection limit is4.72μM.Scanning rate of50mV/s and scanning cycle of65scans is the optimal electrodepositionprocess. Repetitive tests presented that GE-poly-CoTAPc can maintain high catalytic activityover20cycles, indicating that GE-poly-CoTAPc has excellent stability.

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CLC: > Environmental science, safety science > Processing and comprehensive utilization of waste > Light industrial waste disposal and comprehensive utilization > Textile, printing and dyeing industry
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