大环多胺镍配合物催化过氧化氢降解碱性品红催化性能与机理
Catalytic performance and mechanism of nikle chloride hexahydrate in basic fuchsin degradation
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摘要: 以大环多胺镍配合物[NiL]（ClO4）2为催化剂（L=1，8-二甲基-1，3，6，8，10，13六氮杂十四烷），H2O2为氧化剂，碱性品红为底物，研究了催化剂用量、氧化剂投入量、底物浓度、反应溶液pH值、反应温度、常见阴离子和天然有机物对催化反应效率的影响.结果表明，反应体系pH=6，催化剂浓度200 μmol·L-1，碱性品红浓度15 mg·L-1，氧化剂投入量0.12 mol·L-1，在50℃下反应催化速率达最大值，10 min内碱性品红脱色率96.7%.通过自由基淬灭实验和电子顺磁共振测试发现[NiL]（ClO4）2-H2O2反应体系中主要起氧化降解作用的自由基是O2-·，并推测反应机理为：过氧化氢与大环多胺镍配位化合物的中心离子镍配位，形成一个五配位的配位化合物，配位化合物在溶液中分解能给出超氧离子，超氧离子降解碱性品红.Abstract: Nikle chloride hexahydrate[NiL](ClO4)2 was used as catalyst for basic fuchsin (BF) degrodation in the present of H2O2. The effects of catalyst and H2O2 dosage, substrate (BF) concentration, pH and temperature on BF removal were optimized, and impacts of the common anions and natural organic matters on BF degradation were investigated. It was found that[NiL](ClO4)2 had a great catalytic capacity on BF removal and the decoloration rate reached 96.7% in 10 min under the optimal conditions at 50℃, pH=6,[NiL](ClO4)2, H2O2 and BF concentration of 200 μmol·L-1, 0.12 mol·L-1 and 15 mg·L-1, respectively. Moreover, ESR and radical quenching tests indicated that O2-·radicals were the main contributing radicals generated in the[NiL](ClO4)2-H2O2 system which could further degrade BF or other dyes into smaller molecules. The reacion mechanism was proposed as follows. Pentamethene coordination compound was formed through the coordination process of H2O2 with the central nickel ion of nikle chloride hexahydrate, and the coordination compounds could stimulate the generation of O2-·radicals, which could further degradate BF in aqueous solution.
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