多孔材料Cu3(BTB)2和H2O2处理偶氮染料废水及机理

doi:10.16085/j.issn.1000-6613.2017-0455

摘要/Abstract

摘要： 采用溶剂热法合成了Cu₃（BTB）₂（BTB=4，4'，4"-benzenetri benzoate）介孔材料，并进行了SEM、BET、FTIR和XRD表征。该材料呈多孔球形，比表面积为1293m²/g，平均粒径为10μm。应用该材料进行刚果红偶氮染料废水处理，发现Cu₃（BTB）₂单独作用时，废水去除率为10.29%；Cu₃（BTB）₂和H₂O₂共同作用，去除率骤增到91.65%。通过紫外-可见光谱、高效液相色谱、微量热、捕获剂等手段分析其降解机理，Cu₃（BTB）₂与H₂O₂共存时，342nm处紫外特征吸收峰右移，HPLC峰强度显著降低，放热反应标准摩尔反应焓为2068.74kJ/mol，加入自由基捕获剂异丙醇或氯仿后，去除率大幅降低。实验结果表明：Cu₃（BTB）₂单独作用为多孔吸附，去除率较低，与H₂O₂共存时去除率高，归结于Fenton-like反应产生活性自由基（·OH和O₂^-）使CR分子键断裂，且·OH占主导作用。

关键词: 金属-有机框架化合物, Cu₃(BTB)₂, 过氧化氢, 吸附, 降解, 焓, 自由基

Abstract: The mesoporous materials Cu₃(BTB)₂(BTB=4,4',4"-benzenetri benzoate)was synthesized, and then characterized by scanning electron microscopy(SEM),nitrogen adsorption measurements(BET), Fourier transform infrared spectrometer(FTIR),and X-ray powder diffraction(XRD). The results show that the Cu₃(BTB)₂ particles were spherical,with a S_BET of 1293m²/g, and an average particle size of 10μm. In the treatment of Congo red dye wastewater by using Cu₃(BTB)₂ alone, the removal rate was 10.29%, whereas treated by Cu₃(BTB)₂ and hydrogen peroxide(H₂O₂)together,the rate was increased to 91.65%. The mechanism was studied by means of UV-Vis spectroscopy,high performance liquid chromatography,microcalorimetry and free radical trapping agent. When Cu₃(BTB)₂ interacted with H₂O₂,the UV absorption peak at 342nm shifted to the right,the peak intensity of HPLC was reduced by about 500mV,and the exothermic standard molar reaction enthalpy was 2068.74kJ/mol. When we added opropanol(IPA)or chloroform(CF)to capture the ·OH or ·O₂^- radical into the reaction solution,the is removal rate was decreased. The results showed that Cu₃(BTB)₂ porous material could adsorb the CR dye,while H₂O₂ could produce the ·OH and ·O₂^- free-radical to break the CR molecular bond through the Fenton-like reaction,and the OH radicals played a dominant role.

Key words: metal-organic framework(MOF), Cu₃(BTB)₂, hydroen peroxide(H₂O₂)adsorption, degradation, enthalpy, radical

中图分类号:

徐言慧, 尹显洪, 邱江源, 黄在银, 谭春萍, 胡玉平. 多孔材料Cu₃(BTB)₂和H₂O₂处理偶氮染料废水及机理[J]. 化工进展, 2017, 36(12): 4700-4707.

XU Yanhui, YIN Xianhong, QIU Jiangyuan, HUANG Zaiyin, TAN Chunping, HU Yuping. Application and mechanism of azo dye wastewater treatment using Cu₃(BTB)₂ and H₂O₂[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4700-4707.

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多孔材料Cu₃(BTB)₂和H₂O₂处理偶氮染料废水及机理

Application and mechanism of azo dye wastewater treatment using Cu₃(BTB)₂ and H₂O₂

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