节点文献
可用于类芬顿降解染料的铜配合物的合成及其性能研究
Synthesis and Properties of Copper Complexes for Degradation of Dyes
【作者】 王艳；
【导师】 胡瑞祥；
【作者基本信息】 湖南师范大学 ， 无机化学， 2020， 硕士
【摘要】 在有机染料的各种降解方法当中,高级氧化技术（AOPs）因具有高效、能耗低、环保的优点而被广泛使用。其中,Fenton工艺是降解有机废水最有效、最合适的方式之一。由于均相和非均相Fe-Fenton工艺存在反应pH范围较窄、铁离子易浸出等缺点,所以需要寻找新型、经济且高效的替代型非铁类Fenton降解体系。铜配合物是一种催化降解性能优良、极具发展前景的类芬顿催化剂。基于此,合成了两类Cu（I）配合物,通过一系列表征确定了结构与性质,并研究了它们在紫外-可见光下对有机染料的光芬顿降解活性。主要内容如下:（1）以2-巯基乙胺盐酸盐（Cy）为配体,采用快速高温生长法合成了一系列新的[Cu3X（SR）2]（CuCy-X,X=Cl、Br、I）配合物。XRD、红外、元素分析、EDS、Mapping等表征表明CuCy-X属于异质同晶化合物;SEM表征了该系列化合物的形貌;UV-vis和PL测试了化合物的吸收光谱和荧光光谱,CuCy-X在370 nm附近具有最大吸收,最强荧光发射峰位分别为608 nm（CuCy-Cl）,601 nm（CuCy-Br）和580 nm（CuCy-I）;通过分光光度法,UV-vis和PL测试了化合物的稳定性,三种化合物的稳定性顺序为CuCy-Cl<CuCy-Br<CuCy-I;在紫外-可见光辐照下,CuCy-X对亚甲基蓝（MB）具有光芬顿降解活性。探讨了H2O2用量、溶液pH、催化剂用量以及MB浓度对降解效率的影响,确定了最佳降解条件。检测到以CuCy-X为催化剂的Cu-Fenton体系中的活性物质为·OH,?O2-和1O2。实验结果表明,在最佳条件下CuCy-Cl、CuCy-Br在1 h内可将MB完全降解,CuCy-I在2 h内可将MB完全降解。（2）以4,6-二甲基-2-巯基嘧啶（Hdmpymt）、2-巯基嘧啶（Hpymt）、2-巯基-5-正丙烷基嘧啶（HMPP）为配体与二价铜盐反应得到铜配合物{[Cu6（dmpymt）6]·H2O}（CuPy-1）、[Cu6（pymt）6]（CuPy-2）和[Cu2（MPP）Cl]（Cu Py-3）。单晶衍射结果显示配合物CuPy-1和CuPy-2是同构化合物,具有Cu6S6簇单元,而CuPy-3是以2-巯基-5-正丙烷基嘧啶与卤素离子共同参与配位的配合物。测试了配合物的荧光性能,三种化合物在分别在700 nm附近有红光发射,发射强度为CuPy-1>CuPy-2>CuPy-3。通过测试CuPy-n在水溶液中铜离子的浸出量表征了三种铜化合物的稳定性为:CuPy-3>CuPy-1>Cu Py-2。紫外-可见光辐照下,CuPy-2对MB、罗丹明B（RhB）、对硝基苯酚（PNP）、甲基紫（MV）等有机染料均具有光芬顿降解活性。在CuPy-2/H2O2类芬顿反应体系降解MB的过程中,·OH为主要的活性自由基,?O2-和1O2参与了MB的降解。
【Abstract】 Among various degradation methods of organic dyes,advanced oxidation technology（AOPs）has the strong point of high efficiency,energy-saving and environmental friendliness,so it is widely used.Among them,the Fenton method is one of the most effective and suitable methods for degrading organic wastewater.The homogeneous and heterogeneous Fe-Fenton process has the disadvantages of narrow reaction pH range and easy leaching of iron ions.Therefore,it is necessary to find a new,economical and efficient alternative non-ferrous Fenton degradation system.Copper complex is a kind of Fenton-like catalyst with excellent catalytic degradation performance and great development prospect.Based on this,two types of Cu（I）complexes were synthesized,the structure and properties were determined through a series of characterizations,and their photofenton degradation activity on organic dyes under ultraviolet-visible light was studied.The main contents are as follows:（1）Using 2-mercaptoethylamine hydrochloride（Cy）as ligand,a series of new[Cu3X（SR）2]（CuCy-X,X=Cl,Br,I）complexes were synthesized by rapid high-temperature growth method.XRD,infrared,elemental analysis,EDS,Mapping and other characterizations indicate that Cu Cy-X is a heterogeneous isomorphic compound.The UV-vis absorption spectrum of Cu Cy-X display the maximum absorption around370 nm,and the fluorescence spectrum show that Cu Cy-X have maximum emission peaks at 608 nm（CuCy-Cl）,601 nm（CuCy-Br）and580 nm（CuCy-I）respectively.The stability of the compounds was tested by spectrophotometry,UV-vis and PL with the order of CuCy-Cl<CuCy-Br<CuCy-I.Under ultraviolet-visible light irradiation,CuCy-X has photocatalytic Fenton-like degradation activity for methylene blue（MB）.The effects of H2O2 dosage,solution pH,catalyst dosage and MB concentration on degradation efficiency were explored,and the optimal degradation conditions were determined.The active substances in the Cu-Fenton system using CuCy-X as catalysts are·OH,?O2-and 1O2.The results demonstrate that CuCy-Cl and CuCy-Br can completely degrade MB within 1 h,and CuCy-I can completely degrade MB within 2 h under optimal conditions.（2）Using 4,6-dimethyl-2-mercaptopyrimidine（Hdmpymt）,2-mercaptopyrimidine（Hpymt）,2-mercapto-5-n-propanepyrimidine（HMPP）as ligand,threecopper complexes{[Cu6（dmpymt）6]·H2O}（CuPy-1）,[Cu6（pymt）6]（CuPy-2）and[Cu2（MPP）Cl]（CuPy-3）were obtained.Single crystal diffraction results show that the complexes CuPy-1 and Cu Py-2 are isomorphic compounds with Cu6S6 cluster units,while CuPy-3 is a complex in which 2-mercapto-5-n-propanepyrimidine and halogen ion participate in coordination.The fluorescence properties of the complexes were tested.The three compounds had red light emission around 700 nm,and the emission intensity was CuPy-1>CuPy-2>CuPy-3.The stability of CuPy-n,was tested by the leaching of CuPy-n in aqueous solution,is CuPy-3>CuPy-1>Cu Py-2.Under the irradiation of UV-vis,CuPy-2 has photo-Fenton degradation activity on organic dyes such as MB,rhodamine B（RhB）,p-nitrophenol（PNP）,and methyl violet（MV）.In the CuPy-2/H2O2 system for the degradation of MB,·OH is the main radical,and?O2-,1O2 are also involvedin the performance.