Cu(Ⅱ)金属有机骨架中配位环境对类Fenton反应活性的影响  

Effect of Coordination Environment on Fenton-like Reactivity in Cu(Ⅱ)Metal-Organic Frameworks

作　　者：郭彬 杨静[1] 卢文欣 王鹏[1] GUO Bin;YANG Jing;LU Wen-Xin;WANG Peng(College of Chemical and Biological Engineering,Shandong University of Science and Technology,Qingdao,Shandong 266590,China)

机构地区：[1]山东科技大学化学与生物工程学院,青岛266590

出　　处：《无机化学学报》2022年第10期1981-1992,共12页Chinese Journal of Inorganic Chemistry

基　　金：山东省自然科学基金(No.ZR2019BB041);青岛西海岸新区2020年度科技项目(No.2020-91)资助。

摘　　要：以一水合醋酸铜为铜源,以2,6⁃二(4'⁃吡啶基)⁃4⁃甲基苯胺(L)为桥联吡啶配体、间苯二甲酸(H_(2)IPA)为共配体分别合成了一维链状配位聚合物{[(Cu(OAc)_(2))_(2)(L)]·3CH_(3)CN}n(1,OAc-=CH_(3)CO_(2)^(-))和二维网状配位聚合物{[Cu(IPA)(L)(H_(2)O)]_(2)·H_(2)IPA·H_(2)O}_(n)(2)。通过二者的单晶结构分析可以看出,配合物1中的铜原子位于[CuNO_(4)]_(2)簇中的四面体配位环境中心,配合物2中的铜原子处于[CuNO_(3)]变形六面体配位环境的中心,不同的配位环境导致2个配合物具有差异化的光催化降解有机物的活性。通过以亚甲基蓝为底物的类Fenton光催化降解对比实验表明,含有Cu—N、Cu—O配位环境的配合物1的催化效果优于具有相同四面体构型配位环境的HKUST⁃1,且配合物1和2催化性能的对比也证明了开放性单核铜配位中心的光催化降解活性优于簇合物中的铜配位中心。得益于配体的稳定和框架结构的存在,与相同条件下无配体约束的醋酸铜盐的催化性能相比,2个配合物均具有更高的催化活性和可循环利用特性。通过UV⁃Vis光谱计算了二者的带隙,光催化降解前后的粉末X射线衍射及电感耦合等离子质谱证明了配合物的稳定性。通过添加自由基捕捉剂苯醌、叔丁醇和三乙醇胺,证实了该催化过程为羟基自由基过程的类Fenton反应机理。Using copper acetate monohydrate as a copper source,1D chain coordination polymer{[(Cu(OAc)_(2))_(2)(L)]·3CH_(3)CN}n(1,OAc-=CH_(3)CO_(2)^(-))was synthesized using 2,6⁃bis(4'⁃pyridyl)⁃4⁃methylaniline(L)as bridged pyridine ligand,and 2D network coordination polymer{[Cu(IPA)(L)(H_(2)O)]2·H_(2)IPA·H_(2)O}n(2)was prepared by L and isoph⁃thalic acid(H2IPA)as the co⁃ligand.It can be seen from the single crystal structure analysis that the copper atoms in complex 1 are located in the center of the tetrahedral coordination environment in the[CuNO_(4)]_(2) clusters,and the copper atoms in complex 2 are in the[CuNO_(3)]deformed hexahedral coordination environment.The comparative experiments on Fenton⁃like photocatalytic degradation with methylene blue as substrate show that the catalytic effect of complex 1 with Cu—N and Cu—O coordination environment was better than that of HKUST⁃1 with the same tetrahedral coordination environment.The comparison of the catalytic performance of complexes 1 and 2 also proves that the photocatalytic degradation activity of the open mononuclear copper coordination center was better than that of the copper coordination center in the cluster complex.Benefiting from the stability of the ligands and the existence of the framework structure,both complexes had higher catalytic activity and recyclability compared with the catalytic performance of the unconstrained copper acetate under the same conditions.The band gaps of the two complexes were calculated through UV⁃Vis spectra.The stability of the complexes after the reaction was con⁃firmed by X⁃ray diffraction and inductively coupled plasma mass spectrometry.By adding free radical scavengers benzoquinone,tertiary butanol,and triethanolamine,it is confirmed that the catalytic process is a Fenton⁃like reac⁃tion mechanism of the hydroxyl radical process.CCDC:2178802,L;2178799,1;2178801,2.

关 键 词：桥联吡啶配体 Cu(Ⅱ)配合物 类Fenton光降解 羟基自由基机理 

分 类 号：O614.121[理学—无机化学]