基于单-和双-三唑衍生物的三个Cu(II)和Cu(I)多金属氧簇基配合物的水热合成及光催化性能
Three Polyoxometalate-Based Cu(II) and Cu(I) Coordination Polymers with Mono-and Bis-triazole Derivatives: Hydrothermal Assembly and Photocatalytic Properties
作者单位E-mail
刘媛媛 无机-有机杂化功能材料化学教育部重点实验室, 天津师范大学化学学院, 天津 300387
南京大学配位化学国家重点实验室, 南京 210093 
hxxylyy@mail.tjnu.edu.cn 
李欣书 无机-有机杂化功能材料化学教育部重点实验室, 天津师范大学化学学院, 天津 300387  
张慧敏 无机-有机杂化功能材料化学教育部重点实验室, 天津师范大学化学学院, 天津 300387  
丁斌 无机-有机杂化功能材料化学教育部重点实验室, 天津师范大学化学学院, 天津 300387
南京大学配位化学国家重点实验室, 南京 210093 
 
摘要: 在水热条件下,利用多齿的单-和双-三唑衍生物,制备了3种基于多金属氧簇基(POM)的Cu(Ⅱ)和Cu(I)杂化材料,即{[Cu(L12(Mo4O13)]·2H2O}n1),{[Cu1.5(L2)(HL2)(H2O)(Mo4O13)]·2H2O}n2),{[Cu2(L31.5(Mo4O13)]·H2O}n3)(L1=4-pyridine-2-1,2,4-triazole,HL2=3-(4H-1,2,4-triazol-4-yl)benzoic acid,L3=trans-4,4'-azo-1,2,4-triazole)。通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构。在1中,Mo4O132-阴离子和Cu(Ⅱ)中心通过双齿L1相互连接,最终形成了二维(2D)POMs基的Cu(Ⅱ)杂化金属-有机骨架。在2中,Mo4O132-阴离子和Cu(Ⅱ)中心通过桥接水原子(O18),双齿HL2和三齿L2-相互连接,最终形成了三维(3D)POMs基的Cu(Ⅱ)微孔金属-有机骨架。在3中,L3配体桥接相邻的Cu(I)中心和Mo4O132-阴离子,最终形成独特的双重穿插结构的3DPOMs基的Cu(I)杂化配位框架。光催化实验研究表明,样品1~3对于不同有机染料罗丹明B(RhB)、亚甲基蓝(MB)和甲基橙(MO)都具有很好的光催化降解能力。
关键词: 三唑  Cu(Ⅱ)  Cu(I)  多金属氧簇  光催化
基金项目: 国家自然科学基金(No.21301128),天津市自然科学基金(No.14JCQNJC05900),天津市高等学校创新团队培养计划(No.TD12-5038)和天津师范大学大学生创新训练项目(No.201612)资助。
Abstract: Three novel polyoxometalate (POM)-based Cu(Ⅱ) and Cu(I) hybrid materials with multi-dentate mono-and bis-triazole derivatives, namely {[Cu(L1)2(Mo4O13)]·2H2O}n (1), {[Cu1.5(L2)(HL2)(H2O)(Mo4O13)]·2H2O}n (2), {[Cu2(L3)1.5(Mo4O13)]·H2O}n (3) (L1=4-pyridine-2-1,2,4-triazole, HL2=3-(4H-1,2,4-triazol-4-yl)benzoic acid,L3=trans-4,4'-azo-1,2,4-triazole) have been designed and synthesized by hydrothermal method. The structures of 1~3 have been determined by single crystal X-ray diffraction, FT-IR infrared spectra and powder X-ray diffraction analyses. In 1, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked by bidentate L1, which are arranged into 2D POMs-based Cu(Ⅱ) hybrid metal-organic framework. In 2, Mo4O132- anions and Cu(Ⅱ) centers are inter-linked via bridging aqua atoms (O18), bi-dentate HL2 and tri-dentate L2-, which are arranged into 3D POM-based Cu(Ⅱ) micro-porous metal-organic framework. In 3, L3 ligands bridge neighboring Cu(I) centers and Mo4O132- anions, which ultimately forms unique two-fold interpenetrating 3D POM-based Cu(I) hybrid coordination framework. Photocatalytic activities for decomposition of different organic dyes of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) have been investigated for 1~3, indicating that 1~3 are good candidates for photocatalytic degradation of the organic dyes.
Keywords: triazole  Cu (Ⅱ)  Cu (I)  polyoxometalate  photocatalytic
投稿时间:2018-08-06 修订日期:2018-09-26
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