基于5-羟甲基间苯二甲酸和咪唑衍生物的半导体型Ni-MOFs的合成、晶体结构和光催化性质
Semiconductive Ni-MOFs Based on 5-(Hydroxymethyl) Isophthalic Acid and Imidazole Derivatives: Synthesis, Crystal Structures, and Photocatalytic Properties
作者单位E-mail
徐中轩 遵义师范学院化学化工学院, 遵义 563002 xuzhongxuan4201@163.com 
石明凤 遵义师范学院化学化工学院, 遵义 563002
云南民族大学化学与环境学院, 昆明 650504 
 
白旭玲 遵义师范学院化学化工学院, 遵义 563002  
袁婷婷 遵义师范学院化学化工学院, 遵义 563002  
摘要: 利用水热反应制备了2个配合物{[Ni (HIPA)(2,5-DPBI)1.5(H2O)]·2.25H2O}n1)和[Ni (HIPA)(2,5-DPBMI)(H2O)]n2)(H2HIPA=5-(羟甲基)间苯二甲酸,2,5-DPBI=1,1'-(2,5-二甲基-1,4-亚苯基)双(1H-咪唑),2,5-DPBMI=1,1'-(2,5-二甲基-1,4-亚苯基)双(4-甲基-1H-咪唑))。结构分析揭示在不同咪唑配体存在下,配合物的Ni(Ⅱ)中心具有不同的配位环境。配合物1具有拓扑符号为(42.66.82)的五连接三维框架,而配合物2则是dia型的四连接网络。粉末X射线衍射证实配合物12在有机溶剂和紫外可见光照射的水中均非常稳定。此外,紫外可见吸收谱、Mott-Schottky和电化学阻抗谱(EIS)测试显示配合物12都是典型的n型半导体材料,具有较低的电荷传输阻抗。在光催化实验中,配合物12对染料亚甲基蓝的降解有催化活性。
关键词: 三维镍基框架  n型半导体  光催化活性  5-羟基间苯二甲酸  咪唑配体
基金项目: 国家自然科学基金(No.21761036)和贵州省自然科学基金(No.20181182)资助。
Abstract: Two complexes {[Ni(HIPA) (2, 5-DPBI)1.5(H2O)] ·2.25H2O}n (1) and [Ni(HIPA) (2, 5-DPBMI) (H2O)]n (2) (H2HIPA=5-(hydroxymethyl) isophthalic acid, 2,5-DPBI=1,1'-(2,5-dimethyl-1,4-phenylene)bis(1H-imidazole), 2,5-DPBMI=1,1'-(2,5-dimethyl-1,4-phenylene)bis(4-methyl-1H-imidazole)) were synthesized via hydrothermal method. Structural analysis reveals that Ni(Ⅱ) centers have different coordination environments in the existence of different imidazole ligands. As a result, complex 1 possesses a 5-connected framework with the topological symbol of (42.66.82), while complex 2 shows a 4-connected framework with dia net. The powder X-ray diffraction further firms that complexes 1 and 2 are very stable not only in a normal organic solvent but also in water under UV light. Moreover, the UV-Vis spectra, Mott-Schottky measurements, and electrochemical impedance spectroscopy (EIS) demonstrate that complex 1 and 2 are typical n-type semiconductors with low resistance in charge transportation. Finally, photocatalytic tests confirm that complexes 1 and 2 have catalytic activity for the degradation of methylene blue.
Keywords: three-dimensional Ni(Ⅱ)-framework  n-type semiconductor  photocatalytic activity  5-(hydroxymethyl) isophthalic acid  imidazole ligand
投稿时间:2021-10-08 修订日期:2022-05-20
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徐中轩,石明凤,白旭玲,袁婷婷.基于5-羟甲基间苯二甲酸和咪唑衍生物的半导体型Ni-MOFs的合成、晶体结构和光催化性质[J].无机化学学报,2022,38(9):1799-1807.
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