| 四配位Co(Ⅱ)构建的螺旋配位聚合物:合成、结构和对CO2的光催化还原 |
| Helical Coordination Polymers Based on Tetra-coordinated Co(Ⅱ): Syntheses, Structures and Photocatalytic CO2 Reduction Reaction |
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| 摘要: 在水热条件下，对映的乳酸衍生物（R）-4-（1-羧基乙氧基）苯甲酸（（R）-H2CBA）和（S）-4-（1-羧基乙氧基）苯甲酸）（（S）-H2CBA）分别与辅助配体1，3-双（2-甲基-1H-咪唑-1-基）苯（1，3-BMIB）以及Co（Ⅱ）反应，合成出一对结构新颖的金属-有机框架化合物{[Co（（R）-CBA）（1，3-BMIB）]·H2O}n（1-D）和{[Co（（S）-CBA）（1，3-BMIB）]·H2O}n（1-L）。单晶解析揭示在二维的1-D和1-L中，四配位的Co（Ⅱ）中心分别与乳酸衍生物（R）-H2CBA（或（S）-H2CBA）和/或1，3-BMIB一起构建出了3种不同结构的螺旋链。这对螺旋二维化合物在不同pH值的水中有一定的稳定性。紫外-可见吸收光谱显示1-D对420~650 nm范围的可见光有较强的吸收。进一步的Mott-Schottky测试表明1-D是典型的n型半导体。此外其较小的阻抗半径显示其有利于电子传输。在进一步的光催化实验中，1-D实现了光照条件下CO2转化为CO，反应平均速率为577.8 μmol·g-1·h-1。 |
| 关键词: 配位聚合物 螺旋链 四配位Co(Ⅱ)中心 光催化CO2还原 |
| 基金项目: 国家自然科学基金（No.21761036）和贵州省科学技术基金（No.20181181）资助项目。 |
| Abstract: A pair of homochiral coordination polymers, {[Co((R)-CBA)(1,3-BMIB)2]·H2O}n (1-D, (R)-H2CBA=(R)-4-(1-carboxyethoxy)benzoic acid, 1,3-BMIB=1,3-bis(2-methyl-1H-imidazol-1-yl)benzene) and {[Co((S)-CBA)(1,3-BMIB)2]·H2O}n (1-L), were prepared by mixing Co2+, 1,3-BMIB and lactic acid derivates (R)-H2CBA/(S)-H2CBA under hydrothermal condition, respectively. X-ray crystallography reveals there are three types of helical chains constructed by tetra-coordinated Co(Ⅱ) centers, 1,3-BMIB and/or CBA2- ligands in complexes 1-D and 1-L. For unsaturated Co(Ⅱ) centers can act as catalytic active site, complex 1-D with high yield was further used for photo-catalytic research. Mott-Schottky measurements indicate that complex 1-D is a typical n-type semiconductor, while the UV-Vis spectrum confirmed that complex 1-D showed strong absorption in a range of 420~650 nm. Further more, complex 1-D has the small radius and the lowest resistance in charge transportation. Finally, complex 1-D realized photocatalytic reduction of CO2 to CO with an evolution rate of 577.8 μmol·g-1·h-1 in the course of the experiment. |
| Keywords: coordination polymer helical chain tetra-coordinated Co(Ⅱ) center photo-catalytic CO2 reduction |
| 投稿时间：2019-11-20 修订日期：2020-03-27 |
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| 徐中轩,李立凤,白旭玲.四配位Co(Ⅱ)构建的螺旋配位聚合物:合成、结构和对CO2的光催化还原[J].无机化学学报,2020,36(8):1430-1436. |
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