Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering
Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering
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DOI：
10.1039/c9ta05216j
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发表时间：
2019-05
影响因子：
11.9
通讯作者：
M. Taddei;Giulia E. M. Schukraft;Michael E. A. Warwick;D. Tiana;M. McPherson;Daniel R. Jones;C. Petit-C.-Pet
中科院分区：
文献类型：
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作者：
M. Taddei;Giulia E. M. Schukraft;Michael E. A. Warwick;D. Tiana;M. McPherson;Daniel R. Jones;C. Petit-C.-Pet
我们报告了一种缺陷工程方法来调节锆基金属有机骨架UiO-66的带隙，通过在缺陷位点接枝一系列氨基功能化苯甲酸来实现。通过合成后交换和调制合成得到缺陷工程MOFs，其带隙在4.1 ~ 3.3 eV范围内。从头算表明，带隙的缩小主要是由于价带能的向上移动，这是由于吸收光的单羧酸盐的存在。测试了缺陷工程mof在气相中将CO2还原为CO和降解水中罗丹明B的光催化性能，与含有甲酸的缺陷uuo -66作为缺陷补偿物种相比，观察到两者的活性都有所提高。
We report a defect-engineering approach to modulate the band gap of zirconium-based metal-organic framework UiO-66, enabled by grafting of a range of amino-functionalised benzoic acids at defective sites. Defect engineered MOFs were obtained by both post-synthetic exchange and modulated synthesis, featuring band gap in the 4.1-3.3 eV range. Ab-initio calculations suggest that shrinking of the band gap is mainly due to an upward shift of the valence band energy, as a result of the presence of light-absorbing monocarboxylates. The photocatalytic properties of defect-engineered MOFs towards CO2 reduction to CO in the gas phase and degradation of Rhodamine B in water were tested, observing improved activity in both cases, in comparison to a defective UiO-66 bearing formic acid as the defect-compensating species.