Zheng Juan, Sun Luying, Xue Yao, Ye Lingfeng, Fan Qijuan
Shaanxi Environmental Investigation and Assessment Center, Xi'an 712099, China.
Shaanxi Beizhan Anhuan Engineering Technology Co., Ltd, Xi'an 712099, China.
Inorg Chem. 2024 Aug 26;63(34):15841-15850. doi: 10.1021/acs.inorgchem.4c01946. Epub 2024 Aug 13.
Recently, two-dimensional metal-organic frameworks that are photoactive have shown great potential for efficiently converting solar energy into chemical energy. In this work, we successfully synthesized and designed two M-MOFs ([Cu()((CH)NH)] () and [Zn()(CH)NH)] (), H = 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid). Structural analysis suggests that the five-coordinated M(II) ion is surrounded by four oxygen ions from two ligands and one nitrogen atom from one dimethylamine molecule. The ligand spacer acts as a bridge between two SBUs and forms a 2D layer with rhomboid windows. These moieties are arranged in a staggered ABAB pattern, which likely aids in exfoliation. The UV-vis diffuse reflectance spectra (DRS) test shows that when the metal center in the MOF framework is replaced with Cu(II) ions, the light absorption range covers 200-1100 nm, which is much larger than the light absorption range of . Moreover, the photoelectric current, electrochemical impedance spectra (EIS), and Mott-Schottky tests all indicate that has better photoelectric properties. When applied to the photocatalytic reduction of Cr(VI), and can completely reduce Cr(VI) within 100 min under 450 nm LED light irradiation. Under sunlight irradiation, can completely reduce Cr(VI) within 40 min, achieving the removal of Cr(VI) ions, which is much faster than the rate of Cr(VI) removal by .
最近，具有光活性的二维金属有机框架在将太阳能高效转化为化学能方面显示出巨大潜力。在这项工作中，我们成功合成并设计了两种金属有机框架（[Cu()((CH)NH)] () 和 [Zn()(CH)NH)] (), H = 4,4'-(苯并[c][1,2,5]噻二唑-4,7-二基)二苯甲酸）。结构分析表明，五配位的M(II)离子被来自两个配体的四个氧离子和来自一个二甲胺分子的一个氮原子包围。配体间隔基充当两个次级构筑单元之间的桥梁，并形成带有菱形窗口的二维层。这些部分以交错的ABAB模式排列，这可能有助于剥离。紫外可见漫反射光谱（DRS）测试表明，当金属有机框架中的金属中心被Cu(II)离子取代时，光吸收范围覆盖200 - 1100 nm，这比 的光吸收范围大得多。此外，光电流、电化学阻抗谱（EIS）和莫特-肖特基测试均表明 具有更好的光电性能。当应用于光催化还原Cr(VI)时， 在450 nm LED光照射下100分钟内可完全还原Cr(VI)。在阳光照射下， 在40分钟内可完全还原Cr(VI)，实现了Cr(VI)离子的去除，这比 通过 去除Cr(VI)的速率快得多。
