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首页> 外文期刊>RSC Advances >The effect of the aliphatic carboxylate linkers on the electronic structures, chemical bonding and optical properties of the uranium-based metal-organic frameworks
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The effect of the aliphatic carboxylate linkers on the electronic structures, chemical bonding and optical properties of the uranium-based metal-organic frameworks

机译：脂肪族羧酸酯连接基对铀基金属-有机骨架的电子结构，化学键合和光学性质的影响

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摘要

Metal-organic frameworks (MOFs) are drawing increased interest for their high stability and porosity leading to their potential applications in separation, catalysis, and photoelectric processes. Recent studies have identified the role of aminated linkers in band-gap reduction of differentMOFs. Uranyl-containingMOFs are of particular interest due to their photo-luminescent properties and their photocatalytic activity. We recently studied the electronic structures of a series of uranyl containing aliphatic dicarboxylate structures that contain aliphatic dicarboxylate linkers of different lengths. Members of this series are UO2-C4H4O4-H2O (MOF1), UO2-C5H6O4 (MOF2), UO2-C6H8O4-2H(2)O (MOF3), UO2-C7H10O4 (MOF4), UO2-C8H12O4 (MOF5), UO2-C9H14O4 (MOF6), and UO2-C10H6O4 (MOF7). This series of actinide coordination polymers were synthesized by various groups. Our computational study provides a detail analysis of chemical bonding, charge distribution, geometric and electronic structural properties, and optical properties of these MOFs for the first time. The variation in the length of linkers does not significantly influence the electronic properties of these MOFs. All MOFs of this series show semiconducting character, common in other transition metalbased MOFs. The band gap for the whole series is essentially constant at ca. 2.5 eV, independent of the length of linkers. For the first time, we provide an extensive analysis of the bonding environment and characteristics in these MOFs based on the charge density distribution, Bader and Mulliken population analysis as well as electron localization functions (ELF). Our analyses show that the uranyl metallic subunit in all MOFs has ionic bonding characteristics. The organic carboxylate linkers, on the other hand, show predominantly covalent bonding characteristics. Simulated optical properties, such as refractive index n(omega), absorption coefficient alpha(omega), optical conductivity sigma(omega), reflectivity R(omega), and electron energy-loss spectrum L(omega) are obtained from the calculated frequency dependent dielectric constants. These properties indicate some promising application of these MOFs as photo-catalyst. In particular, substantial absorption in the energy range of the visible part of electromagnetic spectrum shown by these MOFs can be explored further for application in solar energy sector. Our results also indicate to a possible way to tune the band gap through, e.g., doping, and hence pave the path to a potential application of theseMOFs as photocatalysts.
机译：金属有机骨架（MOF）的高稳定性和高孔隙率引起人们越来越多的兴趣，从而使其在分离，催化和光电过程中具有潜在的应用前景。最近的研究已经确定了胺化连接体在降低不同MOF的带隙中的作用。含铀酰的MOF由于其光致发光特性和光催化活性而特别受关注。我们最近研究了一系列含铀酰的脂肪族二羧酸酯结构的电子结构，这些结构包含不同长度的脂肪族二羧酸酯连接基。该系列的成员是UO2-C4H4O4-H2O（MOF1），UO2-C5H6O4（MOF2），UO2-C6H8O4-2H（2）O（MOF3），UO2-C7H10O4（MOF4），UO2-C8H12O4（MOF5），UO2- C9H14O4（MOF6）和UO2-C10H6O4（MOF7）。该系列act系配位聚合物是通过各种基团合成的。我们的计算研究首次对这些MOF的化学键，电荷分布，几何和电子结构性质以及光学性质进行了详细分析。接头长度的变化不会显着影响这些MOF的电子性能。该系列的所有MOF都具有半导体特性，这在其他过渡金属基MOF中很常见。整个系列的带隙基本上恒定在大约0。 2.5 eV，与接头的长度无关。我们首次基于电荷密度分布，Bader和Mulliken种群分析以及电子本地化功能（ELF）对这些MOF中的键合环境和特征进行了广泛的分析。我们的分析表明，所有MOF中的铀酰金属亚基均具有离子键特征。另一方面，有机羧酸酯连接基显示出主要的共价键特征。从计算出的频率相关性获得模拟的光学特性，例如折射率nΩ，吸收系数αΩ，光导率σ，反射率RΩ和电子能量损失谱LΩ。介电常数。这些性质表明这些MOF作为光催化剂有一定的应用前景。尤其是，可以进一步探索这些MOF所显示的电磁光谱的可见光部分在能量范围内的大量吸收，以用于太阳能领域。我们的结果还表明了一种通过例如掺杂来调节带隙的可能方法，从而为这些MOF作为光催化剂的潜在应用铺平了道路。

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