Doping properties of the MOF-5 metal–organic framework [Zn₄O(BDC)₃, BDC = benzodicarboxylate] are explored using density functional theory calculations, with hybrid functional. Our investigation primarily focused on the stability, electronic structure, and formation energy of MOF-5 when doped with an M atom (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Al), occupying a single Zn site per unit cell. Our findings reveal that MOF-5 exhibits insulating characteristics with an electronic band gap of 4.8 eV. However, after metal doping, impurity levels are observed throughout the band gap. Sc and Al introduce semioccupied levels close to the conduction band minimum, which can impart donor-like characteristics to the material. Formation energy calculations indicate that Sc, Al, Ti, and V exhibit stability in the single-positive charge state for Fermi energy values lower than 3 eV, while Cr, Mn, Fe, Co, and Ni are stable in neutral charge states. It is noteworthy that dopants with unpaired electrons retain this property when inserted at Zn sites, inducing local magnetization in MOF-5. Consequently, our findings suggest that the electronic properties of MOF-5 undergo drastic modification after the incorporation of specific metal dopants, indicating the potential for the development of metal–organic frameworks as functional materials.

中文翻译：

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MOF-5 金属有机框架中的金属取代：混合密度泛函理论研究

使用混合泛函的密度泛函理论计算探讨了MOF-5 金属有机骨架 [Zn ₄ O(BDC) ₃ ，BDC = 苯并二羧酸盐] 的掺杂特性。我们的研究主要集中在 MOF-5 掺杂 M 原子（M = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu 和 Al）时的稳定性、电子结构和形成能，每个晶胞有一个 Zn 位点。我们的研究结果表明，MOF-5 表现出绝缘特性，电子带隙为 4.8 eV。然而，在金属掺杂之后，在整个带隙中观察到杂质水平。 Sc 和 Al 引入接近导带最小值的半占据能级，这可以赋予材料类似施主的特性。形成能计算表明，Sc、Al、Ti 和 V 在费米能值低于 3 eV 时在单正电荷态下表现出稳定性，而 Cr、Mn、Fe、Co 和 Ni 在中性电荷态下稳定。值得注意的是，具有不成对电子的掺杂剂在插入 Zn 位点时保留了这种特性，从而在 MOF-5 中诱导局部磁化。因此，我们的研究结果表明，加入特定金属掺杂剂后，MOF-5 的电子性能发生了巨大的改变，表明金属有机骨架作为功能材料的潜力。