Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices
Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices
复制标题
DOI：
10.1021/acsaelm.0c01135
复制
发表时间：
2021-04-29
影响因子：
4.7
通讯作者：
Hendon, Christopher H.
中科院分区：
文献类型：
--
作者：
Le, Khoa N.;Mancuso, Jenna L.;Hendon, Christopher H.
多孔电导体为下一代储能解决方案和电催化技术提供了机会。金属-有机骨架是孔隙率最高的支架之一，但由于其高度离子的金属-配体界面，通常具有低导电性。在这篇论文中，我们用计算方法研究了一个已知的导电骨架Ni-3(己氨基苯)(2)中的连接柱的包结。我们假设，由于Ni-3(六亚氨基苯)(2)是平面导体，对这种材料进行改进可能会得到一个在所有晶体方向上都具有金属性的3D连接网络。然而，我们发现，尽管这种策略可能会为Ni2+系统带来不稳定的连接性，但Cr2+或Fe2+的使用提供了一种形成3D连接导体的独特途径。该研究进一步强调了金属d(Z)(2)轨道在形成导电金属-有机骨架方面的关键作用。
Porous electrical conductors offer opportunities for next-generation energy storage solutions and electrocatalytic technologies. Metal-organic frameworks are one of the highest porosity scaffolds but typically feature low electrical conductivity due to their highly ionic metal-ligand interface. In this paper, we use computational approaches to study the inclusion of ligating pillars in a known electrically conductive framework, Ni-3(hexaiminobenzene)(2). We hypothesize that because Ni-3(hexaiminobenzene)(2) is an in-plane conductor, retrofitting this material may yield a 3D-connected network with metallicity in all crystallographic directions. However, we find that while this strategy likely yields unstable connectivity for the Ni2+ system, the use of either Cr2+ or Fe2+ provides a unique avenue to form 3D-connected conductors. The study further highlights the critical role of the metal d(z)(2) orbitals in creating conductive metal-organic frameworks.