Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States.
Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
ACS Nano. 2023 May 23;17(10):9611-9621. doi: 10.1021/acsnano.3c03143. Epub 2023 May 11.
Metal-octaaminophthalocyanine (MOAPc)-based 2D conductive metal-organic frameworks (cMOFs) have shown great potential in several applications, including sensing, energy storage, and electrocatalysis, due to their bimetallic characteristics. Here, we report a detailed metal substitution study on a family of isostructural cMOFs with Co, Ni, and Cu as both the metal nodes and the metal centers in the MOAPc ligands. We observed that different metal nodes had variations in the reaction kinetics, particle sizes, and crystallinities. Importantly, the electronic structure and conductivity were found to be dependent on both types of metal sites in the 2D cMOFs. Ni-NiOAPc was found to be the most conductive one among the nine possible combinations with a conductivity of 54 ± 4.8 mS/cm. DFT calculations revealed that monolayer Ni-NiOAPc has neither the smallest bandgap nor the highest charge carrier mobility. Hence its highest conductivity stems from its high crystallinity. Collectively, these results provide structure property relationships for MOAPc-based cMOFs with amino coordination units.
基于金属卟啉（MOAPc）的二维导电金属有机骨架（cMOFs）由于其双金属特性，在传感、储能和电催化等多个领域都显示出了巨大的应用潜力。在此，我们报告了一系列同构 cMOFs 的详细金属取代研究，其中 Co、Ni 和 Cu 既是金属节点，也是 MOAPc 配体中的金属中心。我们观察到，不同的金属节点在反应动力学、颗粒大小和结晶度方面存在差异。重要的是，电子结构和导电性被发现依赖于二维 cMOFs 中的两种金属位点。在 9 种可能的组合中，Ni-NiOAPc 的电导率最高，为 54±4.8 mS/cm。密度泛函理论（DFT）计算表明，单层 Ni-NiOAPc 的带隙既不是最小的，也不是载流子迁移率最高的。因此，它具有最高的电导率是源于其高结晶度。总的来说，这些结果为具有氨基配位单元的 MOAPc 基 cMOFs 提供了结构-性能关系。
