Two-dimensional metal organic frameworks (2D MOFs) with honeycomb-like porous sheets are of growing interest for applications in electrochemical energy storage and electrocatalysis. Notably, 2D MOFs that host their porous sheets in eclipsed or slipped-parallel stacking modes possess continuous one-dimensional pores (1D) and have been widely studied. In contrast, related 2D MOFs with a staggered stacking mode have reduced porosity, are relatively rare, and are largely unexplored for applications. Here we report 2-fold enhanced redox storage and intercalation of diverse ions in a staggered-stacked, nonporous 2D MOF over its eclipsed-stacked, porous counterpart. Interestingly, both MOFs, despite undergoing similar ligand-centered redox processes, differ by storing four and two electrons per formula unit of the staggered and eclipsed phases, respectively. Taken together, the stacking mode-dependent modulation of a ligand’s redox behavior in 2D MOFs offers a new avenue to tune structure–property relationships and presents important motivation to explore nonporous 2D MOFs.

中文翻译：

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交错堆叠模式增强层状金属有机框架中的氧化还原存储和多样化插层

具有蜂窝状多孔片材的二维金属有机框架（2D MOF）在电化学储能和电催化领域的应用越来越受到人们的关注。值得注意的是，以重叠或滑移平行堆叠模式承载多孔片的 2D MOF 具有连续的一维孔 (1D)，并已得到广泛研究。相比之下，具有交错堆叠模式的相关二维 MOF 孔隙率较低，相对较少，并且在很大程度上尚未探索其应用。在这里，我们报告了交错堆叠的无孔二维 MOF 中不同离子的氧化还原存储和嵌入比其重叠堆叠的多孔对应物提高了 2 倍。有趣的是，尽管两种 MOF 经历了类似的以配体为中心的氧化还原过程，但不同之处在于交错相和重叠相的每个分子式单元分别存储四个和两个电子。综上所述，二维 MOF 中配体氧化还原行为的堆积模式依赖性调节提供了调整结构-性能关系的新途径，并为探索无孔 2D MOF 提供了重要动力。