Enhanced Redox Storage and Diverse Intercalation in Layered Metal Organic Frameworks with a Staggered Stacking Mode
ACS ENERGY LETTERS(2024)
摘要
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.
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