A new porous zirconium metal-organic framework (Zr MOF), Zr6(μ3-O)4(μ3-OH)4(OH)6(H2O)6(BTB)2·6DMF·H2O (1; H3BTB = 5'-(4-carboxyphenyl)[1,1':3',1″-terphenyl]-4,4″-dicarboxylic acid), based on Zr6 clusters and tricarboxylate ligands has been constructed and characterized. The Zr6 clusters were linked by BTB ligands to generate a 2D network of kgd topology. The interpenetrations among the 2D networks gave rise to a 3D porous framework, which represents the first Zr MOF constructed from 2D → 3D interpenetration. The gas uptake and catalytic properties for 1 have also been studied.
Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal‐based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two‐unit cells. The process involves rapid exfoliation of bulk‐layered, MCPs (Ce‐, Ti‐, Zr‐based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high‐yield, room‐temperature, and template‐free approach to synthesize ultrathin holey nanosheets with high‐level functionalities.
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